WO2022024146A1

WO2022024146A1 - Synergistic formulation for plant protective composition comprising prothioconazole

Info

Publication number: WO2022024146A1
Application number: PCT/IN2021/050738
Authority: WO
Inventors: Dipakkumar Patel; Kenal V. Shah; Bhavesh V. Shah; Kawarlal DABHODIA
Original assignee: Rajdhani Petrochemicals Private Limited
Priority date: 2020-07-30
Filing date: 2021-07-30
Publication date: 2022-02-03

Abstract

A synergistic formulation for plant protective composition comprising prothiconazole. More particularly the present invention relates to a synergistic agrochemical composition for foliar application comprising of bioactive amount of Prothioconazole; and one or more Insecticides. The present invention further relates to the process of preparing the said composition in specific ratio. The present invention further relates to a synergistic agrochemical composition, wherein active ingredients present in fixed ratio show synergy in pesticidal activity.

Description

Title:- SYNERGISTIC FORMULATION FOR PLANT PROTECTIVE COMPOSITION COMPRISING PROTHIOCONAZOLE

FIELD OF INVENTION:

The present invention relates to synergistic formulation for foliar application comprising of bioactive amounts of a fungicide Prothioconazole; and an Insecticide compound. The present invention further relates to the preparation of the said formulation comprising agrochemical composition in specific ratio. More particularly the present invention relates to a formulation for plant protection.

BACKGROUND OF INVENTION:

Protection and maintenance of cultivated crops is of prime importance. Crops have to be protected from insect pests and fungal diseases. Hence, foliar application is the best method of prevention of pest infestation and fungal diseases. Combination of insecticides and fungicides are used to broaden the spectrum of control of insect and fungal pests, reduce dosage and decrease the chances of development of resistance. The combinations of insecticides and fungicides at times demonstrate an additive or synergistic effect that results in an improved control on pests and overall crop health and plant vigour in field condition. The present synergistic foliar application combination is absorbed by leaves and is translocated throughout the plant. When insects feed on these crops, the systemic insecticide will kill them. Hence, such a mode of action would promote overall plant health.

Damage to seeds and plants from insect and fungal pests is another major concern for agriculturalist. T There are various fungal diseases such as anthracnose, botrytis rot, downy mildews, powdery mildews, fusarium rots, rhizoctonia rots, sclerotinia rots, sclerotium rots etc and different sapsucking and foliage feeding insects such as aphid, jassid, whitefly, caterpillars, grass hoppers, stem borers etc. which are causes in to considerable decrease in crop yield and causes great economical losses to the farmers. Treating the crops with insecticidal and fungicidal combinations helps to reduce the damage from fungal diseases and insects. Another advantage of treating the plant and plant parts is the increase in yield and improved overall plant health. There are many combinations of insecticide and fungicide known in the prior art for the control of insect pests, mites and fungal diseases. US 10076119B2 relates to pesticidal mixtures comprising one biological compound and at least one fungicidal, insecticidal or plant growth regulating compound as defined herein and respective agricultural uses thereof. In the said invention, prothioconazole and triflumezopyrim are used as fungicide and insecticide respectively.

JP6644681B2 relates to the use of carboxamide derivatives for controlling arthropods, in particular insects and arachnids, (c) mites and / or nematodes. The said invention relates to the use of carboxamide derivatives for controlling soil-living pests by a seed treatment method. In the said invention both prothioconazole and triflumezopyrim are used as pesticidal composition.

EP2910126A1 relates to novel active compound combinations comprising at least one known compound of the formula (I) and at least one further active compound, which combinations are highly suitable for controlling animal pests such as unwanted insects and/or unwanted acarids. Prothioconazole and Triflumezopyrim are both part of the composition of the said invention.

There is however a need for improvement of these combinations. Single active combinations used over a long period of time have resulted in resistance. With the onset of resistance of certain pests, there is a need in the art for a combination of actives that decreases the chances of resistance and improves the spectrum of disease and pest control. In general use, the pesticide actives are used in the form of a dilute aqueous composition because it can attain a good interaction with the target organism, such as plants, fungi and insects. However, most active pesticide compounds that are used as pesticides are only sparingly or even insoluble in water. The low solubility of such compounds present the challenges and difficulties to formulator in formulating pesticide compounds in stable formulations that can be easily stored for a long time and which still have a high stability and effective activity until end use. This problem especially occurs and may get worsen if more than one active compound is present in the composition.

Therefore the object of the present invention is to provide novel synergistic and stable Oil Dispersion formulation, Suspension concentrate (SC) formulation comprising fungicide like Prothioconazole; and one or more Insecticides for foliar application. Yet another object of the present invention is to provide improved, stable and non-phytotoxic fungicides and insecticides for the control of insect pests and fungal diseases. Another object of the present invention is to provide a method and a composition for controlling insect pests and fungal diseases around plant parts and propagation material. Yet another object of the present invention is to provide combinations of fungicides and insecticides that promote plant health and increasing plant vigor in the field. Another object of the present invention is to increase the overall plant yield.

Embodiment of the present invention can ameliorate one or more of the above mentioned problems. Inventors of the present invention have surprisingly found that the synergistic formulation for plant protection comprising agrochemical composition for foliar application comprising of fungicide like Prothioconazole; and one or more Insecticides can provide solution to the above mentioned problems. SUMMARY OF INVENTION:

Therefore an aspect of the present invention provides synergistic formulation for plant protection comprising agrochemical composition comprising (A) Fungicide; and (B) one or more insecticides.

More particularly, the present invention provides synergistic formulation for plant protection comprising agrochemical composition of (A) Fungicide like Prothioconazole; and (B) one or more insecticides selected from the class of class of nicotinic insecticides, chordotonal organs modulators, diamides, metadiamides, isoxazolines and insecticides with unknown mode of action or unclassified.

An aspect of the present invention provides synergistic formulation for plant protection comprising agrochemical composition comprising (A) Fungicide; and (B) one or more insecticides for seed treatment, foliar treatment and soil application

Accordingly, in a further aspect, the present invention provides a method of protecting a plant, seed and other plant parts against pathogenic damage or pest damage by applying to the plant a composition comprising an agrochemical composition defined in the first aspect.

Another aspect of the present invention provides synergistic formulation for plant protection comprising agrochemical composition is Suspension Concentrate (SC) and Oil Dispersion (OD) formulation.

In an aspect of the present invention provides Oil Dispersion (OD) formulation comprises of vegetables oil as carrier that increases penetration into leaf surfaces, especially plant, improves retention of active ingredients on leaf surfaces, increases spreading action, so faster spray coverage on leaf surface and easily dissolve the waxy layer of the leaf surface.

Another aspect of the present invention provides the Oil Dispersion formulation of the present agrochemical composition increases the bioefficacy of targets insect -pests with reduced dose of active ingredient.

Further aspect of the present invention provides the Suspension Concentrate (SC) formulation comprises Trisiloxane Ethoxylate as a wetting spreading and penetrating agent promotes the rapid intake of the pesticide on leaf or the affected plant surface and acts as a ‘superspreader’ of pesticides over moderately hydrophobic surface to a very large area, usually in a short time period. Accordingly, in yet another aspect of the present invention provides the further formulations that can be selected from Capsule suspension (CS), Dispersible concentrate (DC), Emulsifiable concentrate (EC), Emulsion, water in oil (EO), Emulsion, oil in water (EW), Jambo balls or bags (bags in water soluble pouch), Micro-emulsion (ME), Oil dispersion (OD), Oil miscible flowable concentrate (oil miscible suspension (OF), Oil miscible liquid (OL), Suspension concentrate (SC), Suspo-emulsion (SE), Soluble concentrate (SL), Water dispersible granule (WG or WDG), Water soluble granule (SG), Water soluble powder (SP), Wettable powder (WP), A mixed formulation of CS and SC (ZC), A mixed formulation of CS and SE (ZE), A mixed formulation of CS and EW (ZW), Granule (GR) / Soil Applied Granules (SAG), Controlled release granules (CR).

The remainder of the aqueous formulation is preferably wholly water but may comprise other materials, such as inorganic salts. The formulation is preferably, completely free from organic solvents.

Accordingly, in a first aspect, the present invention provides an agrochemical composition comprising (A) Prothioconazole; and (B) one or more Insecticides; show synergistic activity. DETAILED DESCRIPTION OF INVENTION:

The term "health of a plant" or "plant health" is defined as a condition of the plant and/or its products. As a result of the improved health, yield, plant vigor, quality and tolerance to abiotic or biotic stress are increased. Noteworthy, the health of a plant when applying the method according to the invention, is increased independently of the pesticidal properties of the active ingredients used because the increase in health is not based upon the reduced disease pressure but instead on complex physiological and metabolic reactions which result for example in an activation of the plant's own natural defense system. As a result, the health of a plant is increased even in the absence of diseases pressure. Accordingly, in an especially preferred embodiment of the method according to the invention, the health of a plant is increased both in the presence and absence of biotic or abiotic stress factors. The above identified indicators for the health condition of a plant may be interdependent or they may result from each other. An increase in plant vigor may for example result in an increased yield and/or tolerance to abiotic or biotic stress. One indicator for the condition of the plant is the yield. "Yield" is to be understood as any plant product of economic value that is produced by the plant such as grains, fruits in the proper sense, vegetables, nuts, grains, seeds, wood (e.g. in the case of silviculture plants) or even flowers (e.g. in the case of gardening plants, ornamentals). The plant products may in addition be further utilized and/or processed after harvesting.

In an especially preferred embodiment of the invention, the yield of the treated plant is increased. In another preferred embodiment of the invention, the yield of the plants treated according to the method of the invention, is increased synergistically.

According to the present invention, "increased yield" of a plant, in particular of an agricultural, silvicultural and/or horticultural plant means that the yield of a product of the respective plant is increased by a measurable amount over the yield of the same product of the plant produced under the same conditions, but without the application of the mixture according to the invention.

Increased yield can be characterized, among others, by the following improved proper-ties of the plant: increased plant, weight, increased plant height, increased biomass such as higher overall fresh weight (FW), increased number of flowers per plant, higher grain yield, more tillers or side shoots (branches), larger leaves, increased shoot growth, increased protein content, increased oil content, increased starch content, increased pigment content, increased leaf are index.

According to the present invention, the yield is increased by at least 5 %, preferable by 5 to 10 %, more preferable by 10 to 20 %, or even 20 to 30 % compared to the untreated control plants or plants treated with pesticides in a way different from the method according to the present invention. In general, the yield increase may even be higher. A further indicator for the condition of the plant is the plant vigor. The plant vigor becomes manifest in several aspects such as the general visual appearance. In another especially preferred embodiment of the invention, the plant vigor of the treated plant is increased. In another preferred embodiment of the invention, the plant vigor of the plants treated according to the method of the invention, is increased synergistically. Improved plant vigor can be characterized, among others, by the following improved properties of the plant: improved vitality of the plant, improved plant growth, improved plant development, improved visual appearance, improved plant stand (less plant verse/lodging), improved emergence, enhanced root growth and/or more developed root system, enhanced nodulation, in particular rhizobium nodulation, bigger leaf blade, bigger size, increased plant weight, increased plant height, increased tiller number, increased number of side shoots, increased number of flowers per plant, increased shoot growth, increased root growth (extensive root system), increased yield when grown on poor soils or unfavorable climate, enhanced photosynthetic activity (e.g. based on increased stomatal conductance and/or increased C02 assimilation rate), increased stomatal conductance, increased C02 assimilation rate, enhanced pigment content (e.g. chlorophyll content), earlier flowering, earlier fruiting, earlier and improved germination, earlier grain maturity, improved self-defense mechanisms, improved stress tolerance and resistance of the plants against biotic and abiotic stress factors such as fungi, bacteria, viruses, heat stress, cold stress, drought stress, UV stress and/or salt stress, less non-productive tillers, less dead basal leaves, less input needed (such as fertilizers or water), greener leaves, complete maturation under shortened vegetation periods, less fertilizers needed, less seeds needed, easier harvesting, faster and more uniform ripening, longer shelf-life, longer panicles, delay of senescence, stronger and/or more productive tillers, better extractability of ingredients, improved quality of seeds (for being seeded in the following seasons for seed production), better nitrogen uptake, improved reproduction, reduced production of ethylene and/or the inhibition of its reception by the plant. The improvement of the plant vigor according to the present invention particularly means that the improvement of any one or several or all of the above mentioned plant characteristics are improved independently of the pesticidal action of the mixture or active ingredients (components).

Another indicator for the condition of the plant is the "quality" of a plant and/or its products.

In an especially preferred embodiment of the invention, the quality of the treated plant is increased. In another preferred embodiment of the invention, the quality of the plants treated according to the method of the invention, is increased synergistically.

According to the present invention, enhanced quality means that certain plant characteristics such as the content or composition of certain ingredients are increased or improved by a measurable or noticeable amount over the same factor of the plant produced under the same conditions, but without the application of the mixtures of the present invention. Enhanced quality can be characterized, among others, by following improved properties of the plant or its product: increased nutrient content, increased protein content, increased content of fatty acids, increased metabolite content, increased carotenoid content, increased sugar content, increased amount of essential amino acids, improved nutrient composition, improved protein composition, improved composition of fatty acids, improved metabolite composition, improved carotenoid composition, improved sugar composition, improved amino acids composition, improved or optimal fruit color, improved leaf color, higher storage capacity, higher processability of the harvested products.

Another indicator for the condition of the plant is the plant's tolerance or resistance to biotic and/or abiotic stress factors. Biotic and abiotic stress, especially over longer terms, can have harmful effects on plants. Biotic stress is caused by living organisms while abiotic stress is caused for example by environmental extremes. According to the present invention, "enhanced tolerance or resistance to biotic and/or abiotic stress factors" means (1.) that certain negative factors caused by biotic and/or abiotic stress are diminished in a measurable or noticeable amount as compared to plants exposed to the same conditions, but without being treated with a mixture according to the invention and (2.) that the negative effects are not diminished by a direct action of the mixture according to the invention on the stress factors, e.g. by its fungicidal action which directly destroys the microorganisms or diseases, but rather by a stimulation of the plants' own defensive reactions against said stress factors.

The present invention provides a synergistic agrochemical composition for foliar application comprising of (A) Fungicide like Prothioconazole; and (B) one or more insecticides.

More preferably, the present invention provides a synergistic agrochemical composition for foliar application comprising of (A) Prothioconazole; (B) one or more insecticides selected from the class of nicotinic insecticides, chordotonal organs modulators, diamides, metadiamides, isoxazolines and insecticides with unknown mode of action or unclassified. In an embodiment of the present invention, (B) one or more insecticides can be selected from from the class of nicotinic insecticides such as flupyrimin, triflumezopyrim, dichloromezotiaz, cycloxaprid, paichongding, guadipyr, cycloxylidin.

In a further embodiment of the present invention, one or more insecticides can be selected from the class of chordotonal organs modulators such as pyrifluquinazon; and afidopyropen.

In a further embodiment of the present invention, one or more insecticides can be selected from the class of diamides such as cyclaniliprole, cyhalodiamide, cyproflanilide, tetraniliprole, tetrachlorantr aniliprole , tyclopyr azoflor .

In a further embodiment of the present invention, one or more insecticides can be selected from the class of metadiamides such as broflanilide.

In a further embodiment of the present invention, one or more insecticides can be selected from the class of isoxazolines such as fluxametamide, isocycloseram.

In a further embodiment of the present invention, one or more insecticides can be selected from the unclassified insecticides such as benzpyrimoxan (insect growth regulators), oxazosulfyl, dimpropyridaz (pyrazole carboxamide insecticide) and flometoquin.

Prothioconazole:

Prothioconazole is a synthetic compound of the triazolinthione family of compounds. It is a broad spectrum systemic fungicide, with curative, preventative and eradicative action. It can be used as both a seed treatment and a foliar treatment. After absorption it moves into cells of the target organisms, effecting sterol biosynthesis and thereby disrupting membrane structure. This ultimately effects hyphal growth and germ tube elongation. Fungi susceptible to prothioconazole include Early leaf spot (Mycosphaerella arachidis), eyespot, Fusarium spp., powdery mildew, net blotch, phoma leaf spot, Rhynchosporium secalis, Sclerotinia sclerotiorum, Sclerotium rolfsii, Septoria tritici, Septoria nodorum, rust and tan spot. Prothioconazole is approved for use on barley, durum wheat, oats, oilseed rape (winter), rye (winter), and wheat.

Flupyrimin: A novel chemotype insecticide flupyrimin has unique biological properties, including outstanding potency to imidacloprid (IMI)-resistant rice pests together with superior safety toward pollinators. Intriguingly, FLP acts as a nicotinic antagonist in American cockroach neurons, and [3H]FLP binds to the multiple high-affinity binding components in house fly nicotinic acetylcholine (ACh) receptor (nAChR) preparation. One of the [3H] FLP receptors is identical to the IMI receptor, and the alternative is IMI-insensitive subtype. Furthermore, FLP is favorably safe to rats as predicted by the very low affinity to the rat a4b2 nAChR. Structure-activity relationships of FLP analogues in terms of receptor potency, featuring the pyridinylidene and trifluoroacetyl pharmacophores, were examined, thereby establishing the FLP molecular recognition at the Aplysia californica ACh- binding protein, a suitable structural surrogate of the insect nAChR. These FLP pharmacophores account for the excellent receptor affinity, accordingly revealing differences in its binding mechanism from IMI.

Triflume zopy rim:

Triflumezopyrim is an extremely effective hopper insecticide with low impact on non-target organisms including pollinators. This unique class of mesoionic chemistry targets the nicotinic acetylcholine receptor, inducing a physiological action which is distinct from that of neonicotinoids.

Dichloromezotiaz:

A novel class of mesoionic compounds has been discovered, with exceptional insecticidal activity on a range of Hemiptera and Lepidoptera. These compounds bind to the orthosteric site of the nicotinic acetylcholine receptor and result in a highly potent inhibitory action at the receptor with minimal agonism. The synthesis, biological activity, optimization and mode of action will be discussed. Dicloromezotiaz can provide a useful control tool for lepidopteran pests, with an underexploited mode of action among these pests. Pyrifluquinazon:

The market for compounds to treat sucking pests offers many commercial opportunities for innovative new products with novel modes of action (Mo As), high levels of biological efficacy, and low toxicity combined with high selectivity. Currently, three so-called selective feeding blockers are on the market, namely, pymetrozine, flonicamid, and pyrifluquinazon, offering attractive alternatives to current sucking pest products such as carbamates, organophosphates (OPs), synthetic pyrethroids, and neonicotinoids. The physicochemical properties of pymetrozine favor an efficient uptake and translocation in plants. Flonicamid shows a minimal tendency to persist in soil due to its fast degradation, while its moderate soil mobility is negated by its rapid metabolism and mineralization. Pyrifluquinazon shows excellent activity against a broad spectrum of hemipteran pests and some thysanopteran pests. Like pymetrozine, pyrifluquinazon has a favorable safety profile. Pyrifluquinazon is safe to beneficial insects and nontarget arthropods. Pyrifluquinazon is a recently commercialized insecticide that interferes with chordotonal receptor neuron function.

Broflanilide: Broflanilide, discovered by Mitsui Chemicals Agro, Inc., has a unique chemical structure characterized as a meta-diamide and exhibits high activity against various pests, including Lepidopteran, Coleopteran, and Thysanopteran pests. Because broflanilide has a novel mode of action, the Insecticide Resistance Action Committee (IRAC) categorized it as a member of a new group: Group 30. The meta-diamide structure was generated via drastic structural modification of a lead compound, flubendiamide, and the subsequent structural optimization of meta-diamides on each of its three benzene rings led to the discovery of broflanilide. In the present study, the details of the generation of meta-di amides from the lead compound and the structural optimization of meta- diamides are described.

Oxazosulfyl: In 2017, the common name of oxazosulfyl included in the Sumitomo Chemical patent claims was released. Oxazosulfyl is characterized by its aryl ethylsulfonyl moiety and exhibits broad- spectrum control of insect pests, including Hemiptera, Coleoptera, and Lepidoptera. Since this compound group has a broad insecticidal spectrum, it can grow into a large group of insecticides as a highly versatile pest control agent. Dimpropyridaz:

Dimpropyridaz chemically is a pyrazole carboxamide insecticide that has a pyridin-3-yl group, as in tyclopyrazoflor. Dimpropyridaz is effective against aphids. Dimpropyridaz mechanism of action is unknown. BASF recently published PCT patent application covering Form B dimpropyridaz. Dimpropyridaz exhibits polymorphism, e.g. Form-A & Form B. The polymorphic form-A is prior art form, which can be obtained by following process disclosed in compound patent of dimpropyridaz as glassy melt, which contains the crystalline form A. Polymorphic Form-B of dimpropyridaz is more stable than polymorphic Form-A.

The synergistic agrochemical composition has advantageous curative, preventive and systemic fungicidal properties for protecting cultivated plants. As has been mentioned, said active ingredient composition can be used to inhibit or destroy the pathogens that occur on plants or parts of plants of different crops or useful plants from the attack by the pathogens. The synergistic agrochemical composition of specific active ingredient has the special advantage of being highly active against diseases in the soil that mostly occur in the early stages of plant development.

The synergistic agrochemical composition of the present invention is used to protect the crops and plants from insect and fungal pests. Examples of the crops on which the present compositions may be used include but are not limited to GMO (Genetically Modified Organism) and Non GMO varieties of Cotton (Gossypium spp.), Paddy (Oryza sativa), Wheat (Triticum aestavum), Barley (Hordeum vulgare ), Maize (Zea mays), Sorghum (Sorghum bicolor), Oat (Avena sativa), Pearl millet (Pennisetum glaucum), Sugarcane (Saccharum officinarum) , Sugarbeet (Beta vulgaris), Soybean (Glycin max), Peanut (Arachis hypogaea), Sunflower (Helianthus annuus) , Mustard (Brassica juncea), Rape seed (Brassica napus), Linseed (Linum usitatissimum), Sesame (Sesamum indicum), Green gram (Vigna radiata), Black gram (Vigna mungo), Chickpea (Cicer aritinum), Cowpea (Vigna unguiculata), Redgram (Cajanus cajan), Frenchbean (Phaseolus vulgaris), Indian bean (Lablab purpureus), Horse gram (Macrotyloma uniflorum), Field pea (Pisum sativum), Cluster bean (Cyamopsis tetragonoloba), Lentils (Lens culinaris), Brinjal (Solanum melongena), Cabbage (Brassica oleracea var. capitata), Cauliflower (Brassica oleracea var. botrytis), Okra (Abelmoschus esculentus) , Onion (Allium cepa L.), Tomato (Solanum lycopersicun) , Potato (Solanum tuberosum) , Sweet potato (Ipomoea batatas), Chilly (Capsicum annum), Garlic (Allium sativum), Cucumber (Cucumis sativus), Muskmelons (Cucumis melo), Watermelon (Citrullus lanatus), Bottle gourd (Lagenaria siceraria), Bitter gourd (Momordica charantia), Radish (Raphanus sativus), Carrot (Dacus carota subsp. sativus), Turnip (Brassica rapa subsp rapa), Apple (Melus domestica), Banana (Musa spp.), Citrus groups (Citrus spp.), Grape (Vitis vinifera), Guava (Psidium guajava), Litchi (Litchi chinensis), Mango (Mangifera indica), Papaya (Carica papaya), Pineapple (Ananas comosus), Pomegranate (Punica granatum) , Sapota (Manilkara zapota), Tea (Camellia sinensis), Coffea (Coffea Arabica), Turmeric (Curcuma longa), Ginger (Zingiber officinale), Cumin (Cuminum cyminum), Fenugreek (Trigonella foenum-graecum), Fennel (Foeniculum vulgare), Coriander (Coriandrum sativum), Ajwain (Trachyspermum ammi), Psyllium (Plantago ovate), Black Pepper (Piper nigrum), Stevia ( Stevia rebaudiana), Safed musli (Chlorophytum tuberosum), Drum stick (Moringa oleifera), Coconut (Coco nucifera), Mentha ( Mentha spp.), Rose (Rosa spp.), Jasmine (Jasminum spp.), Marigold ( Tagetes spp.), Common daisy (Beilis perennis), Dahlia (Dahlia hortnesis), Gerbera ( Gerbera jamesonii), Carnation (Dianthus caryophyllus).

The synergistic agrochemical mixture also protects vegetables: solanaceous vegetables such as eggplant, tomato, pimento, pepper, potato, etc., cucurbit vegetables such as cucumber, pumpkin, zucchini, water melon, melon, squash, etc., cruciferous vegetables such as radish, white turnip, horseradish, kohlrabi, Chinese cabbage, cabbage, leaf mustard, broccoli, cauliflower, etc., asteraceous vegetables such as burdock, crown daisy, artichoke, lettuce, etc, liliaceous vegetables such as green onion, onion, garlic, and asparagus, ammiaceous vegetables such as carrot, parsley, celery, parsnip, etc., chenopodiaceous vegetables such as spinach, Swiss chard, etc., lamiaceous vegetables such as Perilla fmtescens, mint, basil, etc, strawberry, sweet potato, Dioscorea japonica, colocasia, etc., flowers, foliage plants, turf grasses, fruits: pome fruits such apple, pear, quince, etc, stone fleshy fruits such as peach, plum, nectarine, Prunus mume, cherry fruit, apricot, prune, etc., citrus fruits such as orange, lemon, rime, grapefruit, etc.

Furthermore the synergistic agrochemical composition is capable of protecting nuts such as chestnuts, walnuts, hazelnuts, almond, pistachio, cashew nuts, macadamia nuts, etc. berries such as blueberry, cranberry, blackberry, raspberry, etc., grape, kaki fruit, olive, plum, banana, coffee, date palm, coconuts, etc. , trees other than fruit trees; tea, mulberry, flowering plant, trees such as ash, birch, dogwood, Eucalyptus, Ginkgo biloba, lilac, maple, Quercus, poplar, Judas tree, Liquidambar formosana, plane tree, zelkova, Japanese arborvitae, fir wood, hemlock, juniper, Pinus, Picea, and Taxus cuspidate, etc.

The mixtures according to the invention can be applied to any and all developmental stages of pests, such as egg, larva, pupa, and adult. The pests may be controlled by contacting the target pest, its food supply, habitat, breeding ground or its locus with a pesticidally effective amount of the inventive mixtures or of compositions comprising the mixtures. The present synergistic agrochemical composition of the present invention is used to protect against insect pests such as order Hemiptera, for example, rice leafhopper Nephotettix nigropictus, rice brown plant hopper Nilaparvata lugen, rice white backed plant hopper, Apple Mealy bug Phenococcus aceris, bean aphid Aphis fabae, black citrus aphid Toxoptera aurantii, citrus black scale Saissetia oleae, cabbage aphid Brevicoryne brassicae, Lipaphis erysimi, citrus red scale Aonidiella aurantii, yellow scale Aonidiella citrine, citrus mealybug Planococcus citri, corn leaf aphid Rhopalosiphum maidis, cotton aphid Aphis gossypii, cotton jassid Amrasca biguttula biguttla, cotton mealy bug Planococcus spp. And Pseudococcus spp., cotton stainer Dysdercus suturellus, cotton whitefly Bemisia tabaci, cowpea aphid Aphis crassivora, grain aphid Sitobion avenae, golden glow aphid Uroleucon spp., grape mealybug Pseudococcus maritimus, green peach aphid Myzus persicae, greenhouse whitefly Trialeurodes vaporariorum, papaya mealy bug Pracoccus marginatus, pea aphid Acyrthosiphon pisum, sugarcane mealybug Saccharicoccus sacchari, potato aphid Myzus persicae, potato leaf hopper Empoasca fabae, cotton whitefly Bemisia tabaci, tarnished plant bug Lygus lineolaris, wooly apple aphid Eriosoma lanigerum, mango hopper Amritodus atkinsoni, Idioscopus spp. ; order Lepidoptera, army worm Mythimna unipuncta, asiatic rice borer Chilo suppressalis, bean pod borer Maruca vitrata, beet armyworm Spodoptera exigua, black cutworm Agrotis ipsilon, bollworm Helicoverpa armigera , cabbage looper Trichoplusia ni, codling moth Cydia pomonella, croton caterpillar Achea janata, diamond backmoth Plutella xylostella, cabbage worm Pieris rapae, pink bollworm Pectinophora gossypiella, sugarcane borer Diatraea saccharalis, tobacco budworm Heliothis virescens, tomato fruitworm Helicoverpa zea, velvet bean caterpillar Anticarsia gemmatalis, yellow stem borer Scirpophaga incertulas, spotted bollworm Earias vittella, rice leaffolder Cnaphalocrocis medinalis, pink stem borer Sesamia spp., tobacco leafeating caterpillar Spodoptera litura; brinjal fruit and shoot borer Leucinodes orbonalis, bean pod borer Maruca vitrata, Maruca testulalis, armyworm Mythimna separata, cotton pinkbollworm Pectinophora gossypiella, citrus leafminer Phyllocnistis citrella, cabbage butterfly Pieris bras-sicae, diamond backmoth Plutella xylostella, paddy stem borer Scirpophaga excerptallis, Scirpophaga incertulas, Scirpophaga innotata, wheat stem borer Sesamia inferens, Sitotroga cerealella, Spilosoma obliqua, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Trichoplusia ni, Tryporyza novella, Tuta absoluta.

Additionally the present invention is capable of protecting against the order Coleoptera, for example, apple twig borer Amphicerus spp., corn root worm Diabrotica virgifera, cucumber beetle diabrotica balteata, boll weevil Anthonomus grandis, grape flea beetle Altica chalybea, grape root worm Fidia viticola, grape trunk borer Clytoleptus albofasciatus, radish flea beetle Phyllotreta armoraciae, maize weevil Sitophilus zeamais, northern corn rootworm Diabrotica barberi, rice water weevil Lissorhoptrus oryzophilus, Anthonomus grandis, Bruchus lends, Diabrotica semipunctata, Diabrotica virgifera, Dicladispa armigera, Epila-chna varivestis, various species of white grubs are Holotrichia bicolor, Holotrichia consanguinea, Holotrichia serrata, Leptinotarsa decemlineata, Phyllotreta chrysocephala, Popillia japonica etc; from the order Orthoptera, for example, Gryllotalpa spp., Locusta spp., and Schistocerca is spp.; from the order Thysanoptera, for example, Frankliniella spp., Thrips palmi, Thrips tabaci and Scirtothrips dorsalis; termites (Isoptera), e.g. Calotermes flavicollis, Coptotermes formosanus, Heterotermes aureus, Leucotermes flavipes, Microtermes obesi, Odontotermes obesus, Reticulitermes flavipes, Termes natalensis; from the order Heteroptera, for example, Dysdercus spp., Leptocorisa spp., from the order Hymenoptera, for example, Solenopsis spp. ; from the order Diptera, for example, Antherigona soccata, Dacus spp., Liriomyza spp., Melanagromyza spp., from the order Acarina, for example, Aceria mangiferae, Brevipalpus spp., Eriophyes spp., Oligonychus mangiferus, Oligonychus punicae, Panonychus citri, Panonychus ulmi, Polyphagotarsonemus latus, Tarsonemus spp., Tetranychus urticae, Tetranychus cinnabarinus.

Furthermore the composition in the present invention is also effective against fungal infections such as Disease in rice: Blast (Magnaporthe grisea), Helminthosporium leaf spot (Cochliobolus miyabeanus), sheath blight (Rhizoctonia solani), bakanae disease (Gibberella fujikuroi) and grain discoloration (dirty panicles caused by Alternaria spp., Curvularia spp., Drechslera spp., Fusarium spp., Phoma spp. Etc.)

Diseases in wheat: powdery mildew (Erysiphe graminis), Fusariuin head blight (Fusarium graminearum, F. avenacerum, F. culmorum, Microdochium nivale), rust (Puccinia striiformis, P. graminis, P. recondita), pink snow mold (Micronectriella nivale), Typhula snow blight (Typhula sp.), loose smut (Ustilago tritici) , bunt (Tilletia caries), eyespot (Pseudocercosporella herpotrichoides), leaf blotch (Mycosphaerella graminicola), glume blotch (Stagonospora nodorum), septoria, and yellow spot (Pyrenophora tritici-repentis).

Diseases of barley: powdery mildew (Erysiphe graminis), Fusarium head blight (Fusarium graminearum, F. avenacerum, F. culmorum, Microdochium nivale), rust (Puccinia striiformis, P. graminis, P. hordei), loose smut (Ustilago nuda), scald (Rhynchosporium secalis) , net blotch (Pyrenophora teres), spot blotch (Cochliobolus sativus), leaf stripe (Pyrenophora graminea) , and Rhizoctonia damping-off (Rhizoctonia solani).

Diseases in corn: smut (Ustilago maydis), brown spot (Cochliobolus heterostrophus), copper spot (Gloeocercospora sorghi), southern rust (Puccinia polysora), gray leaf spot (Cercospora zeae- maydis), white spot (Phaeosphaeria mydis and/or Pantoea ananatis) and Rhizoctonia damping-off (Rhizoctonia solani).

Diseases of citrus: melanose (Diaporthe citri), scab (Elsinoe fawcetti), penicillium rot (Penicillium digitatum, P. italicum), and brown rot (Phytophthora parasitica, Phytophthora citrophthora).

Diseases of apple: blossom blight (Monilinia mali), canker (Valsa ceratosperma), powdery mildew (Podosphaera leucotricha), Alternaria leaf spot (Alternaria alternata apple pathotype), scab (Venturia inaequalis), powdery mildew, bitter rot (Colletotrichum acutatum), crown rot (Phytophtora cactorum), blotch (Diplocarpon mali), and ring rot (Botryosphaeria berengeriana).

Diseases of pear: scab (Venturia nashicola, V. pirina), powdery mildew, black spot (Alternaria alternata Japanese pear pathotype), rust (Gymnosporangium haraeanum), and phytophthora fruit rot (Phytophtora cactorum).

Diseases of peach: brown rot (Monilinia fructicola), powdery mildew, scab (Cladosporium carpophilum), and phomopsis rot (Phomopsis sp.).

Diseases of grape: anthracnose (Elsinoe ampelina), ripe rot (Glomerella cingulata), powdery mildew (Uncinula necator), rust (Phakopsora ampelopsidis), black rot (Guignardia bidwellii), botrytis, and downy mildew (Plasmopara viticola).

Diseases of Japanese persimmon: anthracnose (Gloeosporium kaki), and leaf spot (Cercospora kaki, Mycosphaerella nawae).

Diseases of gourd: anthracnose (Colletotrichum lagenarium), powdery mildew (Sphaerotheca fuliginea), gummy stem blight (Mycosphaerella melonis), Fusarium wilt (Fusarium oxysporum), downy mildew (Pseudoperonospora cubensis), Phytophthora rot (Phytophthora sp.), and damping- off (Pythium sp.). Diseases of tomato: early blight (Alternaria solani), leaf mold (Cladosporium fulvum), and late blight (Phytophthora infestans).

Diseases of eggplant: brown spot (Phomopsis vexans), and powdery mildew (Erysiphe cichoracearum) Diseases of cruciferous vegetables: Alternaria leaf spot (Alternaria japonica), white spot (Cercosporeha brassicae), clubroot (Plasmodiophora brassicae), and downy mildew (Peronospora parasitica).

Diseases of onion: rust (Puccinia allii), and downy mildew (Peronospora destructor).

Diseases of soybean: purple seed stain (Cercospora kikuchii), sphaceloma scad (Elsinoe glycines), pod and stem blight (Diaporthe phaseolorum var. sojae), septoria brown spot (Septoria glycines), frogeye leaf spot (Cercospora sojina), rust (Phakopsora pachyrhizi), Yellow rust, brown stem rot (Phytophthora sojae), and Rhizoctonia damping-off (Rhizoctonia solani).

Diseases of kidney bean: anthracnose (Colletotrichum lindemthianum). Diseases of peanut: leaf spot (Cercospora personata), brown leaf spot (Cercospora arachidicola) and southern blight (Sclerotium rolfsii). Diseases of garden pea: powdery mildew (Erysiphe pisi), and root rot (Fusarium solani f. sp. pisi).

Diseases of potato: early blight (Alternaria solani), late blight (Phytophthora infestans) , pink rot (Phytophthora erythroseptica), and powdery scab (Spongospora subterranean f. sp. subterranea).

Diseases of strawberry: powdery mildew (Sphaerotheca humuli), and anthracnose (Glomereha cingulata). Diseases of tea: net blister blight (Exobasidium reticulatum), white scab (Elsinoe leucospila), gray blight (Pestalotiopsis sp.), and anthracnose (Colletotrichum theae-sinensis).

Diseases of tobacco: brown spot (Alternaria longipes), powdery mildew (Erysiphe cichoracearum), anthracnose (Colletotrichum tabacum), downy mildew (Peronospora tabacina), and black shank (Phytophthora nicotianae). Diseases of rapeseed: sclerotinia rot (Sclerotinia sclerotiorum), and Rhizoctonia damping-off (Rhizoctonia solani). Diseases of cotton: Rhizoctonia damping-off (Rhizoctonia solani). Diseases of sugar beet: Cercospora leaf spot (Cercospora beticola), leaf blight (Thanatephorus cucumeris), Root rot (Thanatephorus cucumeris), and Aphanomyces root rot (Aphanomyces cochlioides).

Diseases of rose: black spot (Diplocarpon rosae), powdery mildew (Sphaerotheca pannosa) , and downy mildew (Peronospora sparsa). Diseases of chrysanthemum and asteraceous plants: downy mildew (Bremia lactucae), leaf blight (Septoria chrysanthemi-indici), and white rust (Puccinia horiana).

Diseases of various groups: diseases caused by Pythium spp. (Pythium aphanidermatum, Pythium debarianum, Pythium graminicola, Pythium irregulare, Pythium ultimum), gray mold. (Botrytis cinerea), and Sclerotinia rot (Sclerotinia sclerotiorum).

Disease of Japanese radish: Alternaria leaf spot (Alternaria brassicicola).

Diseases of turfgrass: dollar spot (Sclerotinia homeocarpa), and brown patch and large patch (Rhizoctonia solani).

Disease of banana: Black sigatoka (Mycosphaerella fijiensis), Yellow sigatoka (Mycosphaerella musicola).

Disease of sunflower: downy mildew (Plasmopara halstedii).

Seed diseases or diseases in the early stages of the growth of various plants caused by Aspergillus spp., Penicillium spp., Fusarium spp., Gibberella spp., Tricoderma spp., Thielaviopsis spp., Rhizopus spp., Mucor spp., Corticium spp., Phoma spp., Rhizoctonia spp. and Diplodia spp. Viral diseases of various plants mediated by Polymixa spp. or Olpidium spp. and so on.

The term “seed treatment” comprises all suitable seed treatment techniques known in the art, such as, but not limited to, seed dressing, seed coating, seed dusting, seed soaking, seed film coating, seed multilayer coating, seed encrusting, seed dripping and seed pelleting.

Formulation of the present invention can be in any of the formulations selected from Capsule suspension (CS), Dispersible concentrate (DC), Emulsifiable concentrate (EC), Emulsion, water in oil (EO), Emulsion, oil in water (EW), Jambo balls or bags (bags in water soluble pouch), Microemulsion (ME), Oil dispersion (OD), Oil miscible flowable concentrate (oil miscible suspension (OF), Oil miscible liquid (OL), Suspension concentrate (SC), Suspo-emulsion (SE), Soluble concentrate (SL), Water dispersible granule (WG or WDG), Water soluble granule (SG), Water soluble powder (SP), Wettable powder (WP), A mixed formulation of CS and SC (ZC), A mixed formulation of CS and SE (ZE), A mixed formulation of CS and EW (ZW), Granule (GR) / Soil Applied Granules (SAG), Controlled release granules (CR).

Further (A) Prothioconazole; and (B) one or more Insecticides; which are bioactive ingredients for the present composition are present in specific fixed ratio. Prothioconazole is 0.1% to 80% w/w in the composition. Whereas, Insecticide can be in the ratio of 0.1% to 80% w/w in the mixture.

The composition of the present invention in addition to bioactive amounts of active ingredients further comprises inactive excipients including but not limited to dispersant or dispersing agent, anti-freezing agent, anti-foam agent, wetting agent, suspension aid, thickener, stabilizing agent, suspending agent, emulsifying agent and preservative.

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. Examples of wetting agent used herein for SC (Suspension concentrate) formulation include but not limited to ethylene oxide/propylene oxide block copolymer, polyarylphenyl ether phosphate, ethoxylated fatty alcohol, sodium dioctyl sulfosuccinate, sodium lauryl sulfate and sodium dodecyl benzene sulfonate, alkyl diphenyl sulfonates, sodium isopropyl naphthalene sulfonate, alkyl naphthalene sulfonate, Organosilicone surfactants includes trisiloxane ethoxylate, polydimethylsiloxane, polyoxyethylene methyl polysiloxane, polyoxyalkylene methyl polysiloxane, polyether polymethyl siloxane copolymer, heptamethyl trisiloxane, Polyalkyleneoxide modified heptamethyl trisiloxane, polyether modified polysiloxane, 10 mole ethylene oxide adduct of octylphenol, may or may not be in modified form, may be liquid or powder form or mixture thereof.

Examples of wetting agent used herein for Oil Dispersion (OD) includes but not limited to ethylene oxide/propylene oxide block copolymer, polyarylphenyl ether phosphate, ethoxylated fatty alcohol, sodium dioctyl sulfosuccinate, sodium lauryl sulfate and sodium dodecyl benzene sulfonate, alkyldiphenyl sulfonates, sodium isopropyl naphthalene sulfonate, alkylnaphthalene sulfonate.

More particularly wetting spreading and penetrating agent for the present agrochemical composition and Suspension Concentrate (SC) and Oil Dispersion (OD) formulation thereof is organosilicone surfactants Trisiloxane Ethoxylate.

Trisiloxane ethoxylate is a Non-ionic surfactant that improves the spray coverage and promotes spray volume reduction. In the present invention it acts as a Wetting spreading and penetrating agent for the formulation comprising present agrochemical composition. Trisiloxane Ethoxylate wetting agent/spray adjuvant is a fast spreading surfactant/ wetting agent. It lowers the surface tension of spray solutions, beyond that which is achievable with conventional adjuvants. Trisiloxane ethoxylate promotes rapid uptake of agrochemicals (rainfastness). Trisiloxane ethoxylate surfactants lower the surface tension of the water, allowing the rapid coverage and penetration of cuticular waxes on hydrophobic leaf surfaces and causes an effect known as stomatal flooding; the almost instantaneous entrance of the solution into the openings in the plant surfaces. This fast penetration results in “rainfastness” as the delivery of the pesticide into the plant has occurred and further rainfall cannot remove the residue.

Trisiloxane ethoxylate is also acts as a Superspreader for soluble liquid and emulsifiable concentrate formulations. “Superspreading”, or “superwetting”, is the process by which a small droplet of an aqueous diluted solution of certain Trisiloxane Ethoxylate spreads on a moderately hydrophobic surface to a very large area, usually in a short time period (~ tens of seconds).

Further examples of wetting-spreading-penetrating agent used herein for SC (Suspension concentrate) formulation include but not limited to organosilicone surfactants includes trisiloxane ethoxylate, polydimethylsiloxane, polyoxyethylene methyl polysiloxane, polyoxyalkylene methyl polysiloxane, polyether polymethyl siloxane copolymer, heptamethyl trisiloxane,

Polyalkyleneoxide modified heptamethyl trisiloxane, polyether modified polysiloxane, may or may not be in modified form, may be liquid or powder form or mixture thereof.

Further examples of wetting-spreading-penetrating agent used herein for Oil Dispersion (OD) includes but not limited to organosilicone surfactants includes trisiloxane ethoxylate, polydimethylsiloxane, polyoxyethylene methyl polysiloxane, polyoxyalkylene methyl polysiloxane, polyether polymethyl siloxane copolymer, heptamethyl trisiloxane,

A dispersant or a dispersing agent 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. They are widely used in wettable powders, suspension concentrates and water-dispersible granules. 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. For wettable powder formulations, the most common dispersants are sodium lingo sulphonates. In recent years, new types of very high molecular weight polymeric surfactants have been developed as dispersants. These have very long hydrophobic ‘backbones’ and a large number of ethylene oxide chains forming the ‘teeth’ of a ‘comb’ surfactant. These high molecular weight polymers can give very good long-term stability to suspension concentrates because the hydrophobic backbones have many anchoring points onto the particle surfaces.

Examples of dispersants or dispersing agent used herein for SC (Suspension concentrate) formulation include but not limited to alkylated naphthalene sulfonate, sodium salt, sodium salt of naphthalene sulfonate condensate, sodium ligno sulfonate, sodium ploycarboxylate,EO/PO based copolymer, phenol sulfonate, sodium methyl oleoyl taurate, styrene acrylic acid copolymer, propyleneoxide-ethyleneoxide-copolymer, polyethylene glycol 2,4,6-tristyrylphenyl ether, tristyrylphenol-polyglycolether-phosphate, tristyrylphenole with 16 moles EO, tristyrylphenol- polyglycolether-phosphate, oleyl-polyglycolether with ethylene oxide, tallow fattyamine polyethylene oxide, nonylphenol polyglycolether with 9-10 moles ethylene oxide.

Examples of dispersants or dispersing agent used herein for Oil Dispersion (OD) formulation include but not limited to alkyl sulfonates, alkyl benzene sulfonates, alkyl aryl sulfonates, alkylphenolalkoxylates, tristyrylphenol ethoxylates, natural or synthetic fatty ethoxylate alcohols, natural or synthetic fatty acid alkoxylates, natural or synthetic fatty alcohols alkoxylates, alkoxylated alcohols (such as n-butyl alcohol poly glycol ether), block copolymers (such as ethylene oxide-propylene oxide block copolymers and ethylene oxide -butylene oxide block copolymers), fatty acid-polyalkylene glycol condensates, polyamine-fatty acid condensates, polyester condensates, salts of polyolefin condensates, sodium ligno sulfonate, sodium ploycarboxylate, EO/PO based copolymer, phenol sulfonate, sodium methyl oleoyl taurate, styrene acrylic acid copolymer, propyleneoxide-ethyleneoxide-copolymer, polyethylene glycol 2,4,6-tristyrylphenyl ether, tristyrylphenol-polyglycolether-phosphate, tristyrylphenole with 16 moles EO, tristyrylphenol-polyglycolether-phosphate, oleyl-polyglycolether with ethylene oxide, tallow fattyamine polyethylene oxide, nonylphenol polyglycolether with 9-10 moles ethylene oxide.

Antifoaming agent for the present formulation is selected from various compounds and selectively used according to the formulation. Generally, there are two types of antifoam agents, namely silicones and non-silicones. Silicones are usually aqueous emulsions of dimethyl poly siloxane 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.

Examples of Antifoaming agent used herein for SC (Suspension concentrate) formulation include but not limited to silicone oil, silicone compound, C10~C20 saturated fat acid compounds or C8 ~C10 aliphatic alcohols compound, silicone antifoam emulsion, dimethylsiloxane, polydimethyl siloxane, vegetable oil based antifoam, tallow based fatty acids, polyalkyleneoxide modified polydimethylsiloxane. Examples of Antifoaming agent used herein for Oil Dispersion (OD) formulation include but not limited to silicone oil, silicone compound, C10~C20 saturated fat acid compounds or C8~C10 aliphatic alcohols compound, silicone antifoam emulsion, dimethylsiloxane, polydimethyl siloxane, vegetable oil based antifoam, tallow based fatty acids, polyalkyleneoxide modified polydimethylsiloxane.

Anti-freezing agent for the present formulation is selected from various compounds and selectively used according to the formulation.

Examples of Anti-freezing agent used herein for SC (Suspension concentrate) formulation include but not limited to ethylene glycol, propane diols, glycerine or the urea, glycol (monoethylene glycol, diethylene glycol, polypropylene glycol, polyethylene glycol), glycerine, urea, magnesium sulfate heptahydrate, sodium chloride.

Examples of Anti-freezing agent used herein for Oil Dispersion (OD) formulation include but not limited to ethylene glycol, propane diols, glycerine or the urea, glycol (monoethylene glycol, diethylene glycol, polypropylene glycol, polyethylene glycol), glycerine, urea, magnesium sulfate heptahydrate, sodium chloride.

Preservative used herein for the SC (Suspension concentrate) formulation include but not limited to l,2-benzisothiazolin-3(2H)-one, sodium salt, Sodium benzoate, 2-bromo-2-nitropropane-l,3-diol, Formaldehyde, Sodium o-phenylphenate, 5-chloro-2-methyl-4-isothiazolin-3-one & 2-methyl-4- isothiazolin-3-one. Preservative used herein for Oil Dispersion (OD) formulation include but not limited to 1,2- benzisothiazolin-3(2H)-one, sodium salt, sodium benzoate, 2-bromo-2-nitropropane-l,3-diol, formaldehyde, sodium o-phenylphenate, 5-chloro-2-methyl-4-isothiazolin-3-one & 2-methyl-4- isothiazolin-3-one.

Thickeners or gelling agents are used mainly in the formulation of suspension concentrates, emulsions and suspoemulsions to modify the rheology or flow properties of the liquid and to prevent separation and settling of the dispersed particles or droplets. Thickening, gelling, and anti-settling agents generally fall into two categories, namely water-insoluble particulates and water-soluble polymers. Examples of thickeners used herein for SC (Suspension concentrate) formulation include but not limited to xanthan gum, PVK, carboxymethylcelluloses, polyvinyl alcohols, gelatin, sodium carboxymethylcellulose, hydroxyethylcellulose, sodium polyacrylate, modified starch;

Suspension aid or the suspending agent in the present description denotes a natural or synthetic, organic or inorganic material with which the active substance is combined in order to facilitate its application to the plant, to the seeds or to the soil. This carrier is hence generally inert, and it must be agriculturally acceptable, in particular to the plant being treated. The carrier may be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, and the like or mixtures thereof) or liquid (water, alcohols, ketones, petroleum fractions, aromatic or paraffinic hydrocarbons, chlorinated hydrocarbons, liquefied gases, and the like or mixtures thereof).

Examples of suspending agent used herein for SC (Suspension concentrate) formulation include but not limited to Aluminum Magnesium Silicate, Bentonite clay, Silica, Attapulgite clay.

Examples of Emulsifying agent used herein for Oil Dispersion (OD) formulation includes but not limited to castor oil ethoxylates, alcohol ethoxylates, fatty acid ethoxylates, sorbitan ester ethoxylates, sulphosuccinate, calcium salts of dodecylbenzene sulphonate, alkylammonium salts of alkyl benzene sulphonate, alkyl sulphosuccinate salts, ethylene oxide-propylene oxide block copolymers, ethoxylated alkylamines, ethoxylated alkyl phenols, polyoxyethylene sorbitan monolaurate.

Examples of stabilizer used herein for Oil Dispersion (OD) formulation includes but not limited to hectorite clay, aluminium magnesium silicate, bentonite clay, silica, attapulgite clay.

Carrier for the present formulation is selected from selected from various compounds and selectively used according to the formulation. Certain vegetables/plan t/seed oils as a carrier, increases the bioefficacy and residual control of products through increase in penetration of active ingredients into leaf surface, improves the retention of active ingredients on leaf surface especially on waxy leaf surface, improves the spreading properties and thereby improves the spray coverage.

More particularly Carrier for the present Oil Dispersion (OD) formulation is blend of methylated seed oil, polyalkyleneoxide modified polydimethylsiloxane and alkylphenol ethoxylate.

Methylated seed oil (MSO) is a kind of fatty acid from seed oil esterified with methyl alcohol. For oil-based adjuvant, droplet spread on leaf surfaces and herbicide penetration seem to be the two predominant factors regarding the mechanism of the enhancement in pesticide efficacy. MSO decrease the surface tension and contact angle and then increase the wetted areas of droplets on both waxy and hairy leaves. Further MSO enhances the efficacy by increasing the absorption of the pesticide. Methylated seed oils (MSO) are better solvents than petroleum-based oils. They have good spreading and penetration properties. Polyalkyleneoxide modified polydimethylsiloxane (PDMS) is a surfactant and is a component of defoamers. PDMS, in a modified form, is used as a penetrant and is a critical ingredient in water-repelling coatings. A biochemical penetrant is a chemical that increases the ability of a poison to apply its toxic effect to a living organism. PDMS with its inherent chemical properties it acts as Surfactant, Emulsifier, Dispersant, Flow Control Agent, and Lubricant in formulation preparation. Alkylphenol ethoxylates are nonionic surfactants, consisting of branched-chain alkylphenols, which react with ethylene oxide, producing an ethoxylate chain. Alkylphenol ethoxylates is having inherent emulsifying activity and acts as an excellent carrier when blended with other formulation adjuvants.

Further examples of Carrier or diluting agent used herein for Oil Dispersion (OD) formulation includes but not limited to as solvent for the present formulation is selected from and not limited to vegetable oil (plant, seed or tree) or its alkylated. The alkylated vegetable oil may be methylated vegetable oil or ethylated vegetable oil. The vegetable oils include olive oil, kapok oil, castor oil, papaya oil, camellia oil, sesame oil, corn oil, rice bran oil, cotton seed oil, soybean oil, groundnut oil, rapeseed-mustard oil, linseed oil, tung oil, sunflower oil, safflower oil, coconut oil. The alkyl ester of vegetable oils includes methyl ester, ethyl ester, propyl ester or butyl ester of vegetable oils. Some of the examples are rapeseed oil methyl ester, rapeseed oil ethyl ester, rapeseed oil propyl esters, rapeseed oil butyl esters, soybean oil methyl ester, soybean oil ethyl ester, soybean oil propyl ester, soybean oil butyl ester, castor oil methyl ester, castor oil ethyl ester, castor oil propyl ester, castor oil butyl ester, cotton seed oil methyl ester, cotton seed oil ethyl ester, cotton seed oil butyl ester, cotton seed oil propyl ester, tall oil fatty acids esters-tallow methyl ester, tallow ethyl ester, tallow propyl ester, diesel, mineral oil, fatty acid amides (e.g. Cl -C3 amines, alkylamines or alkanolamines with C6-C18 carboxylic acids), fatty acids, alkyl esters of fatty acids, methyl and ethyl oleate, methyl and ethyl soyate, alkyl benzenes and alkylnaphthalenes, polyalkylene glycol ethers, fatty acid diesters, fatty alkylamides and diamides, dialkylene carbonates, ketones and alcohols. The above oil based carrier/diluting agents may be used as solo or mixture of two or more if desired. The process for preparing the present novel synergistic composition can be modified accordingly by any person skilled in the art based on the knowledge of the manufacturing the formulation. However all such variation and modification is still covered by the scope of present invention.

Following the right use of the invented technology and the synergistic fungicidal composition of the invention with a formulations having a multi-pesticide components i.e. pesticide mixture, formulation prepared with an extra care of physical compatibility by purposefully specially selected solvents, dispersing agents, carriers and the surfactants, thickeners, stabilizers etc. exhibits better fungal and pest management and boost plant health.

While the foregoing written description of the invention enables one of ordinary skill to make and use what is considered presently to be the best mode thereof, those of ordinary skill will understand and appreciate the existence of variations, combinations, and equivalents of the specific embodiment, method, and examples herein. The invention should therefore not be limited by the above described embodiment, method, and examples, but by all embodiments and methods within the scope and spirit of the invention. The invention shall now be described with reference to the following specific examples. It should be noted that the example(s) appended below illustrate rather than limit the invention, and that those skilled in the art will be able to design many alternative embodiments without departing from the scope of the present invention.

These and other aspects of the invention may become more apparent from the examples set forth herein below. These examples are provided merely as illustrations of the invention and are not intended to be construed as a limitation thereof.

EXAMPLE 1:

SC (Suspension Concentrate) formulation of Prothioconazole 15%+Flupyrimin 10%

Storage stability-

Prothiocon azole 15%+Flupyrimin 10% SC (Suspension Concentrate)

Procedure: Manufacturing process of Suspension Concentrate (SC)

EXAMPLE 2: SC (Suspension Concentrate) formulation of Prothioconazole 20% + Triflumezopyrim 3.33%

Storage stability-

Prothioconazole 20%+ Triflumezopyrim 3.33% SC (Suspension concentrate)

Procedure: Manufacturing Process as per Example 1

EXAMPLE 3:

OD (Oil Dispersion) formulation of Prothioconazole 20%+Broflanilide 1.2%

Storage stability- Prothioconazole 20% + Broflanilide 1.2% OD (Oil Dispersion) formulation

Procedure: Manufacturing process of Oil dispersion (OD) formulation:

EXAMPLE 4:

OD (Oil Dispersion) formulation of Prothioconazole 15% + Flupyrimin 10%

Storage stability-

Prothioconazole 15%+Flupyrimin 10% OD (Oil Dispersion)

Procedure: Manufacturing Process as per Example 3

EXAMPLE 5: Lists of preferred formulations:

Biological Examples:

A synergistic effect exists wherever the action of a combination of active ingredient is greater than the sum of the action of each of the components alone. Therefore, a synergistically effective amount or an effective amount of a synergistic composition or combination is an amount that exhibits greater pesticidal activity than the sum of the pesticidal activities of the individual components. In the field of agriculture, it is often understood that the term “synergy” is as defined by Colby S.R. in an article entitled “ Calculation of the synergistic and antagonistic responses of herbicide combinations” published in the journal Weeds, 1967, 15, p.20-22, incorporated herein by reference in its entirety. The action expected for a given combination of two or three active components can be calculated as follows:

FIELD BIO-EFFICACY STUDIES:

Various formulations of Prothioconazole and insecticide has been developed in the laboratory and evaluated under the field condition for its efficacy and synergism. Experiment 1-Cotrol of insect-pests and diseases in paddy (Oryza sativa) crop.

Crop & Variety Paddy, BPT 5204 Location Kurud, Chhattisgarh Treatments 8 Plot size 60 sq.m. Cropp agge : 90 days after transplanting.

Spray water volume 420 liter per hectare

Method of Application: Foliar spray with battery operated knapsack sprayer fitted with hollow cone nozzle.

Agronomic Practices : Except insecticidal and fungicidal applications, all agronomic practices followed as per the crop requirement.

Observation Methods:

Brown Plant Hopper (BPH, Nilaparvata lugens) : The observation was recorded by counting the no. of live BPH per hill. Record the observations from 10 hills per plot at 5^th day after application. The percent insect control was worked out by below formula:

Grain discoloration (caused by different species of fungus Rhizoctonia spp.Drechslera spp., Curvularia spp., Alternaria spp.): Count the number of diseased grains and healthy grains from randomly selected 10 earhead per plot. Calculate % grain discoloration (as disease incidence) and then re-calculated % disease control (or % reduction in grain discoloration).

Table 1: Control of brown plant hopper in paddy

Colby’s ratio >1, means synergism

Table 2: Control of grain discoloration disease in paddy

All the ready-mix combinations of Prothiocon azole and insecticides (T1,T2 and T3) shows synergism in terms of insect control (BPH) and disease (grain discoloration) control and also produces higher number of productive tiller and grain yield per plot.

Experiment 2-Cotrol of insect-pests and diseases in paddy (Oryza sativa) crop.

Crop & Variety : Paddy, Sugandha Location : Dhamtari, Chhattisgarh Treatments : 10 Plot size : 50 sq.m. Crop age : 32 days after transplanting.

Spray water volume : 380 liter per hectare

Agronomic Practices : Except insecticidal and fungicidal applications, all agronomic practices were followed as per the crop requirement.

Observation Methods:

Stem borer (Scirpophaga incertulas) control- Count the number of healthy and damaged tillers (dead heart) per hill at 15 days after application. Record the observations from 10 hills per plot. Calculate dead heart (%) and recalculate stem borer control. Apply Colby’s formula to check synergism.

Sheath blight (Rhizoctonia solani) control : Observations was recorded on disease severity in each treatment before and at 14 days after spray. The observations of severity of sheath blight disease were recorded using 0-9 grade (SESJRRI 1996). Twenty randomly selected hills were scored as per scale. The percent disease index (PD I) of plants was calculated by the following formula.

Sheath blight disease Grading (0-9 scale) :

Table 3-Control of paddy stem borer

Table 4-Control of Paddy sheath blight

The synergistic combination of Prothiocon azole with insecticides (Tl, T2, T3 and T4) provides synergistic control of paddy stem borer and sheath blight and also produces higher grain yield. All the synergistic combinations were not phytotoxic to paddy crop and also found safe to the beneficial insects mainly to spider in the paddy crop ecosystem.

Experiment 3: Control of insect-pests and diseases in chilly (Capsicum annum)

Crop & Variety : Chilly, Rani Location : Umreth, Dist. Anand, Gujarat Treatments : 14 Plot size : 40 sq.m. Crop age : 72 days after transplanting.

Spray water volume : 510 liter per hectare

Agronomic Practices : All agronomic practices followed as per the crop requirement except insecticidal and fungicidal sprays.

Observation Methods:

Fruit borer (mixed infestation of Helicoverpa armigera and Spodoptera exigua) larval control (%)- Count the number of live larvae per plant. Record observations from 10 plants per plot on 7^th day after application.

Fruit rot (Colletotrichum capsici) control: Observations was recorded on disease severity in each treatment before and at 14 days after spray. The observations of severity of fruit rot disease were recorded using 0-9 grade. 100 randomly selected fruits per plot were scored as per scale. The percent disease index (PDI) was calculated by the following formula.

Fruit rot disease Grading (0-9 scale) :

% Fruit borer larval control and fruit rot disease control data were used to check the synergism by applying Colby’s formula given above.

Table 5: Control of fruit borer in chilly crop

Table 6-Control of fruit rot disease in Chilly

The synergistic combination of Prothioconazole with insecticides (Tl, T2, T3, T4, T5 and T6) provides synergistic control of chilly fruit borer larvae and fruit rot disease and also yielded higher number of green healthy fruits per plant.

The field trials results shows many benefits/advantages of ready-mix combination of Prothioconazole and insecticides

• synergism in terms of insect control, disease control

• Produces/yield higher yield of grains and fruits

• Provides residual control as per the visual observations

• Increase in number of fruits, flowers, grain, tillers and twigs per plant

Claims

We claim;

1) A synergistic formulation for plant protective agrochemical composition comprising: a. a fungicide Prothiconazole present in an amount of 0.1 to 80% by weight; b. an insecticide selected from the class of nicotinic insecticides, chordotonal organs modulators, diamides, metadiamides, isoxazolines, insecticides with unknown mode of action or unclassified present in an amount of 0.1 to 80% by weight or mixture thereof; c. formulation excipients.

2) The synergistic formulation for plant protective agrochemical composition as claimed in claim 1, wherein an insecticide from nicotinic insecticide is selected from flupyrimin, triflumezopyrim, dichloromezotiaz, cycloxaprid, paichongding, guadipyr, cycloxylidin.

3) The synergistic formulation for plant protective agrochemical composition as claimed in claim 1, wherein an insecticide from chordotonal organs modulators is selected from pyrifluquinazon; and afidopyropen.

4) The synergistic formulation for plant protective agrochemical composition as claimed in claim 1, wherein an insecticide from the class of diamides is selected from cyclaniliprole, cyhalodiamide, cyproflanilide, tetraniliprole, tetrachlorantraniliprole, tyclopyrazoflor.

5) The synergistic formulation for plant protective agrochemical composition as claimed in claim 1 , wherein an insecticide from metadiamide is broflanilide.

6) The synergistic formulation for plant protective agrochemical composition as claimed in claim 1, wherein an insecticide from class of isoxazolines is selected from fluxametamide, isocycloseram.

7) The synergistic formulation for plant protective agrochemical composition comprising as claimed in claim 1, wherein an insecticide from the unclassified is selected from benzpyrimoxan, oxazosulfyl, dimpropyridaz and flometoquin. 8) The synergistic formulation for plant protective agrochemical composition as claimed in claim 1 , wherein the formulation for the said composition is selected from Capsule suspension (CS), Dispersible concentrate (DC), Emulsifiable concentrate (EC), Emulsion, water in oil (EO), Emulsion, oil in water (EW), Jambo balls or bags (bags in water soluble pouch), Microemulsion (ME), Oil dispersion (OD), Oil miscible flowable concentrate (oil miscible suspension (OF), Oil miscible liquid (OL), Suspension concentrate (SC), Suspo-emulsion (SE), Soluble concentrate (SL), Water dispersible granule (WG or WDG), Water soluble granule (SG), Water soluble powder (SP), Wettable powder (WP), A mixed formulation of CS and SC (ZC), A mixed formulation of CS and SE (ZE), A mixed formulation of CS and EW (ZW), Granule (GR) / Soil Applied Granules (SAG), Controlled release granules (CR).

9) The synergistic formulation for plant protective agrochemical composition as claimed in claim 1 to claim 7, wherein the preferred composition for the Suspension Concentrate (SC) formulation comprises: i. Prothioconazole 15 % + Flupyrimin 10 %; ii. Prothioconazole 20 % + Triflumezopyrim 3.33 %; iii. Prothioconazole 20 % + Benzpyrimoxan 10 %; iv. Prothioconazole 15 % + Tetraniliprole 7.5 %; v. Prothioconazole 15 % + Cyclaniliprole 7.5 %; vi. Prothioconazole 15 % + Cyhalodiamide 7.5 %; vii. Prothioconazole 15 % + Cyproflanilide 7.5 %.

10) The synergistic formulation for plant protective agrochemical composition as claimed in 8, wherein the Suspension Concentrate (SC) formulation comprises: a. A fungicide present in an amount of 0.1 to 80% by weight of the composition is Prothiconazole; b. an insecticide from the class of nicotinic insecticides, chordotonal organs modulators, diamides, metadiamides, isoxazolines, insecticides with unknown mode of action or unclassified present in an amount of 0.1 to 80% by weight is selected from Flupyrimin, Triflumezopyrim, Benzpyrimoxan, Tetraniliprole, Cyclaniliprole, Cyhalodiamide, Cyproflanilide; c. Wetting-spreading-penetrating agent in an amount of 2 to 6 % by weight; d. Dispersing agent 1 in an amount of 2 to 8 % by weight; e. Dispersing agent 2 in an amount of 1 to 5 % by weight; f. Suspending agent in an amount of 0.2 to 4.0 % by weight; g. Antifoaming agent in an amount of 0.1 to 1.5 % by weight; h. Preservative in an amount of 0.1 to 0.5 % by weight; i. Antifreezing agent in an amount of 2 to 6 % by weight; j. Thickner in an amount of 0.1 to 1.0 % by weight; k. Diluent Water in an amount of 40 to 70 % by weight.

11) The synergistic formulation for plant for plant protective agrochemical composition as claimed in claim 9, wherein wetting-spreading-penetrating agent is trisiloxane ethoxylate.

12) The synergistic formulation for plant protective agrochemical composition as claimed in claim 9, wherein dispersing agent is selected from alkylated naphthalene sulfonate, sodium salt, sodium salt of naphthalene sulfonate condensate, sodium ligno sulfonate, sodium ploycarboxylate,EO/PO based copolymer, phenol sulfonate, sodium methyl oleoyl taurate, styrene acrylic acid copolymer, propyleneoxide-ethyleneoxide-copolymer, polyethylene glycol 2,4,6-tristyrylphenyl ether, tristyrylphenol-polyglycolether-phosphate, tristyrylphenole with 16 moles EO, tristyrylphenol-polyglycolether-phosphate, oleyl-polyglycolether with ethylene oxide, tallow fattyamine polyethylene oxide, nonylphenol polyglycolether with 9-10 moles ethylene oxide.

13) The synergistic formulation for plant protective agrochemical composition as claimed in claim 9, wherein antifoaming agent is selected from silicone oil, silicone compound, C10~C20 saturated fat acid compounds or C8~C10 aliphatic alcohols compound, silicone antifoam emulsion, dimethyl siloxane, polydimethyl siloxane, vegetable oil based antifoam, tallow based fatty acids, polyalkyleneoxide modified polydimethylsiloxane.

14) The synergistic formulation for plant protective agrochemical composition as claimed in claim 9, wherein Preservative is selected from l,2-benzisothiazolin-3(2H)-one, sodium salt, Sodium benzoate, 2-bromo-2-nitropropane-l,3-diol, Formaldehyde, Sodium o-phenylphenate, 5- chloro-2-methyl-4-isothiazolin-3-one & 2-methyl-4-isothiazolin-3-one. 15) The synergistic formulation for plant protective agrochemical composition as claimed in claim 9, wherein suspending agent is selected from Aluminum Magnesium Silicate, Bentonite clay, Silica, Attapulgite clay.

16) The synergistic formulation for plant protective agrochemical composition as claimed in claim 1- claim 7, wherein the preferred composition for the Oil Dispersion (OD) formulation comprises: i. Prothioconazole 20 % + Dichloromezotiaz 24.00 %; ii. Prothioconazole 20 % + Tyclopyrazoflor 25.00 %; iii. Prothioconazole 20 % + Broflanilide 21.20 %; iv. Prothioconazole 20 % + Flux am et amide 21.50 %; v. Prothioconazole 20 % + Isocycloseram 28.00 %; vi. Prothioconazole 20 % + Oxazosulfyl 30.00 %; vii. Prothioconazole 15 % + Dimpropyridaz 20.00 %; viii. Prothioconazole 15 % + Flumetoquin 20.00 %; ix. Prothioconazole 15 % + Pyrifluquinazon 20.00 %; x. Prothioconazole 15 % + Afidopyropen 20.00%.

17) The synergistic formulation for plant protective agrochemical composition as claimed in 8, wherein the Oil Dispersion (OD) formulation comprises: a. A fungicide present in an amount of 0.1 to 80% by weight of the composition is Prothiconazole; b. an insecticide from the class of nicotinic insecticides, chordotonal organs modulators, diamides, metadiamides, isoxazolines, insecticides with unknown mode of action or unclassified present in an amount of 0.1 to 80% by weight is selected from Dichloromezotiaz, Tyclopyrazoflor, Broflanilide, Fluxametamide, Isocycloseram, Oxazosulfyl, Dimpropyridaz, Flumetoquin, Pyrifluquinazon, Afidopyropen; c. Wetting-spreading-penetrating agent in an amount of 2 to 6 % by weight; d. Dispersing agent in an amount of 2 to 8 % by weight; e. Emulsifying agent in an amount of 6 to 10 % by weight; f. Stabilizer in an amount of 0.5 to 4% by weight; g. Antifoaming agent in an amount of 0.1 to 1.5 % by weight; h. Preservative in an amount of 0.1 to 0.5 % by weight; i. Antifreezing agent in an amount of 2 to 6 % by weight; j. Carrier as solvent in an amount of 40 to 70% by weight.

18) The synergistic formulation for plant protective agrochemical composition as claimed in claim 16, wherein carrier as a solvent is blend of Methylated seed oil, polyalkyleneoxide modified polydimethylsiloxane and alkylphenol ethoxylate.

19) The synergistic formulation for plant protective agrochemical composition as claimed in claim 16, wherein wetting-spreading-penetrating agent is selected from organosilicone surfactants includes trisiloxane ethoxylate, polydimethylsiloxane, polyoxyethylene methyl polysiloxane, polyoxyalkylene methyl polysiloxane, polyether polymethyl siloxane copolymer, heptamethyl trisiloxane, Polyalkyleneoxide modified heptamethyl trisiloxane, polyether modified polysiloxane, may or may not be in modified form, may be liquid or powder form or mixture thereof.

20) The synergistic formulation for plant protective agrochemical composition as claimed in claim 16, wherein dispersing agent is selected from alkyl sulfonates, alkyl benzene sulfonates, alkyl aryl sulfonates, alkylphenolalkoxylates, tristyrylphenol ethoxylates, natural or synthetic fatty ethoxylate alcohols, natural or synthetic fatty acid alkoxylates, natural or synthetic fatty alcohols alkoxylates, alkoxylated alcohols (such as n-butyl alcohol poly glycol ether), block copolymers (such as ethylene oxide -propylene oxide block copolymers and ethylene oxide- butylene oxide block copolymers), fatty acid-polyalkylene glycol condensates, polyamine- fatty acid condensates, polyester condensates, salts of polyolefin condensates, sodium ligno sulfonate, sodium ploycarboxylate, EO/PO based copolymer, phenol sulfonate, sodium methyl oleoyl taurate, styrene acrylic acid copolymer, propyleneoxide-ethyleneoxide- copolymer, polyethylene glycol 2,4,6-tristyrylphenyl ether, tristyrylphenol-polyglycolether- phosphate, tristyrylphenole with 16 moles EO, tristyrylphenol -polyglycolether-phosphate, oleyl-polyglycol- ether with ethylene oxide, tallow fattyamine polyethylene oxide, nonylphenol polyglycolether with 9-10 moles ethylene oxide. 21) The synergistic formulation for plant protective agrochemical composition as claimed in claim 16, wherein antifoaming agent is selected from silicone oil, silicone compound, C10~C20 saturated fat acid compounds or C8~C10 aliphatic alcohols compound, silicone antifoam emulsion, dimethyl siloxane, polydimethyl siloxane, vegetable oil based antifoam, tallow based fatty acids, polyalkyleneoxide modified polydimethylsiloxane.

22) The synergistic formulation for plant protective agrochemical composition as claimed in claim 16, wherein Preservative is selected from l,2-benzisothiazolin-3(2H)-one, sodium salt, Sodium benzoate, 2-bromo-2-nitropropane-l,3-diol, Formaldehyde, Sodium o- phenylphenate, 5-chloro-2-methyl-4-isothiazolin-3-one & 2-methyl-4-isothiazolin-3-one.

23) The synergistic formulation for plant protective agrochemical composition as claimed in claim 16, wherein emulsifying agent is selected from castor oil ethoxylates, alcohol ethoxylates, fatty acid ethoxylates, sorbitan ester ethoxylates, sulphosuccinate, calcium salts of dodecylbenzene sulphonate, alkylammonium salts of alkyl benzene sulphonate, alkyl sulphosuccinate salts, ethylene oxide -propylene oxide block copolymers, ethoxylated alkylamines, ethoxylated alkyl phenols, polyoxyethylene sorbitan monolaurate.

24) The synergistic formulation for plant protective agrochemical composition as claimed in claim 16, wherein stabilizer is selected from hectorite clay, aluminium magnesium silicate, bentonite clay, silica, attapulgite clay.