DESC:FORM 2

THE PATENTS ACT 1970
(SECTION 39 OF 1970)

&

THE PATENT RULES, 2003

COMPLETE SPECIFICATION
(Section 10 and Rule 13)

PESTICIDAL COMPOSITION COMPRISING INSECTICIDE AND FUNGICIDE

We, COROMANDEL INTERNATIONAL LIMITED,
an Indian company incorporated under the Companies Act, 1956 having its
principal place of business at Coromandel House, Sardar Patel Road,
Secunderabad – 500 003, Telangana, India

The following specification particularly describes the invention and the manner in which it is to be performed.

FIELD OF THE INVENTION
The present invention relates to pesticidal compositions and methods of using such compositions for control of a wide variety of undesired phytopathogenic micro-organisms, insect pests and mites.
The present invention relates to pesticidal compositions comprising an insecticide and fungicide combinations.
Particularly, the present invention relates to pesticidal compositions comprising combination of broad-spectrum insecticide, a strobilurin fungicide and an azole fungicide with one or more suitable additives.
More particularly, the present invention relates to pesticidal compositions comprising combination of Fipronil, Pyraclostrobin and Cyproconazole with one or more suitable additives.
BACKGROUND OF THE INVENTION
Pesticides are substances or mixtures of substances that are mainly used in agriculture or in public health protection programs in order to protect plants from pests, weeds or diseases, and humans from vector-borne diseases, such as malaria, dengue fever, and schistosomiasis. Insecticides, fungicides, herbicides, rodenticides, and plant growth regulators are typical examples of pesticides.
In many economically important crops and cash crops such as rice, peppers, grapes and other agricultural crops, fungal infection and insect infestation may occur simultaneously. In order to control this farmer usually apply compositions comprising either single active or combinations of actives. Control of plant diseases and pests is an inevitable work in efficiently performing the agricultural production, and in order to achieve this purpose, synthetic pesticides have been used, resulting in making a remarkable achievement.
Fipronil is a broad-spectrum insecticide that belongs to the phenylpyrazole chemical family. It was first registered for use in the United States in the 1990s. Agricultural use of Fipronil in the United States increased from 1998 to 2005. Fipronil has been widely used in seed coatings and granular soil treatments to control unwanted arthropods in many kinds of food, horticultural, and turf plants. Various spray and spot on products containing Fipronil have been widely utilized to control fleas, ticks, and mange mites on pet animals. Targeted pests and non-target organisms are poisoned by feeding upon or having contact with treated hosts (plant or animal), as well as through exposure to the insecticide in the environment.
Fipronil is not volatile. It binds to soils and sediment particles, and it is biodegraded in soil, which provides some protection against runoff and surface water contamination. Soils with higher organic carbon concentrations are more effective at binding Fipronil than soils with low organic carbon. Soil binding and biodegradation also help protect against percolation into groundwater.
Because of its effectiveness on various pests, Fipronil is used as the active ingredient in flea control products for pets and home roach traps as well as field pest control for corn, golf courses, and commercial turf. Its widespread use makes its specific effects the subject of considerable attention. This includes ongoing observations on possible off-target harm to humans or ecosystems as well as the monitoring of resistance development.
Fipronil, chemically known as 5-Amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-(trifluoromethanesulfinyl)-1H-pyrazole-3-carbonitrile. The structure of Fipronil is represented as below:

Pyraclostrobin is a quinone outside inhibitor (QoI)-type fungicide used in agriculture. Among the QoIs, it lies within the strobilurin chemical class. Quinone outside inhibitors (QoI) are powerful fungicides, which have been reported, additionally to their fungicide activity, to increase plant capacity to activate cellular defense responses and to promote plant growth. Their wide range of activity relies on their ability to disrupt the energy cycle of the fungus by binding to the quinone outside ubiquinol oxidation center of the cytochrome bc1 complex (complex III) in the inner mitochondrial membrane.
Pyraclostrobin is used against Botrytis cinerea and Alternaria alternata. Pyraclostrobin is used to protect Fragaria, Rubus idaeus, Vaccinium corymbosum, Ribes rubrum, Ribes uva-crispa, blackberry (various Rubus spp.),and Pistachio vera.
Pyraclostrobin a carbamate ester chemically known as the methyl ester of [2-({[1-(4-chlorophenyl)-1H-pyrazol-3-yl] oxy} methyl) phenyl] methoxycarbamic acid. The structure of pyraclostrobin is represent as below:

The azoles, 14-alpha demethylase inhibitors, have been the fungicide class used most widely to control fungal plant diseases for more than four decades. More than 25 different azoles have been developed for the control of plant diseases in crops and the group has a world market value share of 20-25%. Azoles have proven to provide long-lasting control of many target plant pathogens and are categorized to have moderate risk for developing fungicide resistance. Azoles target a broad spectrum of fungal pathogens in various crops. As one of the first azoles, imazalil was registered in the late 1970s as a seed treatment widely used in cereals and the protection of seed potatoes. Over time, the first azoles introduced have been replaced to a large extent by other active ingredients, such as tebuconazole, cyproconazole, difenoconazole, epoxiconazole, bromuconazole and prothioconazole. These newer azoles have been extensively used to control seed-borne, leaf and ear blight diseases.
Cyproconazole is an agricultural fungicide of the class of azoles, used on cereal crops, coffee, sugar beet, fruit trees and grapes, on sod farms and golf courses and on wood as a preservative. Cyproconazole inhibits demethylation, a particular step in the synthesis of a component of the fungal cell wall called sterol. This means it affects fungal growth, but not the fungal sporulation. Hence, it is preferably used when fungal growth is maximum, early in the infection, because in late infections fungal growth slows down and the agent is ineffective.
Cyproconazole is used against powdery mildew, rust on cereals and apple scab, and applied by air or on the ground to cereal crops, coffee, sugar beet, fruit trees and grapes. It controls the following pests: Puccinia graminis, Puccinia spp., Pseudocercosporella herpotrichoides and Septoria species. It can be used on above-ground wood to prevent it from decay from fungi.
Cyproconazole chemically known as 2-(4-Chlorophenyl)-3-cyclopropyl-1-(1H-1,2,4-triazol-1-yl) butan-2-ol. The structure of Cyproconazole is represented as below:

Tebuconazole is a triazole fungicide used agriculturally to treat plant pathogenic fungi. It is a systemic fungicide and delivers both curative and preventative control of diseased plants. Tebuconazole is used in a number of different popular fungicide products to control fungi, bacteria, and viruses affecting plants.
Some of the common fungal and disease problems Tebuconazole is known to treat are rust fungus, sheath blight, leaf spot, and anthracnose.
WO 2005/058040 A1 discloses a mixture for crop protection comprising carbamate compound, Fipronil and optionally other excipients selected from strobilurins or azoles with other class of fungicides. However, this application does not disclose pesticidal compositions comprising combination of Fipronil, Pyraclostrobin and Cyproconazole.
WO 2008/095913 A2 discloses a mixtures comprising, as active components, 1) an insecticidal compound I selected from fipronil and ethiprole; and 2) a fungicidal compound IIA selected from azoles, strobilurins, carboxamides, heterocylic compounds, carbamates, and other active compounds, and optionally 3) one or two fungicidal compounds IIB selected from List B which is defined as List A plus triticonazole, orysastrobin, in synergistically effective amounts, all as further defined in the description. However, this application does not disclose pesticidal compositions comprising combination of Fipronil, Pyraclostrobin and Cyproconazole.
The mixing of insecticides with fungicides results in incompatibility of physical nature and also may alter efficacy of the active ingredients. Hence, it requires due trial and experimentation to assess the compatibility of fungicides with insecticides and their influence on crops. Many pesticides with combination of one or more actives have been used by farmers. But still there is requirement for new combinations which can provide efficacy, low-cost benefit ratio, broad spectrum protection and decreased environmental load.
With increased use of chemical compounds as insecticides, herbicides, fungicides it has been observed that crops are becoming tolerant and resistant to use of composition comprising single active. Hence, there is a need for combination of actives belonging to different classes and groups to allow for broader disease control spectrum that combines curative and preventive actives and has a lower dosage.
There is a need in the art for new combinations of broad-spectrum insecticidal compound like Fipronil with different fungicides that help improve spectrum.
OBJECT OF THE INVENTION
One object of the present invention is to provide a pesticidal composition comprising combination of broad-spectrum insecticide Fipronil, a strobilurin fungicide Pyraclostrobin, and an azole fungicide Cyproconazole.
Another object of the present invention is to provide a pesticidal composition comprising a combination of Fipronil, Pyraclostrobin and Cyproconazole with one or more agrochemical additives.
Yet another object of the present invention is to provide an oil dispersion composition comprising of Fipronil, Pyraclostrobin and Cyproconazole with one or more agrochemical additives.
Yet another object of the present invention is to provide pesticidal composition to control broad spectrum of phytopathogenic microorganisms and insect pests.
In yet another object of the present invention is to provide a pesticidal composition with low toxicity to humans or other mammals.
In yet another object of the present invention is to provide a pesticidal composition resulting in increased yield of the crop.
In yet another object of the present invention is to provide a pesticidal composition comprising an insecticidal and fungicidal combination that causes an enhanced insecticidal and fungicidal activity.
SUMMARY OF THE INVENTION
One aspect of the present invention is to provide a pesticidal composition comprising combination of broad-spectrum insecticide Fipronil, a strobilurin fungicide Pyraclostrobin, and an azole fungicide Cyproconazole.
Another aspect of the present invention is to provide a pesticidal composition comprising a combination of Fipronil, Pyraclostrobin and Cyproconazole with one or more agrochemical additives.
Yet another aspect of the present invention is to provide a pesticidal composition comprising combination of Fipronil present in a range from 1% to 25% (w/w), Pyraclostrobin present in a range from 1% to 30% (w/w), Cyproconazole present in a range from 1% to 35% (w/w).
Yet another aspect of the present invention, the pesticidal composition comprises one or more agrochemical additives selected from the group comprising, a dispersing agent, an emulsifier, a rheology modifier, and a base oil.
Yet another aspect of the present invention is to provide an oil dispersion composition comprising of:
a) Fipronil is present in a range from 1% to 25% (w/w),
b) Pyraclostrobin is present in a range from 1% to 30% (w/w),
c) Cyproconazole is present in a range from 1% to 35% (w/w),
d) dispersing agent is present in a range from 1% to 10% (w/w),
e) emulsifier is present in a range from 1% to 10% (w/w),
f) rheology modifier is present in a range from 0.1% to 5% (w/w), and
g) base oil is present in a range from 10% to 70% (w/w).
Yet another aspect of the present invention is to provide an oil dispersion composition comprising of:
a) Fipronil is present in an amount of 8% (w/w),
b) Pyraclostrobin is present in an amount of 14% (w/w),
c) Cyproconazole is present in an amount of 20% (w/w),
d) calcium salt alkyl benzene sulphonate in 2-ethylhexanol is present in an amount of 3% (w/w),
e) castor oil ethoxylate with 36 EO is present in an amount of 7% (w/w),
f) fumed silica surface treated with a hexadecyl silane is present in an amount of 0.5%, and
g) methyl soyate oil is present in an amount of 47.5% (w/w).
In yet another aspect of the present invention is to provide a process for the preparation of an oil dispersion composition comprising of Fipronil, Pyraclostrobin and Cyproconazole with one or more agrochemical additives.
In yet another aspect of the present invention is to provide a process for the preparation of an oil dispersion composition, wherein the process comprising steps of:
a) adding base oil in a disperser under stirring followed by heating to 40-45°C,
b) adding dispersing agent and emulsifier at 40-45°C, and start homogenization at 6000 rpm for 20 min to get the homogenized solution,
c) adding specific quantity of Fipronil, Pyraclostrobin and Cyproconazole technical under continuous stirring over a period of 15 min,
d) adding rheology modifier and continue the stirring for further 1 hr,
e) milling the obtained material through dyno mill till the desired particle size distribution is achieved (D90 should be < 10 microns),
f) transferring the milled material into a separate vessel, and
g) packing the obtained oil dispersion into the drum.
The present invention relates to pesticidal composition with synergistic activity. The composition contains three components that mutually complement each other when used together and exhibit activity that is greater than the activities of individual components when used alone.

DESCRIPTION OF THE INVENTION
It is to be noted that, as used in the specification, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to a composition containing “a compound” includes a mixture of two or more compounds. It should also be noted that the term “or” is generally employed in its sense including “and/or” unless the content clearly dictates otherwise.
As used herein, the terms "crops" and "vegetation" can include, for instance, dormant seeds, germinant seeds, emerging seedlings, plants emerging from vegetative propagules, immature vegetation, and established vegetation.
As used herein, immature vegetation may be understood to include small vegetative plants prior to reproductive stage, and mature vegetation may be understood to include vegetative plants during and after the reproductive stage.
The novel pesticidal composition of the present invention may be formulated as Granular composition (GR), Capsule suspension (CS), Dispersible concentrate (DC), Dustable powder (DP), Powder for dry seed treatment (DS), Emulsifiable concentrate (EC), Emulsifiable granule (EG), Emulsion water-in-oil (EO), Emulsifiable powder (EP), Emulsion for seed treatment (ES), Emulsion oil-in-water (EW), Flowable concentrate for seed treatment (FS), Granules (GR), Micro-emulsion (ME), Oil-dispersion (OD), Oil miscible flowable concentrate (OF), Oil miscible liquid (OL), Oil dispersible powder (OP), Suspension concentrate (SC), Suspension concentrate for direct application (SD), Suspo-emulsion (SE), Water soluble granule (SG), Soluble concentrate (SL), Spreading oil (SO), Water soluble powder (SP), Water soluble tablet (ST), Ultra-low volume (ULV) suspension, Tablet (TB), Ultra-low volume (ULV) liquid, Water dispersible granules (WG), Wettable powder (WP), Water dispersible powder for slurry seed treatment (WS), Water dispersible tablet (WT), a mixed formulation of CS and SC (ZC), a mixed formulation of CS and SE (ZE), a mixed formulation of CS and EW (ZW). Preferably composition of the present invention is an oil dispersion (OD).
One embodiment of the invention, the pesticidal composition comprising of a combination of broad-spectrum insecticide Fipronil, a strobilurin fungicide Pyraclostrobin, and an azole fungicide Cyproconazole.
Another embodiment of the present, the pesticidal composition comprising a combination of Fipronil, Pyraclostrobin, and Cyproconazole with one or more agrochemical additives.
Another embodiment of the present invention, the pesticidal composition comprising combination of Fipronil present in a range from 1% to 25% (w/w), Pyraclostrobin present in a range from 1% to 30% (w/w), Cyproconazole present in a range from 1% to 35% (w/w).
Another embodiment of the present invention, the pesticidal composition comprises one or more agrochemical additives selected from the group comprising a dispersing agent, an emulsifier, a rheology modifier and a base oil.
Yet another embodiment of the present invention is to provide an oil dispersion composition comprising of:
a) Fipronil is present in a range from 1% to 25% (w/w),
b) Pyraclostrobin is present in a range from 1% to 30% (w/w),
c) Cyproconazole is present in a range from 1% to 35% (w/w),
d) dispersing agent is present in a range from 1% to 10% (w/w),
e) emulsifier is present in a range from 1% to 10% (w/w),
f) rheology modifier is present in a range from 0.1% to 5% (w/w), and
g) base oil is present in a range from 10% to 70% (w/w).
Yet another embodiment of the present invention is to provide an oil dispersion composition comprising of:
a) Fipronil is present in an amount of 8% (w/w),
b) Pyraclostrobin is present in an amount of 14% (w/w),
c) Cyproconazole is present in an amount of 20% (w/w),
d) calcium salt alkyl benzene sulphonate in 2-ethylhexanol is present in an amount of 3% (w/w),
e) castor oil ethoxylate with 36 EO is present in an amount of 7% (w/w),
f) fumed silica surface treated with a hexadecyl silane is present in an amount of 0.5%, and
g) methyl soyate oil is present in an amount of 47.5% (w/w).
The pesticidal composition in addition to insecticidal and fungicidal actives further contains a support, an adjuvant and/or a surfactant. During application, a common adjuvant can be mixed with the composition.
Suitable agrochemical additives of the present invention may be a solid or liquid and are generally a substance commonly used in formulation processing process, for example, natural or regenerated minerals, dispersing agents, emulsifier, rheology modifiers, base oil and its derivatives.
The dispersing agent as used herein is selected from Calcium salt alkyl benzene sulphonate in 2-ethylhexanol, Poly aryl alkylphenol polyethylene glycol phosphoric acid ester-Triethanol ammonium salt, polymeric ester and acrylic copolymer surfactant. The dispersing agent is present in a range from 1% to 10% (w/w).
Emulsifier as used herein is selected from Castor oil ethoxylate with 36 EO, Polyacrylate copolymer, non-ionic surfactant blend, and Polyoxyethylene (40) sorbitol hexaoleate. The emulsifier is present in a range from 1% to 10% (w/w).
Rheology modifiers plays an important role in keeping the viscosity of the composition to minimize the oil separation and maintains the homogeneity.
Rheology modifier as used herein is selected from fumed silica surface treated with a hexadecyl silane, organic derivative of a hectorite clay, hydrophilic fumed silica, and its combination thereof. The rheology modifier is present in a range from 0.1% to 5% (w/w).
Base oil as used herein is selected from methyl soyate oil, Sunflower oil, paraffin oil, vegetable oil and its derivatives. The base oil is present in a range from 10% to 70% (w/w).
The present novel active ingredients composition has very 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 (fruit, blossoms, leaves, stems, tubers, roots) of different crops or useful plants, while at the same time those parts of plants which grow later are also protected from attack by such pathogens. Active ingredient composition has the special advantage of being highly active against diseases in the soil that mostly occur in the early stages of plant development.
Specifically, the compositions of Fipronil, Pyraclostrobin and Cyproconazole are suitable for controlling to control seed and soil borne fungal diseases, foliar diseases in many agricultural, horticultural and forestry crops. It controlled following fungal species Albugo spp. (white rust) on ornamentals, vegetables (e. g. A. candida) and sunflowers (e. g. A. tragopogonis); Alternaria specie on vegetables, fruit, cereals, oilseed and pulses, Alternaria solani and Alternaria alternate on tomato, potato, chillies; Ascochyta species in pulse crops; Aspergillus species (A. niger, A. flavus, A. funigatus) on Groundnut, Soybean, Oilseeds and Pulses, Maize, Wheat and other cereals; Bipolaris and Drechslera species on cereals, maize, rice and turf; Blumeria graminis (powdery mildew) on cereals; Botrytis cinerea (gray mold) in vegetables, ornamentals, strawberries, tomatoes, sunflower and grapes; Ceratocystis spp. (rot or wilt) on fruit trees, Cercospora spp. (Cercospora leaf spots) on corn, rice, sugar beets (e. g. C. beticola), sugar cane, vegetables, coffee, soybeans (e. g. C. sojina or C. kikuchii) and rice; Cercospora arachidicola in groundnuts; Cladosporium spp. on tomatoes (e. g. C. fulvum: leaf mold) and cereals, e. g. C. herbarum (black ear) on wheat; Claviceps purpurea (ergot) on cereals; Cochliobolus sativus in cereals; Colletotrichum species in cotton, vegetables, pulse crops, oilseeds, Colletotrichum capsici on chillies; Corticium spp. on Rice, Corynespora spp. on soybeans and ornamentals, Didymella species on various plants; Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits, Erysiphe graminis in cereals; Fusarium graminearum in cereals and maize; Fusarium culmorum in cereals; Fusarium solani in cotton and vegetables; Fusarium spp. in cotton, soybean and potatoes; Fusarium oxysporum, Fusarium moniliforme, Fusarium proliferatum in maize; Fusarium and Mycosphaerella species on cereals, bananas, peanuts and soybean; Gaumannomyces graminis in cereals and lawns; Giberella fujikuroi in rice; Helminthosporium maydis in maize; Helminthosporium oryzae in rice; Helminthosporium solani on potatoes; Hemileia vastatrix on coffee; Macrophomina phaseolina on Soybean, Groundnut, Pulses and Oilseeds; Microdochium nivale in wheat and rye; Monilinia fructicola on stone fruits; Monilinia fructigena on fruits; Monilinia laxa on stone fruits; Mycosphaerella pinoides in peas; Penicillium digitatum on citrus; Penicillium expansum on apples; and Penicillium italicum on citrus; Phakopsara pachyrhizi and Phakopsara meibomiae on soybeans and pulses; Phragmidium mucronatum in roses; Phoma spp. in sugarbeet; Phoma exigua in potatoes; Phytophthora 15 aphanidermatum in Tobacco, Chillies, Tomato, Phytophthora sojae in Soybean and Pulses; Plasmopara halstedii in sunflowers; Pyrenophora graminea in barley; Pyricularia oryzae in rice; Plasmopara viticola on grapevines; Podosphaera leucotricha on apples; Pseudocercosporella herpotrichoides on wheat and barley, Pseudoperonospora species on hops and cucumbers; Puccinia species on cereals, Pyricularia oryzae on rice; Pythium spp. in cereals, cotton, maize and soybean; Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton, rape, sunflowers, soybeans, sugar beets, vegetables and various other plants (e. g. P. ultimum or P. aphani- dermatum); Ramularia spp., e. g. R. collo-cygni (Ramularia leaf spots, Physiological leaf spots) on barley and R. beticola on sugar beets; Rhizoctonia spp. on cotton, rice, potatoes, turf, corn, rape, potatoes, sugar beets, vegetables and various other plants, e. g. Rhizoctonia solani (root and stem rot) on cotton, chillies, tomatoes, soybeans, R. solani (sheath blight) on rice or R. cerealis (Rhizoctonia spring blight) on wheat or barley; Sclerotinia spp. (stem rot or white mold) on vegetables and field crops, such as rape, sunflowers (e. g. S. sclerotiorum); Sclerotium rolfsii on soybeans, groundnut, potato, tomato, chillies; Septoria spp. on various plants, e.g. S. glycines (brown spot) on soybeans, S. tritici (Septoria blotch) on wheat and S. (syn. Stagonospora) nodorum (Stagonospora blotch) on cereals, Septoria tritici and Stagonospora nodorum on wheat, Setospaeria spp. (leaf blight) on corn (e.g. S. turcicum, syn. Helminthosporium turcicum) and turf, Sphacelotheca spp. (smut) on corn, (e.g. S. reiliana: head smut), sorghum und sugar cane, Sphaerotheca fuliginea (powdery mildew) on cucurbits, Spongospora subterranea (powdery scab) on potatoes and thereby transmitted viral diseases, Stagonospora spp. on cereals, e.g. S.nodorum (Stagonospora blotch, teleomorph: Leptosphaeria [syn. Phaeosphaeria] nodorum) on wheat, Synchytrium endobioticum on potatoes (potato wart disease), Sphacelotheca reilliana in maize; Tilletia species in cereals; Typhula incarnata in barley; Thielaviopsis species on various plants; Uncinula necator, Guignardia bidwellii and Phomopsis viticola in vines; Urocystis occulta in rye; Ustilago species on cereals, maize and sugar cane ; Venturia species (scab) on apples and pears; Verticillium spp. (wilt) on various plants, such as fruits and ornamentals, vines, soft fruits, vegetables and field crops, e. g. V. dahliae on straw- berries, rape, potatoes and tomatoes.
Suitable targets for seed treatment are various crop seeds, fruit species, vegetables, spices and ornamental seed, for example corn/maize (sweet and field), durum wheat, soybean, groundnut, wheat, barley, oats, rye, triticale, bananas, rice, cotton, sunflower, potatoes, pasture, alfalfa, grasses, turf, sorghum, rapeseed, Brassica spp., sugar beet, egg-plants, tomato, lettuce, iceberg lettuce, pepper, cucumber, squash, melon, bean, dry-beans, peas, leek, garlic, onion, cabbage, carrot, tuber such as sugar cane, tobacco, coffee, turf and forage, cruciferous, cucurbits, grapevines, pepper, fodder beet, oil seed rape, pansy, impatiens, petunia and geranium.
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. The active ingredient composition according to the invention are especially advantageous for seed treatment of oil seed rape, wheat, corn, rye, barley, oats, sorghum, sunflowers, rice, maize, turf and forage, sugar beet, beans, peas, soybeans, ornamentals, and vegetables such as cucurbits, tomatoes, eggplant, potatoes, pepper, lettuce, cabbage, carrots, cruciferous.
The pesticidal composition of Fipronil, Pyraclostrobin, and Cyproconazole is having good sticking property, penetration and rain fasting properties, saves operational cost by milling the material, requires low dose, and economically feasible composition.
In yet another aspect of the present invention is to provide a process for the preparation of an oil dispersion composition comprising of Fipronil, Pyraclostrobin and Cyproconazole with one or more agrochemical additives.
In yet another aspect of the present invention is to provide a process for the preparation of an oil dispersion composition, wherein the process comprising steps of:
a) adding base oil in a disperser under stirring followed by heating to 40-45°C,
b) adding dispersing agent and emulsifier at 40-45°C, and start homogenization at 6000 rpm for 20 min to get the homogenized solution,
c) adding specific quantity of Fipronil, Pyraclostrobin and Cyproconazole technical under continuous stirring over a period of 15 min,
d) adding Rheology modifier and continue the stirring for further 1 hr,
e) milling the obtained material through dyno mill till the desired particle size distribution is achieved (D90 should be < 10 microns),
f) transferring the milled material into a separate vessel, and
g) packing the obtained oil dispersion into the drum.
In addition, by treating the pesticidal composition of the present invention in the soil, it becomes possible to simultaneously control pests inhabiting the soil and pests inhabiting the ground. In addition, in this method, since the dosage and the number of times of application of the active ingredient are reduced and the long-lasting effect is long, it is possible to provide a comprehensive control method.
The present invention provides combinations of insecticides and fungicides that possess an enhanced efficacy over the individual active compound used in isolation.
The above and other features and aspects of the present invention will be more clearly described in the complete specification which will be filed pursuant to the present provisional specification.

Examples:
Example-1: Fipronil 8% + Pyraclostrobin 14% + Cyproconazole 20% (OD)
S. No. Components Function Quantity
(in %w/w)
1. Fipronil Insecticide 8.0
2. Pyraclostrobin Fungicide 14.0
3. Cyproconazole Fungicide 20.0
4. Calcium salt alkyl benzene sulphonate in 2-ethylhexanol Dispersing agent 3.0
5. Castor oil ethoxylate with 36 EO Emulsifier 7.0
6. Fumed silica surface treated with a hexadecyl silane Rheology modifier 0.5
7. Methyl soyate oil Base oil 47.5
Total 100

Manufacturing Process:
Charged specified quantity of methyl soyate oil in the High sheer disperser and start stirring followed by heating to 40-45°C. Castor oil ethoxylate with 36 EO, followed by calcium salt alkyl benzene sulphonate in 2-ethylhexanol were added at the same temptation and start the homogenization (6000 rpm for 20 min) to get the homogenization solution. To this solution added specified quantity of Fipronil technical over a period of 15 minutes, Pyraclostrobin technical, after 15 min Cyproconazole technical, fumed silica surface treated with a hexadecyl silane were added and continued the stirring for further 1hr. Milled the obtained material through dyno mill to achieve desired Particle Size Distribution (D90 should be < 10 micron), transferred the milled material into a separate vessel, and packed the obtained oil dispersion into the drum.
Example-2: Fipronil 5% + Pyraclostrobin 10% + Cyproconazole 10% (OD)
S. No. Components Function Quantity
(in %w/w)
1. Fipronil Insecticide 5.0
2. Pyraclostrobin Fungicide 10.0
3. Cyproconazole Fungicide 10.0
4. Calcium salt alkyl benzene sulphonate in 2-ethylhexanol Dispersing agent 4.0
5. Castor oil ethoxylate with 36 EO Emulsifier 4.0
6. Hydrophilic fumed silica Rheology modifier 1.0
7. Sunflower oil Base oil 66.0
Total 100

Manufacturing Process:
Charged specified quantity of sunflower oil in the High sheer disperser and start stirring followed by heating to 40-45°C. Castor oil ethoxylate with 36 EO, followed by Calcium salt alkyl benzene sulphonate in 2-ethylhexanol were added at the same temptation and start the homogenization (6000 rpm for 20 min) to get the homogenization solution. To this solution added specified quantity of Fipronil technical over a period of 15 minutes, Pyraclostrobin technical, after 15 min Cyproconazole technical, hydrophilic fumed silica were added and continued the stirring for further 1hr. Milled the obtained material through dyno mill to achieve desired Particle Size Distribution (D90 should be < 10 micron), transferred the milled material into a separate vessel, and packed the obtained oil dispersion into the drum.
Example-3: Fipronil 12% + Pyraclostrobin 20% + Cyproconazole 15% (OD)
S. No. Components Function Quantity
(in %w/w)
1. Fipronil Insecticide 12.0
2. Pyraclostrobin Fungicide 20.0
3. Cyproconazole Fungicide 15.0
4. Organic derivative of a hectorite clay Rheology modifier 1.0
5. Tristyryl phenol-polyethylene glycol-phosphoric acid ester, tri ethanol ammonium salt. Dispersing agent 4.0
6. Polyacrylate copolymer Emulsifier 4.0
7. Hydrophilic fumed silica Rheology modifier 1.0
8. Paraffin oil Base oil 43
Total 100

Manufacturing Process:
Charged specified quantity of paraffin oil in the High sheer disperser and start stirring followed by heating to 40-45°C. Polyacrylate copolymer, followed by Tristyryl phenol-polyethylene glycol-phosphoric acid ester, tri ethanol ammonium salt was added at the same temptation and start the homogenization (6000 rpm for 20 min) to get the homogenization solution. To this solution added specified quantity of Fipronil technical over a period of 15 minutes, Pyraclostrobin technical, after 15 min Cyproconazole technical, Organic derivative of a hectorite clay and hydrophilic fumed silica were added and continued the stirring for further 1hr. Milled the obtained material through dyno mill to achieve desired Particle Size Distribution (D90 should be < 10 micron), transferred the milled material into a separate vessel, and packed the obtained oil dispersion into the drum.
Example-4: Fipronil 16% + Pyraclostrobin 5% + Cyproconazole 5% (OD)
S. No. Components Function Quantity
(in %w/w)
1. Fipronil Insecticide 16.0
2. Pyraclostrobin Fungicide 5.0
3. Cyproconazole Fungicide 5.0
4. Organic derivative of a hectorite clay Rheology modifier 1.0
5. Polymeric ester Dispersing agent 4.0
6. Non-ionic surfactant blend Emulsifier 4.0
7. Hydrophilic fumed silica Rheology modifier 1.0
8. Paraffin oil Base oil 64
Total 100

Manufacturing Process:
Charged specified quantity of paraffin oil in the High sheer disperser and start stirring followed by heating to 40-45°C. Non-ionic surfactant blend, followed by polymeric ester was added at the same temptation and start the homogenization (6000 rpm for 20 min) to get the homogenization solution. To this solution added specified quantity of Fipronil technical over a period of 15 minutes, Pyraclostrobin technical, after 15 min Cyproconazole technical, Organic derivative of a hectorite clay and hydrophilic fumed silica were added and continued the stirring for further 1hr. Milled the obtained material through dyno mill to achieve desired Particle Size Distribution (D90 should be < 10 micron), transferred the milled material into a separate vessel, and packed the obtained oil dispersion into the drum.
Example-5: Fipronil 20% + Pyraclostrobin 25% + Cyproconazole 30% (OD)
S. No. Components Function Quantity
(in %w/w)
1. Fipronil Insecticide 20.0
2. Pyraclostrobin Fungicide 25.0
3. Cyproconazole Fungicide 30.0
4. Organic derivative of a hectorite clay Rheology modifier 1.0
5. Polymeric surfactant Dispersing agent 4.0
6. Polyoxyethylene (40) sorbitol hexaoleate Emulsifier 4.0
7. Hydrophilic fumed silica Rheology modifier 1.0
8. Vegetable oil Base oil 15
Total 100

Manufacturing Process:
Charged specified quantity of vegetable oil in the High sheer disperser and start stirring followed by heating to 40-45°C. Polyoxyethylene (40) sorbitol hexaoleate, followed by polymeric surfactant was added at the same temptation and start the homogenization (6000 rpm for 20 min) to get the homogenization solution. To this solution added specified quantity of Fipronil technical over a period of 15 minutes, Pyraclostrobin technical, after 15 min Cyproconazole technical, Organic derivative of a hectorite clay and hydrophilic fumed silica were added and continued the stirring for further 1hr. Milled the obtained material through dyno mill to achieve desired Particle Size Distribution (D90 should be < 10 micron), transferred the milled material into a separate vessel, and packed the obtained oil dispersion into the drum.

SYNERGY STUDIES:
After calculating % disease control, the synergism was calculated by below formula: The synergistic pesticidal action of the inventive mixtures calculated by Colby’s formula as follows:
Appropriate analysis of plant response to pesticide combination is critical in determining the type of activity observed. The most widely used model is one Gowing* derived and Colby** modified. Gowing described a mathematical formula for calculating the predicting response values for pesticide mixtures. He suggested the expected (E) percent inhibition of growth induced by pesticide A plus pesticide B and plus pesticide C is as follows, *(Jerry Flint et al, 1988) ***

In which, E = Expected percentage of Insecticidal or fungicidal control for the combination of three active ingredient,
A = observed efficacy of active ingredient A at the same concentration as used in the mixture.
B = observed efficacy of active ingredient B at the same concentration as used in the mixture.
C = observed efficacy of active ingredient C at the same concentration as used in the mixture.
When the percentage of pesticidal control observed for the combination is greater than the expected percentage, there is a synergistic effect. (Ratio of O/E > 1, means synergism observed.)
Reference:
*Gowing, D. P. 1960. Comments on tests of herbicide mixtures. Weeds 8:379–391.
**Colby, S. R. 1967. Calculating synergistic and antagonistic responses of herbicide combinations. Weeds 15:20–22.
*** Jerry Flint et al, 1988. Analysing Herbicide Interactions: A Statistical Treatment of Colby's Method. Weed Technology 2: 304-309.
Field efficacy trials:
Bio efficacy studies were carried out in different crops. An oil dispersion formulation of Fipronil, Pyraclostrobin and Cyproconazole is developed and evaluated for their efficacy against onion purple blotch and onion Thrips.
Trial 1: Bio-efficacy against Onion purple blotch -
Purple Blotch is caused by the fungus Alternaria porri. It is an important disease in warm, humid onion-growing regions around the world. Garlic and leeks may be affected as well as onions. Most long-day onion cultivars are susceptible, but sweet Spanish onions are generally more susceptible than common yellow cultivars. All short-day cultivars are susceptible.
The disease often begins on older leaves as small, sunken, water-soaked lesions with light centres. Lesions enlarge as disease progresses and turn purple to brown, often with yellow rings that create a distinctive bull’s-eye pattern. Leaves turn yellow/brown and wilt and may be girdled. Younger leaves become more susceptible as the bulb matures. Bulbs may become infected through neck wounds. Yields may be reduced due to undersized bulbs and diseased bulbs may rot in storage. Bulb rot symptoms begin as soft, water-soaked areas; eventually, bulbs turn dark reddish-purple, then brown/black. The pathogen overwinters in crop residue on or near the soil surface. Spores are produced and new plants infected during periods of warm (77-85°F) humid weather. Symptoms appear 1-4 days after infection and black spores are produced by fresh lesions within 5 days. Spores are produced at night and released in the morning as humidity decreases. The spores are spread by wind and splashing rain or irrigation. Typical lesions occur when the leaf wetness duration is > 16 hours; flecking may occur at 12 hours.
The field trial was conducted to evaluate the efficacy of innovative mixtures of Fipronil, Pyraclostrobin, and Cyproconazole against Alternaria porri fungus in Onion crop. Trial was conducted with randomized block design with net plot size of 5m x 6m. Onion crop was raised with all standard agronomic practices. Spraying was done with manual operated backpack knapsack sprayer with 500 L of water spray volume per hectare at 40-45 days after transplanting. The visual observations were recorded for % disease control from ten plants per plot. The observations were recorded at before spraying, 7 DAA (Days after application) and 14 DAA (Days after application).
Table 1: Purple blotch disease control in Onion:
Compositions Dose
(g AI/ha) % Control – Onion purple blotch
07 DAA 14 DAA
Pyraclostrobin 70 70 60
Cyproconazole 100 65 40
Fipronil 40 25 20
Fipronil 8% + Pyraclostrobin 14% + Cyproconazole 20% (OD) 210 90 85
OD – oil dispersion, and DAA - Days after application.
The trial results show excellent efficacy of and Fipronil 8%, Pyraclostrobin 14%, and Cyproconazole 20% OD formulations against purple blotch disease of Onion. The solo application of three active ingredients tested here, were also not able to provide satisfactory control of purple blotch disease. The combination of Fipronil 8%, Pyraclostrobin 14%, and Cyproconazole 20% OD found very promising against Onion purple blotch in terms of efficacy as well as residual control.
Table 2: Percent Onion purple blotch disease control at 14DAA:
Compositions Dose
(g or ml/ha) % Purple blotch disease control
Actual
Pyraclostrobin 70 60
Cyproconazole 100 40
Fipronil 40 20
Fipronil 8% + Pyraclostrobin 14% + Cyproconazole 20% OD 210 85
Ratio of O/E 1.11

The table 2 results clearly demonstrate synergy between Fipronil, Pyraclostrobin, and Cyproconazole in controlling Onion purple blotch disease. The large difference between the observed and the expected efficacy clearly demonstrates the synergistic effect of the combination.
Trial 2: Bio-efficacy against Onion Thrips:
Onion thrips are tiny insects that range in colour from yellow to black and are only 1/16” in length. They spend the winter as adults in crop remnants, alfalfa, wheat, greenhouses, and weeds along the border of crop fields. Adults lay eggs singly in the epidermis, nymphs feed on leaves, and pupation occurs in the soil. There are at least two generations per year in the Northeast. Thrips have rasping mouth parts which they use to tear open plant cells to feed on plant juices. Populations are favoured by hot, dry weather.
In onions feeding occurs in protected, succulent areas where new leaves are emerging, deep between the leaf blades. Adults and nymphs pierce the epidermis and cell walls and remove cell contents. Damage may appear as silver lines, white patches, tip dieback, curling and twisting of leaves, slowed growth, reduced bulb size and yields, or if severe enough can result in plant death. The irregular and blotchy whitening of the plants is known as 'blast'. Plants are most sensitive when bulbs are forming. Scallions are particularly sensitive because the whole plant is marketed. Thrips damage can increase occurrence of purple blotch (Alternaria porri), as fungus can penetrate the plant through wounds caused by feeding.
The field trial was conducted to evaluate the efficacy of innovative mixtures of Fipronil, Pyraclostrobin, and Cyproconazole against Thrips tabaci in Onion crop. Trial was conducted with randomized block design with net plot size of 5m x 6m. Onion crop was raised with all standard agronomic practices. Spraying was done with manual operated backpack knapsack sprayer with 500 L of water spray volume per hectare at 40-45 days after transplanting. The visual observations were recorded for % pest damage from ten plants per plot. The observations were recorded at before spraying, 7 DAA (Days after application) and 14 DAA (Days after application).

Table 3: % Thrips control in Onion:
Compositions Dose
(g AI/ha) % Control – Onion Thrips
07 DAA 14 DAA
Pyraclostrobin 70 45 40
Cyproconazole 100 38 35
Fipronil 40 75 65
Fipronil 8% + Pyraclostrobin 14% + Cyproconazole 20% OD 210 85 80
OD – oil dispersion, and DAA - Days after application.
The trial results show excellent efficacy of Fipronil 8%, Pyraclostrobin 14%, and Cyproconazole 20% OD formulation against Thrips of Onion. The solo application of three active ingredients tested here were also not able to provide satisfactory control of Onion Thrips. The combination of Fipronil 8%, Pyraclostrobin 14%, and Cyproconazole 20% found very promising against Onion Thrips in terms of efficacy as well as residual control.
Table 4: Percent thrips control at 14 DAA:
Compositions Dose
(g or ml/ha) % Thrips control
Actual
Pyraclostrobin 75 35
Cyproconazole 125 30
Fipronil 30 65
Fipronil 8% + Pyraclostrobin 14% + Cyproconazole 20% OD 230 84
Ratio of O/E 1.23

The table 4 results clearly demonstrate synergy between Fipronil, Pyraclostrobin, and Cyproconazole in controlling Onion Thrips. The large difference between the observed and the expected efficacy clearly demonstrates the synergistic effect of the combination.
The pesticidal combination of Fipronil + Pyraclostrobin + Cyproconazole provided excellent control of onion purple blotch disease and thrips pest. The same combination had shown synergistic effect on insect and disease control in Onion. ,CLAIMS:WE CLAIM:
1. A pesticidal composition comprising a combination of Fipronil present in a range from 1% to 25% (w/w), Pyraclostrobin present in a range from 1% to 30% (w/w) and Cyproconazole present in a range from 1% to 35% (w/w).

2. The composition as claimed in claim 1, wherein said agrochemical additives selected from a dispersing agent, an emulsifier, a rheology modifier, and a base oil.

3. The pesticidal composition as claimed in claim 1, comprising:
a) Fipronil is present in a range from 1% to 25% (w/w),
b) Pyraclostrobin is present in a range from 1% to 30% (w/w),
c) Cyproconazole is present in a range from 1% to 35% (w/w),
d) dispersing agent is present in a range from 1% to 10% (w/w),
e) emulsifier is present in a range from 1% to 10% (w/w),
f) rheology modifier is present in a range from 0.1% to 5% (w/w), and
g) base oil is present in a range from 10% to 70% (w/w).

4. The pesticidal composition as claimed in claim 3, wherein the composition is formulated as an oil dispersion (OD).

5. The pesticidal composition as claimed in claim 3, wherein the dispersing agent is selected from calcium salt alkyl benzene sulphonate in 2-ethylhexanol, poly aryl alkylphenol polyethylene glycol phosphoric acid ester-triethanol ammonium salt, polymeric ester, and acrylic copolymer surfactant.

6. The pesticidal composition as claimed in claim 3, wherein the emulsifier as used herein is selected from castor oil ethoxylate with 36 EO, polyacrylate copolymer, non-ionic surfactant blend, and polyoxyethylene (40) sorbitol hexaoleate.

7. The pesticidal composition as claimed in claim 3, wherein the rheology modifier as used herein is selected from fumed silica surface treated with a hexadecyl silane, organic derivative of a hectorite clay, hydrophilic fumed silica, and its combination thereof.

8. The pesticidal composition as claimed in claim 3, wherein the base oil as used herein is selected from methyl soyate oil, Sunflower oil, paraffin oil, vegetable oil and its derivatives.

9. The process for the preparation of the pesticidal composition as claimed in claims 1 to 3, wherein the process comprising steps of:
a) adding base oil in a disperser under stirring followed by heating to 40-45°C,
b) adding dispersing agent and emulsifier at 40-45°C, and start homogenization at 6000 rpm for 20 min to get the homogenized solution,
c) adding specific quantity of fipronil, pyraclostrobin and cyproconazole technical under continuous stirring over a period of 15 min. and adding Rheology modifier and continue the stirring for further 1 hr,
d) milling the obtained material through dyno mill till the desired particle size distribution is achieved (D90 should be < 10 microns),
e) transferring the milled material into a separate vessel, and
f) packing the obtained oil dispersion into the drum.

Dated this Twenty Seventh (27th) day of February, 2023

__________________________________
Dr. S. Padmaja
Agent for the Applicant
IN/PA/883