DESC:FORM 2

THE PATENTS ACT, 1970
(SECTION 39 OF 1970)
&
The Patents Rules, 2003

COMPLETE SPECIFICATION
(Section 10 and Rule 13)

SYNERGISTIC INSECTICIDAL NEONICOTINOID COMBINATION FORMULATIONs, PROCESS FOR PREPARING AND USE THEREOF

We, COROMANDEL INTERNATIONAL LIMITED,
an Indian company incorporated under Companies Act of 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 synergistic insecticidal composition comprising combination of a neonicotinoid insecticide and second insecticide.

The present invention also relates to synergistic insecticidal composition comprising combination of a Nitenpyram and second insecticide, wherein said second insecticide is selected from Fipronil or Diafenthiuron.

The present invention also relates to synergistic insecticidal wettable powder (WP) composition comprising combination of Nitenpyram and second insecticide, wetting agent, dispersing agent and other agrochemical auxiliaries, wherein said second insecticide is selected from Fipronil or Diafenthiuron.

The present invention specifically relates to wettable powder composition comprising combination of Nitenpyram and second insecticide at a weight in the ratio of 1 : 10 to 10 :1 of first active ingredient to the second active ingredient, more preferably in the ratio of 1 : 5 to 5 : 1.

The present invention also relates to a process for the preparation of wettable powder composition comprising combination of Nitenpyram and second insecticide, wherein said wettable powder is prepared by simple blending and milling process.

BACKGROUND OF THE INVENTION
Nitenpyram is a synthetic, nicotine-related insecticide, has an effect on the nicotinic acetylcholine receptors. This compound is an insect neurotoxin belonging to the class of neonicotinoids which works by blocking neural signaling of the central nervous system. It does so by binding irreversibly to the nicotinic acetylcholine receptor (nACHr) causing a stop of the flow of ions in the postsynaptic membrane of neurons leading to paralysis and death.
Nitenpyram is chemically known as (E)-N-(6-chloro-3-pyridylmethyl)- N-ethyl-N'- methyl-2-nitrovinylidenediamine and has the following structure:

Nitenpyram has been used on many commercial crops, such as cotton, corn, and can be applied in various ways. Commonly used techniques are dusting and seed treatment. Seed treatment allows for a long lasting immunity to insects damaging the crops. The use of Nitenpyram has been shown to be highly effective in protecting crops, as it's generally less toxic for non-target organisms, while killing off crop-destroying insects.

Nitenpyram is used for controlling of aphids, thrips, leafhoppers, whitefly, and other sucking insects on rice and glasshouse crops. Nitenpyram applied on rice, applied at 15-75 g/ha (foliar), 75-100 g/ha (dust) or 300-400 g/ha (soil treatment) and also for control of fleas on cats and dogs.

Fipronil is a broad-spectrum insecticide which belongs to the phenylpyrazole chemical family. Fipronil disrupts the insect central nervous system by blocking GABA-gated chloride channels and glutamate-gated chloride (GluCl) channels. Fipronil is an insecticide used to control a broad range of insect pests mainly in horticultural crops and it is a chiral molecule. Fipronil is an isomeric mixture of two enantiomers (±; S/R). Fipronil was first registered for use by the United States Environmental Protection Agency (U.S.EPA) in May 1996.

Fipronil is chemically known as 5-amino-1-[2,6-dichloro-4-(trifluoromethyl) phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile and has the following structure:

Fipronil is used to control ants, beetles, cockroaches, fleas, ticks, termites, mole crickets, thrips, rootworms, weevils, and other insects. Uses for individual Fipronil products vary widely. Always read and follow the label when applying pesticide products.

Fipronil is used in granular turf products, seed treatments, topical pet care products, gel baits, liquid termiticides, and in agriculture.

Diafenthiuron is a pro-insecticide, which has first to be converted to its active form. The active compound then acts on a specific part of the energy-producing enzymes in the mitochondria. These results in immediate paralysis of the pest after intake or contact with the product. Diafenthiuron is chemically known as (4RS, 5RS)-5-(4-chlorophenyl)-N-cyclohexyl-4-methyl-2-oxo-1,3-thiazolidine-3-carboxamide and has the following structure.

Diafenthiuron was first reported in 1988 and first marketed in 1990. This product is not registered in EU under EC regulation 1107/2009.

Though, conventionally each of these active ingredients are used individually, combination product is not approved which has applications compared to the mono product. Hence, there is increased interest in the use of active ingredients in combination to give synergistic results.

The given below prior-art references show the use of combinations of Nitenpyram and Fipronil generically in different ratios.

US 8,790,674 B2 enables combination of Nitenpyram and Fipronil for killing fleas on a domestic animal by topical administration, wherein Nitenpyram and Fipronil is in the weight ratio comprises between 1/10 and 10/1. However, wetting agents and dispersing agents were not disclosed.

US 10,492,489 B2 generically enables combination of different active ingredients. However, the specific compositions of Nitenpyram and Fipronil combination are not disclosed.

Accordingly, there is a need in the art to provide insecticidal synergistic compositions which are environmentally safer and stable insecticidal / acaricidal compositions having two active ingredients with different physical and chemical properties, which are environmentally safe, easy, effective combination formulation of two active with enhanced efficacy and stable product during storage.

It was surprisingly and unexpectedly found by the present inventors that a selective combination composition of two active ingredients comprising Nitenpyram, and second insecticide selected form Fipronil or Diafenthiuron, a wetting agent, dispersing agent and other agrochemical auxiliaries, possesses enhanced efficacy, improved penetration and long duration control of phytopathogens as compared to its other traditional formulations with long storage stability across a wide temperature range having no adverse impact on photosynthetic activity in plant and seed quality.
OBJECTIVE OF INVENTION
The main objective of the present invention is to provide synergistic insecticidal composition comprising combination of neonicotinoid insecticide and second insecticide.

Another objective of the present invention is to provide synergistic insecticidal composition comprising combination of a Nitenpyram and second insecticide, wherein said second insecticide is selected from Fipronil or Diafenthiuron.

Another objective of the present invention is to provide synergistic insecticidal comprising combination of Nitenpyram and second insecticide, wetting agent, dispersing agent and other agrochemical auxiliaries, wherein said second insecticide is selected from Fipronil or Diafenthiuron.

Another objective of the present invention is to provide wettable powder composition comprising combination of Nitenpyram and second insecticide, wherein said second insecticide is selected from Fipronil or Diafenthiuron.

Another objective of the present invention is to provide wettable powder composition comprising combination of Nitenpyram and second insecticide at a weight in the ratio of 1 : 10 to 10 :1 of first active ingredient to the second active ingredient, more preferably in the ratio of 1 : 5 to 5 : 1.

Another objective of the present invention is to provide a process for the preparation of WP composition comprising combination of Nitenpyram and second insecticide, wherein said wettable powder is prepared by simple blending and milling process.

SUMMARY OF INVENTION
Accordingly, the present invention provides synergistic insecticidal composition comprising combination of neonicotinoid insecticidal, and second insecticidal.

In one embodiment, the present invention provides synergistic insecticidal composition comprising combination of neonicotinoid insecticidal, and second insecticidal, wherein said second insecticide is selected from Fipronil or Diafenthiuron.

In one embodiment, the present invention provides an insecticidal wettable powder composition comprising combination of Nitenpyram and second insecticide, wetting agent, dispersing agent and other agrochemical auxiliaries, wherein said second insecticide is selected from Fipronil or Diafenthiuron.

In another embodiment, the present invention provides an insecticidal wettable powder composition comprising combination of Nitenpyram and second insecticide, wherein said second insecticide is selected from Fipronil or Diafenthiuron.

In another embodiment, the present invention provides an insecticidal wettable powder composition comprising Nitenpyram and second insecticide, wetting agent, dispersing agent and other agrochemical auxiliaries, wherein said other agrochemical auxiliaries are selected from fillers/carriers, defoamer and rheology modifiers.

In another embodiment, the present invention provides an insecticidal wettable powder composition comprising combination of Nitenpyram and second insecticide at a weight in the ratio of 1 : 10 to 10 :1 of first active ingredient to the second active ingredient, more preferably in the ratio of 1 : 5 to 5 : 1.

In another embodiment, the present invention provides an insecticidal wettable powder composition comprising:
10% to 30 % (w/w) of Nitenpyram,
10% to 60% (w/w) of second insecticide which is selected from Fipronil or Diafenthiuron,
1% to 15% (w/w) of wetting agents,
1% to 15% (w/w) of dispersing agents, and
0.1% to 70% (w/w) of other additives / auxiliaries.

In another embodiment, the present invention provides an insecticidal wettable powder composition comprising:
10% to 30 % (w/w) of Nitenpyram,
10% to 60% (w/w) of Fipronil,
1% to 15% (w/w) of sodium salt of naphthalene formaldehyde condensate and alpha olefin sulphonate,
1% to 15% (w/w) of sodium salt of naphthalene sulfonate condensate, and
0.1% to 70% (w/w) of other additives / auxiliaries.

In another embodiment, the present invention provides an insecticidal wettable powder composition comprising:
10% to 30 % (w/w) of Nitenpyram,
10% to 60% (w/w) of Diafenthiuron,
1% to 15% (w/w) of linear alcohol derivative powder,
1% to 15% (w/w) of sodium polycarboxylate, and
0.1% to 70% (w/w) of other additives / auxiliaries.

In another embodiment, the present invention provides an insecticidal wettable powder composition comprising:
10% to 30 % (w/w) of Nitenpyram,
10% to 60% (w/w) of second insecticide which is selected from Fipronil or Diafenthiuron,
1% to 15% (w/w) of wetting agents,
1% to 15% (w/w) of dispersing agents,
30% to 70% (w/w) of inert carrier or fillers, and
1% to 50% (w/w) of other auxiliaries.

In another embodiment, the present invention provides an insecticidal wettable powder composition comprising:
10% to 30 % (w/w) of Nitenpyram,
10% to 60% (w/w) of Fipronil,
1% to 15% (w/w) of sodium salt of naphthalene formaldehyde condensate and alpha olefin sulphonate,
1% to 15% (w/w) of sodium salt of naphthalene sulfonate condensate,
10% to 60% (w/w) of lactose monohydrate,
1% to 15% (w/w) of ammonium sulfate, and
0.1% to 5% (w/w) of poly dimethylsiloxane.

In another embodiment, the present invention provides an insecticidal wettable powder composition comprising:
10% to 30 % (w/w) of Nitenpyram,
10% to 60% (w/w) of Diafenthiuron,
1% to 15% (w/w) of linear alcohol derivative powder,
1% to 15% (w/w) of sodium polycarboxylate,
10% to 60% (w/w) of hydrated aluminium silicate,
1% to 15% (w/w) of ammonium sulfate, and
1% to 10% (w/w) of precipitated silica.

In another embodiment, the present invention provides a process for the preparation of wettable powder composition comprising the steps of:
a. pre-blending active ingredients, wetting agent, dispersing agent along with other auxiliaries to form a homogenous mixture,
b. milling the blended mixture through air jet mill to obtain particles of size in the range of below 10µ, and
c. post blending the material obtained in step (b) to obtain powder .

In another embodiment, the present invention provides a process for the preparation of wettable powder composition comprising the steps of:
a. pre-blending all the Nitenpyram, Fipronil, sodium salt of naphthalene formaldehyde condensate and alpha olefin sulphonate, sodium salt of naphthalene sulfonate condensate, ammonium sulphate, lactose monohydrate and poly dimethylsiloxane to form a homogenous mixture,
b. milling the blended mixture through air jet mill to obtain particles of size in the range of below 10µ, and
c. post blending the material obtained in step (b) to obtain powder .

In another embodiment, the present invention provides a process for the preparation of wettable powder composition comprising the steps of:
a. pre-blending all the Nitenpyram, Diafenthiuron, linear alcohol derivative powder, sodium polycarboxylate, hydrated aluminium silicate, ammonium sulfate and precipitated silica to form a homogenous mixture,
b. milling the blended mixture through air jet mill to obtain particles of size in the range of below 10µ, and
c. post blending the material obtained in step (b) to obtain powder .

DETAILED DESCRIPTION OF THE INVENTION
The term "comprising", which is synonymous with "including", "containing", or "characterized by" here is defined as being inclusive or open-ended, and does not exclude additional, unrecited elements or method steps, unless the context clearly requires otherwise.

The present invention provides synergistic composition comprising combination of 1 : 5 to 5 : 1 of first active ingredient to the second active ingredient. However, variables of the ratios of each of the active ingredients can be used and the selection of the particular amount is dependent upon many factors including, for example, type of formulations, the crop, disease sought to be controlled and environmental conditions. The selection of the proper quantity of active agent to be applied, however, is within the expertise of one skilled in the art.

The combination compositions of the present invention can be used on a number of fruits, vegetables and ornamental varieties such as Alfalfa, Apple, Apricot, Artichoke, Avocado, Banana, Barley, Beans, Broccoli, Brussel, Cabbage, Canola, Cauliflower, Citrus, Cocoa, Coffee, maize, Cotton, Cranberry, Cucumber, aubergines (eggplant), Elderbery, Feijoya, Gooseberry, Grapes, Guava, Hop, Leek, Lettuce, Lingonbery, Lychee, Mango, Melon, Mustard, Nectarine, Oats, Okra, Olive, Onion, Ornamentals, Papaya, Passion Fruit, Pear, Pecan, Pepper, Persimmon, Pineapple, Plum, potatoes, Rape Seed, Rice, Rye, Sorghum, Soybean, Sprouts, Squash, Strawberry, Sugarbeet, Sugarcane, Tea, Tobacco, Tomato, Watercress, Watermelon, Wheat, Cereals, Lupins, Millet, Pasture and Sunflower.

The composition of the present invention could be applied to plants, seeds, fruits, soil as preventive and curative state.

The wetting agent aids in the incorporation of the wettable powder into the water phase at the time of dilution and functions at the solid/liquid interface. Wetting agents reduce the surface tension between the solid powder surface and the water surface, with the result that the powder wets and mixes with the water in the spray tank more easily. The wetting agent is a compound that facilitates rapid wetting of the powder when added to the water. The wetting agent employed in the formulation composition is selected from the group consisting of non-ionic surfactants, anionic surfactant, a mixture of anionic and non-ionic surfactant and polymeric surfactant.

The wetting agent may also be used as a dispersing agent.

The wetting agent used herein is selected from and not limited to polycondensation product of naphthalene sulfonic acid, which is alkyl naphthalene sulphonate sodium salt, sodium salt of naphthalene formaldehyde condensate and alpha olefin sulphonate (Propol 990N, Propol SLS, Propol DSN), linear alcohol derivative powder (Geropon L-wet RP), polyalkyl naphthalene sulphonate; Aqarius BP14332 Yellow IH, salts of alkylphenol condensates, salts of sulphonated lignins, salts of poly acid resin copolymers, salts of polyphenol formaldehyde resins, salts of polyarylether sulphates such as tristyrylphenolethoxylate sulphate salts, alkoxylated alkylphenols and alcohols as well as block copolymers of ethyleneoxide and propylene oxide. Preferred wetting agent used in the composition of the present invention is sodium salt of naphthalene formaldehyde condensate and alpha olefin sulphonate (Propol 990N) and linear alcohol derivative powder (Geropon L-wet RP).

The wetting agent is present in the composition in a range of about 1% to 15%, more preferably 1% to 10% of the total weight of the composition.

The dispersing agent is required to maintain the particles in suspension and prevent them from agglomerating once the powder has been diluted in water and is ready for spraying with the aid of the wetting agent.
The compositions of the present invention contain dispersing agents selected from and not limited to sodium lignosulphonates; sodium naphthalene sulphonate formaldehyde condensates; tristyrylphenol ethoxylate phosphate esters; aliphatic alcohol ethoxylates; alky ethoxylates; EO-PO block copolymers; and graft copolymers, polycarboxylates, sodium polycarboxylate (Geropon T-36), alkyl naphthalene sulfonates (such as Morwet IP, Morwet EFW), sodium salt of naphthalene sulfonate condensate (Morwet D-425), phenol sulphonic acid condensates, alkyl sulfonates, alkenyl sylfonates, mixture of alkyl sulfonates and alkenyl sylfonates (Lissapol D), alkyl suflosuccinates (Geropon), L-Wet, methyl oleyltaurates and poly vinyl alcohols. Preferred dispersing agents are polycarboxylates, alkyl naphthalene sulfonates, phenol sulphonic acid condensates, lignosulphonates, methyl oleyltaurates and poly vinyl alcohols, STEPSPERSE DF-600 is a blend of nonionic surfactant and sodium lignosulfonate, BREAK-THRU® DA 646 is a non-ionic dispersant based on a specialty polyether, BREAK-THRU® DA 647, a modified polyether, is a non-ionic dispersant, BREAK-THRU® DA 655 is a polyether phosphate, BREAK-THRU® DA 675 is a non-ionic, aqueous based organically modified polymer, Atlox Metasperse™ 550S Modified styrene acrylic polymer. Dispersing agents disclosed in US 6,677,399; US 6,767,865; EP 1 16 470; US 9,526,241 can be used in the present invention. Once the granule has been diluted in water, ready for spraying (with the aid of the wetting agent), a dispersant is required to maintain the particles in suspension and prevent them from agglomerating. The dispersing agent is a compound which ensures that the particles remain suspended in water. The dispersing agent can be ionic or non-ionic or a mixture of such surface active agents or graft co-polymer dispersant. Preferred dispersing agent used in the composition of the present invention is sodium salt of naphthalene sulfonate condensate (Morwet D-425) and sodium polycarboxylate (Geropon T-36).

The dispersing agent is present in the composition in a range of about 1 to 15%, more preferably 1 to 10% of the total weight of the composition.
The defoamer as used herein is selected from and not limited to absorbed polydimethyl siloxane, stearates; silicones (SILFOAM®, SILFAR®, PULPSIL® and WACKER® AK) and ethoxylates. The defoamer is preferably polydimethyl siloxane (Rhodosil EP-6703, Defomer APW-4253).

The defoamer is present in the composition in a range of about 0.1 to 5%, more preferably 0.1 to 1% of the total weight of the composition.

The inert carriers or fillers as used in the present invention are includes but are not limited to natural minerals such as ammonium sulphate, calcite, talc, china clay series, and montmorillonite or attapulgite clays including various forms of Bentonite, Kaolin; lactose, starches, lactose, calcium carbonate, calcium sulphate, calcium phosphate, sodium tripoly phosphate (STPP), woodflours, activated carbon, sugars, diatomaceous earth, cereal flours, fine-grain inorganic solids, and the like. Clays and inorganic solids which may be used include calcium bentonite, perlite, mica, vermiculite, silicas, quartz powder, montmorillonite and mixtures thereof. Sugars which may be useful include dextrin and maltodextrin. Cereal flours include wheat flour, oat flour and barley flour and a mixture thereof. Preferred inert carriers are ammonium sulphate, hydrated aluminum silicate (china clay) and lactose monohydrous. Highly disperse silica or highly disperse absorptive polymers may also be used to improve physical properties.

The inert carriers are present in the composition in a range of about 30% to 70%, more preferably 30% to 55% of the total weight of the composition.

The compositions of the present invention contain a rheology modifier which is selected from the group consisting of hydrophobic and hydrophilic fumed and precipitated silica particles, gelling clays including bentonite, hectorite, laponite, attapulgite, sepiolite, smectite, hydrophobically/organophilic modified bentonite, hectorite, hydrogentated castor oil (trihydroxystearin) or castor oil organic derivatives.

Preferred rheological modifiers are for example organically modified hectorite clays such as Bentone® 38 and SD3. organically modified bentonite clays, such as Bentone® 34, SD1 and SD2, organically modified sepeolite such as Pangel® B20, hydrophilic silica such as Aerosil® 200, hydrophobic silica such as Aerosil® R972, R974 and R812S, attapulgite such as Attagel® 50, or organic rheological modifiers based on modified castor oil such as Thixcin® R and Thixatrol® ST.

The rheology modifier is present in the composition in a range of about 1 to 10%, more preferably 1 to 5% of the total weight of the composition.

Nitenpyram and Fipronil may be present in the composition or applied in any amounts relative to each other, to provide the enhanced or synergistic effect of the mixture. Nitenpyram and Fipronil may be present in the synergistic insecticidal composition in any suitable amount, and is generally present in an amount of from 10% to 70% by weight of the composition, preferably from 20% to 45% by weight of the composition. However, variables of the ratios of each of the active ingredients can be used and the selection of the particular amount is dependent upon many factors including, for example, type of formulations, the crop, disease sought to be controlled and environmental conditions. The selection of the proper quantity of active agent to be applied, however, is within the expertise of one skilled in the art.

Nitenpyram and Diafenthiuron may be present in the composition or applied in any amounts relative to each other, to provide the enhanced or synergistic effect of the mixture. Nitenpyram and Diafenthiuron may be present in the synergistic pesticidal composition in any suitable amount, and is generally present in an amount of from 10% to 80% by weight of the composition, preferably from 30% to 70% by weight of the composition. However, variables of the ratios of each of the active ingredients can be used and the selection of the particular amount is dependent upon many factors including, for example, type of formulations, the crop, disease sought to be controlled and environmental conditions. The selection of the proper quantity of active agent to be applied, however, is within the expertise of one skilled in the art.

Formulation includes water soluble concentrate (SL), an emulstifiable concentrate (EC), an emulsion (EW), a microemulsion (ME), a suspension concentrates (SC), an oil-based suspension concentrates (OD), a flowable suspension (FS), water soluble powder (WS), water-dispersible granule (WDG), water-soluble granule (SG), a water-dispersible powder (WP), a water soluble powder (SP), a granule (GR), an encapsulated granule (CG), a fine granule (FG), a macrogranule (GG), an aqueous suspoemulsion (SE), capsule suspension (CS) and a microgranule (MG).

Preferably, the synergistic fungicidal composition can be formulated as water soluble powder (WS), water-dispersible or wettable powder (WP) or water-dispersible granule (WDG). Most preferably, the synergistic insecticidal composition can be formulated as wettable powder (WP).

The WP composition according to the invention can comprise from 0.5 to 20 wt% of adjuvants commonly used in this field and well known to those expert in the art, such as antidrift agents, adhesives, penetrants, stickers and spreaders.

The WP compositions of the present invention can be diluted with water or water solutions of agronomic compounds before use to produce a sprayable suspension composition which is used in treating plants or increasing plant growth, Dilution in water usually results in suspensions, emulsions, suspoemulsions or solutions of the agrochemical active ingredient at a concentration of at least 0.001 g/l.

A particular mode of administering the composition of the present invention is the administration to the aboveground parts of plants, in particular to the leaves thereof (leaf-application). The number of applications and the administered doses are chosen in accordance with the biological and climatic conditions of life of the causative agent. The antifungal compositions though, can also be applied to the soil and get into the plants through the root system (systemic activity), in case the locus of the plants is sprayed with a liquid composition or if the components are added to the soil in a solid formulation e.g. in the form of wettable powder (soil application).

When using the active compound combinations according to the invention, the application rate can be varied within a relatively wide range, depending on the kind of application. For the treatment of parts of plants, the active-compound combination application rates are generally between 0.1 and 10000 g/ha, preferably between 100 and 2500 g/ha. For seed dressing, the active compound combination application rates are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 20 g per kilogram of seed. For the treatment of the soil, the active-compound combination application rates are generally between 0.1 and 10000 g/ha preferably between 1 and 5000 g/ha.

The following examples describes the nature of the invention which are given only for the purpose of illustrating the present invention in more detail and are not limitative and relate to solutions, which have been particularly effective on bench scale.

EXAMPLES

Example 1: Composition of Nitenpyram 15% and Fipronil 20% WP
S. No. Ingredients/Raw Materials quantity (% w/w)
1. Nitenpyram technical @97.1% (b)15% 15.46
2. Fipronil technical @93.02% (b) 20% 21.5
3. Sodium salt of naphthalene formaldehyde condensate and alpha olefin sulphonate (Propol 990N) 1.0
4. Sodium salt of naphthalene sulfonate condensate (Morwet D-425) 4.0
5. Ammonium sulphate 5.0
6. Lactose monohydrate 52.04
7. Poly dimethylsiloxane (Defomer APW-4253) 1.0
Total 100

Manufacturing process:

All the raw materials were weighed dispensed and the mixture was mixed in a ribbon blender for 20 minutes. The mixture was passed through air jet milling instrument, with the Inlet pressure - 4kg/cm2 and Grinding pressure - 6kg/ cm2 for milling the sample. After Milling particle size distribution(PSD) should be <10 µ. The milled material was collected and packed.

Example 2: Composition of Nitenpyram 15% + Diafenthiuron 50% WP
S. No. Ingredients/Raw Materials quantity (% w/w)
1. Nitenpyram technical @ 98.2 (b) 15.0% 15.42
2. Diafenthiuron technical @ 96 (b) 50.0 % 52.08
3. Sodium polycarboxylate (Geropon T-36) 3.0
4. Alcohol derivative powder (Geropon L-wet RP). 3.0
5. Precipitated silica 2.0
6. Ammonium sulfate 10.0
7. Hydrated aluminum silicate (China clay) 14.5
Total 100

Manufacturing process

All the raw materials were weighed, dispensed and the mixture was blended in a ribbon blender. The mixture was micronized using airjet mill and the milled material was further blended. The blend was collected and packed.

Field efficacy trials for Nitenpyram + Fipronil combination

Trial: 1 – Cotton
Cotton (Gossypium hirsutum L.) is the most important cash crop in India with an expanse of 9-11 million hector area under cultivation. One among the major constraints in cotton production is higher incidence of insect and pest attack to the crop. Sucking pest complex of cotton includes Aphid, Jassids, Whiteflies, Thrips, Red cotton bug, Mealy bug, and Dusky cotton bug. Amongst which, first four pests are economically most important in many parts of the cotton growing region.

Field efficacy trials were conducted in cotton on sucking pest complex. The sucking pests viz., leafhopper, Amrasca biguttula biguttula (Ishida), aphid, Aphis gossypii (Glover), Whitefly Benicia tabaci (Gennadius) and Thrip, Thrips tabaci (Linnman) cause severe damage and serious threat to many field crops at early stage and can also affect the crop stand and yield. Few sucking pests like whiteflies, thrips are polyphagous and widely distributed in tropical, subtropical, and temperate regions which are vectors for a number of viral diseases in plants.
Table 1: Sucking Pests control in Cotton

Compositions
Dose Gram Active/ha % Insect Control at 10 DAA
Whiteflies adults Wflies Nymphs Thrips Jassids Aphids
Nitenpyram 15% + Fipronil 20% WP (Example 1)
60+80
85.6
88.7
92.8
95.2
90.0
Nitenpyram 25% SP
60 35.0 37.5 32.8 40.5 41.5

Fipronil 5% SC
80 38.9 40.5 45.2 35.5 38.7
Nitenpyram 15% + Fipronil 20% WP 75+100 90.6 92.6 95.9 97.5 93.2

Nitenpyram 25% SP
75 39.8 39.4 34.8 42.6 43.9
Fipronil 5% SC
100 38.7 42.9 48.9 39.7 40.5
SP- Soluble powder, WP Wettable Powder, SC Suspense Concentrate DAA Days after Application

The trial results as seen in Table 1, had shown excellent efficacy of Nitenpyram + Fipronil insecticide against sucking pest complex. The solo application as well as the combination of two active ingredients tested here against Whitefly nymphs and adults, Thrips, Jassids and Aphids. Solo alone were not able to provide satisfactory control of sucking pest complex. The combination of Nitenpyram + Fipronil has shown excellent synergistic activity against cotton sucking pest complex, which also has very good residual activity.

Trial 2: Citrus Pests
Citrus is one of the most important fruits and one of the largest fruit industries in the world, grown in more than 52 countries around the world. In India, 250 species of insects attack Citrus crop, of these insect pests such as scale insects, mealy bugs, whiteflies, psyllids, thrips and aphids are very important pests and infest , affect foliage, twigs, and fruit of citrus deteriorating the tree health and fruit quality and thus impact mature fruiting as well as newly planted groves and resets.

The field trials were conducted to evaluate the efficacy of innovative mixtures of Nitenpyram and Fipronil against sucking pests of Citrus viz., Citrus Psyllids, Diaphorina citri, aphid, Toxoptera sp. Thrips, Thrips nilgiriensis, Citrus leaf minor Phyllocnistic citrella. These are serious threat to citrus orchards after pruning, even it can affect serious crop yield. The field trials were conducted to evaluate the efficacy of innovative mixtures of Nitenpyram and Fipronil.

Table 2: Sucking Pest control in Citrus

Compositions
Dose Gram Active/hectare
% Insect Control at 10 DAA

Citrus psyllids Leaf minor Thrips Aphids
Nitenpyram 15% + Fipronil 20% WP (Example 1) 60+80 83.7 85.6 87.8 92.2
Nitenpyram 25% SP 60 38.6 39.5 37.8 40.5
Fipronil 5% SC 80 41.5 42.5 50.2 48.7
Nitenpyram 15% + Fipronil 20% WP 75+100 88.5 90.5 90.0 95.3
Nitenpyram 25% SP 75 40.5 41.9 39.5 41.6
Fipronil 5% SC 100 43.5 44.2 52.1 51.8
SP- Soluble powder, WP Wettable Powder, SC Suspense Concentrate, SL Soluble Liquid, WG Wettable granule DAA Days after Application

In Table No 2, excellent efficacy has been seen of Nitenpyram + Fipronil combination against Psyllids, Leaf minor Thrips and Aphids. The solo application as well as the combination of two active ingredients tested here against Psyllids, Thrips, Leaf minor and Aphids. Solo alone was not able to provide satisfactory control of sucking pest’s complex, whereas synergistic effect has been seen in combination treatment along with very good residual control.

Field efficacy trials for Nitenpyram + Diafenthiuron combination

Trial 1: Cotton
To reduce losses in sucking pests, field efficacy trials were conducted in cotton on sucking pest complex viz., Leafhopper, Amrasca biguttula biguttula (Ishida), Aphid, Aphis gossypii (Glover), Whitefly, Bemisia tabaci (Gennadius) and Thrip, Thrips tabaci (Linnman) which cause severe damage.

Trials were conducted to evaluate the efficacy of innovative mixtures of Nitenpyram and Diafenthiuron, these trials were conducted with randomized block design with net plot size of 5m x 6m. Cotton crop was raised with all standard agronomic practices. Spraying was done with manual operated backpack sprayer with 500 liter of water spray volume per hectare at 60 days after sowing. The observations were recorded by counting the no. of sucking insects (whitefly adult, nymph, Jassids and thrips) per leaf, six leaves per plant and five plants per plot. The observations were recorded before spraying and 10 DAA (Days After Application).

Table 3: Sucking Pests control in Cotton

Compositions
Dose Gram Active/hectare % Insect Control at 10 DAA
Whiteflies adults Wflies Nymphs Thrips Jassids Aphids
Nitenpyram 15% + Diafenthiuron 50 % WP (Example 2) 60+200 86.5 90.0 79.8 85.0 75.0
Nitenpyram 25% SP 60 33.0 35.0 35.0 55 43.8
Diafenthiuron 50% WP 200 50.1 56.0 45.3 35 37.0
Nitenpyram 15% + Diafenthiuron 50 % WP 75+250 90.5 92.5 83.2 90.8 80.5
Nitenpyram 25% SP 75 38.5 36.0 38.5 71.5 45.0
Diafenthiuron 50% WP 250 53.7 57.8 49.5 42.5 40.8
SP- Soluble powder, WP-Wettable Powder, DAA-Days after Application

Results given in Table No 3, show excellent efficacy of Nitenpyram + Diafenthiuron WP over the Nitenpyram 25% SP, Diafenthiuron 50% WP against sucking pest complex whiteflies, Thrips, Jassids and Aphids.

The solo application as well as the combination of two active ingredients tested here against Whiteflies, Thrips, Jassids and Aphids. Solo application was not able to provide satisfactory control of Whiteflies, Thrips, Jassids and Aphids, whereas synergistic effect has been seen in combination of Nitenpyram + Diafenthiuron WP in controlling sucking pest complex, which has excellent efficacy as well as residual control.

,CLAIMS:WE CLAIM:
1. An insecticidal wettable powder composition comprising combination of Nitenpyram and second insecticide, wetting agent, dispersing agent and other agrochemical auxiliaries, wherein said second insecticide is selected from Fipronil or Diafenthiuron.

2. The insecticidal wettable powder composition as claimed in claim 1, wherein said other agrochemical auxiliaries are selected from fillers/carriers, defoamer and rheology modifiers.

3. The insecticidal wettable powder composition as claimed in claim 1, wherein said composition comprising:
10% to 30 % (w/w) of Nitenpyram,
10% to 60% (w/w) of second insecticide which is selected from Fipronil or Diafenthiuron,
1% to 15% (w/w) of wetting agents,
1% to 15% (w/w) of dispersing agents, and
0.1% to 70% (w/w) of other additives / auxiliaries.

4. The insecticidal wettable powder composition as claimed in claim 3, wherein said composition comprising:
10% to 30 % (w/w) of Nitenpyram,
10% to 60% (w/w) of Fipronil,
1% to 15% (w/w) of sodium salt of naphthalene formaldehyde condensate and alpha olefin sulphonate,
1% to 15% (w/w) of sodium salt of naphthalene sulfonate condensate, and
0.1% to 70% (w/w) of other additives / auxiliaries.

5. The insecticidal wettable powder composition as claimed in claim 3, wherein said composition comprising:
10% to 30 % (w/w) of Nitenpyram,
10% to 60% (w/w) of Diafenthiuron,
1% to 15% (w/w) of linear alcohol derivative powder,
1% to 15% (w/w) of sodium polycarboxylate, and
0.1% to 70% (w/w) of other additives / auxiliaries.

6. The insecticidal wettable powder composition as claimed in claims 2 and 4, wherein said composition comprising:
10% to 30 % (w/w) of Nitenpyram,
10% to 60% (w/w) of Fipronil,
1% to 15% (w/w) of sodium salt of naphthalene formaldehyde condensate and alpha olefin sulphonate,
1% to 15% (w/w) of sodium salt of naphthalene sulfonate condensate,
10% to 60% (w/w) of lactose monohydrate,
1% to 15% (w/w) of ammonium sulfate, and
0.1% to 5% (w/w) of poly dimethylsiloxane.

7. The insecticidal wettable powder composition as claimed in claims 2 and 5, wherein said composition comprising:
10% to 30 % (w/w) of Nitenpyram,
10% to 60% (w/w) of Diafenthiuron,
1% to 15% (w/w) of linear alcohol derivative powder,
1% to 15% (w/w) of sodium polycarboxylate,
10% to 60% (w/w) of hydrated aluminium silicate,
1% to 15% (w/w) of ammonium sulfate, and
1% to 10% (w/w) of precipitated silica.

8. A process for the preparation of insecticidal wettable powder composition as claimed in claim 1, wherein said process comprising the steps of:
a. pre-blending active ingredients, wetting agent, dispersing agent along with other auxiliaries to form a homogenous mixture,
b. milling the blended mixture through air jet mill to obtain particles of size in the range of below 10µ, and
c. post blending the material obtained in step (b) to obtain powder .

Dated this Twenty Seventh (27th) day of July, 2021

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