DESC:
FORM 2
THE PATENTS ACT, 1970
(39 OF 1970)
&
The Patents Rules, 2003
COMPLETE SPECIFICATION
(See section 10; rule 13)

1. TITLE OF THE INVENTION – PESTICIDAL FORMULATION OF FLONICAMID AND FIPRONIL

2. Applicant(s)
a) NAME: MEGHMANI ORGANICS LIMITED
b) NATIONALITY: INDIAN
c) ADDRESS: MEGHMANI HOUSE, BEHIND SAFAL PROFITAIRE, CORPORATE ROAD, PRAHLADNAGAR, AHMEDABAD, GUJARAT, INDIA-380015

3. PREAMBLE TO THE DESCRIPTION

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

PESTICIDAL FORMULATION OF FLONICAMID AND FIPRONIL

FIELD OF THE INVENTION:
The present invention relates to pesticidal formulation of Flonicamid and Fipronil. The present invention particularly relates to suspension concentrate (SC) formulation of Flonicamid and Fipronil with one or more other excipients. Also providing process for preparing pesticidal formulation of Flonicamid and Fipronil.

BACKGROUND OF THE INVENTION:
Flonicamid (IKI220; N-cyanomethyl-4-trifluoromethylnicotinamide), a pyridinecarboxamide compound, is a novel systemic insecticide with selective activity against hemipterous pests, such as aphids and whiteflies, and thysanopterous pests. It disrupts insect chordotonal organs that can affect hearing, balance, movement to cause cessation of feeding, but the specific target site of the chemical is unknown. Flonicamid is very active against aphids, regardless of differences in species, stages and morphs. Flonicamid exhibits excellent performance for control of almost all important aphid species in apples, peaches, wheat, potato vegetables, cotton and ornamentals, etc. Flonicamid has no negative impact on pollinating insects or natural enemies, and thus, ¬Flonicamid provide a new option for integrated pest management programs. Flonicamid also has a good toxicological, environmental and ecotoxicological properties.

Flonicamid was first disclosed in EP0580374B1 and chemically represented as below structure:

Flonicamid is having molecular formula C9H6F3N3O and molecular weight is 229.16 g/mol and having water solubility of 5.2 g/L at 20C. Flonicamid is stable at pH 4 and pH 5. The amide TFNG-AM is formed from this reaction (under alkaline conditions) and can then be hydrolyzed to TFNG (N-(4- trifluoromethylnicotinoyl)glycine)

Good insecticidal activity against other sucking insect pests such as thrips, whiteflies, plant hoppers, leaf hoppers, plant bugs, and mealybugs in fruit trees, cereals, rice, potatoes, cotton, vegetables and ornamentals. Flonicamid soil applications also provide control of the foliar pests

Flonicamid is the only insecticide from IRAC Group 29 class. Flonicamid rapidly inhibits the feeding behavior of aphids, and has better action through ingestion than by contact which is unique compared to existing insecticides.

Flonicamid is useful to provide protection in crops like Fruit trees, Cereals, Potatoes, Cotton, Vegetables, Ornamentals, etc.

Flonicamid is commercially marketed as a soluble or wettable granule containing 50% Flonicamid, which is to be mixed with water before spraying

Fipronil is a broad-spectrum insecticide that belongs to the phenylpyrazole chemical family. Fipronil was first disclosed in EP 295117, chemically known as (±)-5-amino-1-(2,6-dichloro-a,a,a-trifluoro-p-tolyl)- 4-trifluoromethylsulfinylpyrazole-3-carbonitrile and is represented as chemical structure as below;

Fipronil blocks GABA-gated chloride channels in the central nervous system. Disruption of the GABA receptors by Fipronil prevents the uptake of chloride ions resulting in excess neuronal stimulation and death of the target insect. Fipronil is used to control ants, beetles, cockroaches, fleas, ticks, termites, mole crickets, thrips, rootworms, weevils, and other insects. Fipronil is used in granular turf products, seed treatments, topical pet care products, gel baits, liquid termiticides, and in agriculture.

Fipronil kills insects when they eat it or come in contact with it. Fipronil works by disrupting the normal function of the central nervous system in insects. Fipronil is more toxic to insects than people and pets because it is more likely to bind to insect nerve endings.

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. Fipronil containing gel baits and sprays have been used to kill ants, roaches and termites in homes. Various spray and spot on products containing fipronil have been widely utilized to control fleas, ticks and mange mites on pet animals.

In India or anywhere in the world, in agricultural production, using synthetic or chemical agent is the most effectively means of control plant pest. However, the main disadvantage of the such insecticide or pesticide is that on long run, the insects or pets develop the resistance to that insecticide or pesticide and as a result to produce effective result, higher concentration of the insecticide or pesticide is to be used. Here again using higher dose of insecticide or pesticide may result in some detrimental effect to soil as well as environment. Therefore in general practice, usually combination of pesticide with another pesticide or another herbicide or fungicide is used in different concentration as per requirement.

However, when combination of one or more pesticide are used, the main challenge comes is to develop a formulation or composition which is stable, easy to use and effective.

There are few formulations of Flonicamide and fipronil are reported individually as well in combination with other pesticides.

CN102246766A describes an insecticidal composition containing flonicamid and Pymetrozine. The insecticidal composition formed by the binary mixing of the flonicamid and the Pymetrozine which serve as active ingredients, wherein a weight ratio of the two active ingredients is (1-80):(85-1), and preferably is (5-40):(75-10); the total mass percentage content of the active ingredients in the insecticidal composition is between 1 and 90 percent, and preferably is between 8 and 70 percent, and the rest is auxiliary ingredients which are permitted to be used and acceptable in pesticides.

CN103300036A discloses an insecticidal composition containing flonicamid. The insecticidal composition contains an active component A and an active component B, wherein the active component A is selected from flonicamid, and the active component B is selected from any one of the following compounds: pyriproxyfen, methoxyfenozide, metaflumizone and chromafenozide; and the weight ratio of the active component A to the active component B is (1:70)-(70:1).

CN103371164B insecticidal composition containing fluorine lice sulfanilamide. The insecticidal composition comprises an active component A and an active component B, wherein the active component A adopts the fluorine lice sulfanilamide; the active component B is one of flonicamid, cyantraniliprole, chlorantraniliprole, flubendiamide, tolfenpyrad and sulfoxaflor; the weight ratio of the active component A to the active component B is 1:70 to 70:1.

CN103271035A relates to an insecticide composition containing flonicamid and pyriproxyfen. Effective ingredients of the insecticide composition are compounded by flonicamid and pyriproxyfen in a binary manner; a mass ratio of flonicamid and pyriproxyfen is 1-40: 40-1; the total mass of the effective ingredients including flonicamid and pyriproxyfen in the preparation is 1%-80% of the mass of the whole preparation, and the others are auxiliary elements

CN102696608B describes a flonicamid water emulsion and a method for preparing the flonicamid water emulsion. The flonicamid water emulsion comprises the following components in percent by weight: 1-15% of flonicamid, 3-25% of solvent, 4-15% of emulsifying agent, 0.5-2% of dispersing agent, 1-5% of stabilizing agent, 1-5% of anti-freezing agent and the balance of deionized water.

CN103004818A describes an insecticide composition containing fipronil and spirotetramat. The active ingredients are obtained by binary compounding of fipronil and spirotetramat, wherein the mass ratio of the fipronil to the spirotetramat is (14-32): (24-6); the mass fraction of the active ingredient fipronil to the active ingredient spirotetramat in the preparation is 1%-80%, the rest is auxiliary element which is allowed for use or accepted in pesticide.

CN107372547A discloses Pesticidal combination containing butene-fipronil and its application, said composition mainly includes one kind in the butene-fipronil as the first active component and the chlorfenapyr, thiocyclam, fenoxycarb as the second active component, the wherein weight of the first active component and the second active component ratio is 20: 1~1: 20, and the cumulant of the first active component and the second active component is the 5%~80% of the composition total weight. Composition of the present invention can be configured to agriculturally allow suspending agent, water dispersible granules, aqueous emulsion, microemulsion or the miscible oil formulation applied.

However there is no any formulation or composition available where Flonicamid and fipronil are combined in a single formulation which is stable and yet effective.

Inventors of present invention have arrived to a pesticidal formulation of Flonicamid and Fipronil in the form of suspension concentrate which is stable, effective and overcome all the problems mentioned in prior art as described herein.

OBJECT OF THE INVENTION
The main objective of the present invention is to provide a pesticidal formulation of Flonicamid and Fipronil which is stable.

The main objective of the present invention is to provide a pesticidal formulation of Flonicamid and Fipronil which reduces the harmful effects to environment.

The main objective of the present invention is to provide a pesticidal formulation of Flonicamid and Fipronil which is effective against crops pests.

The main objective of the present invention is to provide a pesticidal formulation of Flonicamid and Fipronil which is easy to manufacture.

The main objective of the present invention is to provide a pesticidal formulation of Flonicamid and Fipronil which is to use in the field.

SUMMARY OF THE INVENTION
The main aspect of the invention is to provide a pesticidal formulation of Flonicamid and Fipronil.

Another aspect of the present invention is to provide pesticidal suspension concentrate formulation of Flonicamid and Fipronil with one or more other excipients.

Yet another aspect of the present invention is to provide a process for preparing pesticidal suspension concentrate formulation of Flonicamid and Fipronil with one or more other excipients.

DESCRIPTION OF THE INVENTION
The present invention is all about providing a pesticidal formulation of Flonicamid and Fipronil.

The detailed description set forth below is intended as a description of exemplary embodiments and is not intended to represent the only forms in which the exemplary embodiments may be constructed and/or utilized. The description sets forth the functions and the sequence of steps for constructing and/or operating the exemplary embodiments. However, it is to be understood that the same or equivalent functions and sequences which may be accomplished by different exemplary methods are also intended to be encompassed within the spirit and scope of the invention.

As defined herein, all scientific and technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention belongs.

Although any process and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, the preferred methods and materials are now described.

As stated in the present invention herein, the singular forms “a,” “an” and “the” specifically also encompass the plural forms of the terms to which they refer, unless the content clearly dictates otherwise. The term “about” is used herein to means approximately, in the region of, roughly, or around.

As stated herein, that it follows in a transitional phrase or in the body of a claim, the terms “comprise(s)” and “comprising” are to be interpreted as having an open ended meaning. That is, the terms are to be interpreted synonymously with the phrases “having at least” or “including at least”. When used in the context of a process, the term “comprising” means that the process includes at least the recited steps, but may include additional steps. When used in the context of a composition, the term “comprising” means that the composition includes at least the recited features or components, but may also include additional features or components.

As used herein, the terms "pesticidal effect" and "pesticidal activity" means any direct or indirect action on the target pest that results in reduced feeding damage on the seeds, roots, shoots and foliage of plants grown from treated seeds as compared to plants grown from untreated seeds.

As used herein, the term “dispersing agent” means that a substance which added to a suspension of solid or liquid particles in a liquid to improve the separation of the particles and to prevent their settling or clumping.

As used herein, the term “suspending agent” means that a liquid substance which promotes dispersion or solid particles or which can hold a solid substance in suspension.

As used herein the term “wetting agents” are agents which lower the surface tension of water by a considerable amount, although they may be present only in very low concentration. It is well within the competence of those skilled in the art to determine whether a particular surface active agent (surfactant) is a wetting agent or not.

As used herein the term “anti-freezing agent” means that an additive that, when added to a water-based formulation, will reduce the freezing point of the formulation.
As used herein the term “anti-foaming agent” means that an additive that reduces and hinders the formation of foam in industrial process liquids.

As used herein the term “thickening agent” means that a substance which can increase the viscosity of a liquid without substantially changing its other properties.

As used herein the term “preservative” means that a natural or synthetic chemical that is added to products to prevent decomposition by microbial growth or by undesirable chemical changes.

As used herein the term “biocide” means that a chemical substance or microorganism intended to destroy, deter, render harmless, or exert a controlling effect on any harmful organism.

As used herein the term “surfactant” means that a substance which is when added to a liquid, reduces its surface tension, thereby increasing its spreading and wetting properties.

As per one main embodiment, the present invention provides a pesticidal formulation comprising Flonicamid and Fipronil as active agent with one or more other excipients.

Another main embodiment of the present invention, provides a pesticidal formulation comprising,
a) Flonicamid,
b) Fipronil,
c) One or more dispersing agent,
d) One or more suspending agent,
e) One or more wetting agent,
f) Anti-freezing agent,
g) Anti-foaming agent,
h) Thickening agent,
i) Preservative,
j) Surfactant and
k) Water

As per one embodiment, Flonicamid is present in the range from 1 to 90 % w/w, preferably 1 to 50% w/w, more preferably 1 to 30% w/w, most preferably 1 to 25% w/w.

As per one embodiment, Fipronil is present in the range from 1 to 90 % w/w, preferably 1 to 50% w/w, more preferably 1 to 20% w/w, most preferably 1 to 15% w/w.

As per one embodiment, dispersing agent for the present invention is selected from group consisting of sodium salt of alkylated naphthalene sulfonate, sodium naphthalene sulfonate formaldehyde condensates, modified styrene Acrylic polymer, Tristyrylphenol ethoxylate phosphate esters, nonionics such as alkylarylethylene oxide condensates and EO-PO block copolymers, sodium lignosulfonates; sodium naphthalene sulfonate formaldehyde condensates; tristyrylphenol ethoxylate phosphate esters; aliphatic alcohol ethoxylates; alkyl ethoxylates; EO-PO block copolymers; and graft copolymers or combination thereof.

As per preferred embodiment, the present invention contains one or more dispersing agents, preferably combination of two dispersing agents. As per another preferred embodiment, the present invention comprises combination of modified styrene Acrylic polymer and Alkylated naphthalene sulfonate, sodium salt as dispersing agent.

As per one embodiment, the dispersing agents are present in the range from 1-15% w/w preferably 1 to 12% w/w, more preferably 1 to 10% w/w, most preferably 1 to 5% w/w.

As per one embodiment, suspending agent for the present invention is selected from group consisting of polyalkoxylated butyl ether, carboxymethyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxymethyl cellulose, succinoglycan, polycarboxylate polymer thickener, preferably (preferably slightly) crosslinked polyacrylate, Magnesium aluminium silicate, carrageenan, Silicon Dioxide, colloidal silicon dioxide or combination thereof.

As per preferred embodiment, the present invention contains one or more suspending agents, preferably combination of two suspending agents. As per another preferred embodiment, the present invention comprises combination of Polyalkoxylated butyl ether and Silicon Dioxide.

As per one embodiment, the suspending agents are present in the range from 0.01-5% w/w preferably 0.01 to 4% w/w, more preferably 0.01 to 2% w/w, most preferably 0.5 to 2% w/w.

As per one embodiment, wetting agent for the present invention is selected from group consisting of polyaryl alkoxylated phosphate esters and their potassium salts sodium dioctyl sulfosuccinates, and ethoxylated fatty alcohols, aliphatic alcohol ethoxylates, Trisiloxane ethoxylate, polyoxyethylene sorbitan fatty acid esters, such as polyoxyethylene sorbitan monooleate also known as polysorbate 80, polyoxyethylene-polyoxypropylene copolymers which are poloxamers such as poloxamer 124, 188, 237, 388 and 407, sodium lauryl sulfate Dodecyl benzene sulphonate; or combination thereof.

As per preferred embodiment, the present invention contains one or more wetting agents, preferably combination of two wetting agents. As per another preferred embodiment, the present invention comprises combination of Ethoxylated Fatty Alcohol and Trisiloxane ethoxylate.

As per one embodiment, the suspending agents are present in the range from 1-15% w/w preferably 1 to 12% w/w, more preferably 1 to 10% w/w, most preferably 1 to 5% w/w.

As per one embodiment, anti-freezing agent for the present invention is selected from group consisting of Glycerin, urea, diethylene glycol, polypropylene glycol, polyethylene glycol, polypropylene glycol and monoethylene glycol. As per preferred embodiment, Polypropylene glycol is used as anti-freezing agent.

As per one embodiment, the anti-freezing agent is present in the range from 1-20% w/w preferably 1 to 12% w/w, more preferably 1 to 10% w/w, most preferably 1 to 6% w/w.

As per one embodiment, anti-foaming agent for the present invention is selected from certain alcohols (cetostearyl alcohol), insoluble oils (castor oil), stearates, polydimethylsiloxane and other silicones derivatives. As per preferred embodiment, polydimethylsiloxane is used as anti-foaming agent.

As per one embodiment, the anti-foaming agent is present in the range from 0.01-5% w/w preferably 0.01 to 4% w/w, more preferably 0.01 to 2% w/w, most preferably 0.01 to 1% w/w.

As per one embodiment, thickening agent for the present invention is selected from polysaccharides, agar, corn starch, pre-gelatinized starch, sodium alginate, gum tragacanth, guar gum. As per preferred embodiment, polysaccharides is used as thickening agent.

As per one embodiment, the thickening agent is present in the range from 0.01-5% w/w preferably 0.01 to 4% w/w, more preferably 0.01 to 2% w/w, most preferably 0.01 to 1% w/w.

As per one embodiment, preservative for the present invention is selected from l, 2-benzisothiazol-3-one, 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. As per preferred embodiment, 1, 2-benzisothiazol-3-one is used as preservative. The 1, 2 benzisothiazol-3-one is also act as biocide in the formulation.

As per one embodiment, the preservative is present in the range from 0.01-2% w/w preferably 0.01 to 2% w/w, more preferably 0.01 to 1% w/w, most preferably 0.05 to 0.5% w/w.

As per one embodiment, surfactant for the present invention is selected from vegetable oil, 4-(5-dodecyl)benzenesulfonate, docusate (dioctyl sodium sulfosuccinate), alkyl ether phosphates, benzalkaonium chloride (BAC), and perfluorooctanesulfonate (PFOS). As per preferred embodiment, vegetable oil is used as surfactant.

As per one embodiment, the surfactant is present in the range from 1-20% w/w preferably 1 to 15% w/w, more preferably 1 to 12% w/w, most preferably 1 to 10% w/w.

As per another main embodiment, the process of preparation of the pesticidal formulation of Flonicamid and Fipronil comprises steps of:
a) Preparing a Gum solution by adding preservative to De-Mineralized water;
b) Stirring step (a) solution for 10 min and then adding thickening agent;
c) Stirring step (b) solution for about 5 hours and heating the vessel at 45-60?;
d) Allowing step (c) solution to stand for 5 hours before using;
e) Charging De-Mineralized water in another vessel and agitating;
f) Adding and mixing dispersing agent, suspending agent, wetting agent, anti-freezing agent, antifoaming agent, into the step (e) solution for half an hour;
g) Adding Flonicamid to step (f) and mixing;
h) Adding Fipronil to step (g) and mixing;
i) Homogenizing step (h) solution under high shear homogenization for 2 hours;
j) Milling / Grinding the material of step (h) through bead milling and achieving required particle size;
k) Collecting the milled material of step (j) in a post mixing vessel;
l) Adding gum solution of step (d) and surfactant into the milled material of step (k) and stirring till it gets completely homogenized solution;
m) Storing the final solution of step (l) into the suitable container.

As per one embodiment of the present invention, the pesticidal formulation of Flonicamid and Fipronil is preferably in the form of suspension.

EXAMPLE
The following examples are illustrated to describe the scope of the invention.

EXAMPLE 1

Sr. No. Chemical Composition Percent (% w/w)
1 Flonicamid 20.60
2 Fipronil 8.45
3 modified styrene Acrylic polymer 3.00
4 Ethoxylated Fatty Alcohol 2.00
5 Polyalkoxylted butyl ether 0.50
6 Alkylated naphthalene sulfonate,sodium salt 0.50
7 Trisiloxane ethoxylate 2.00
8 Polydimethylsiloxane 0.50
9 Silicon Dioxide 0.50
10 Polysaccharides 0.20
11 1,2-benzisothiazol-3-one 0.25
12 Vegetable Oil 8.00
13 Polypropylene glycol 5.00
14 DM Water 48.50
Total 100.00

Table 1: Formulation of a pesticidal formulation of Flonicamid and Fipronil

Procedure:
The process of preparing the a pesticidal formulation of Flonicamid and Fipronil comprising the steps;
a) A gum solution was prepared by adding 1,2-benzisothiazol-3-one to De-Mineralized water;
b) The step (a) solution was stirred for 10 min and then polysaccharides was added;
c) The step (b) solution was stirred for about 5 hours and the jacketed vessel was heated at 45-60?;
d) The step (c) solution was allowed to stand for 5 hours before using;
e) De-Mineralized water was charged in a another vessel and agitated;
f) Then modified styrene Acrylic polymer, Alkylated naphthalene sulfonate, sodium salt, Polyalkoxylated butyl ether, Silicon Dioxide, Ethoxylated Fatty Alcohol, Trisiloxane ethoxylate, Polypropylene glycol, Polydimethylsiloxane was added into the step (e) solution and mixed for half an hour;
g) Flonicamid was added to step (f) and mixed;
h) Fipronil was added to step (g) and mixed;
i) The step (h) solution was homogenized under high shear homogenization for 2 hours;
j) The material of step (i) was Milled / Grinded through bead milling and required particle size was achieved;
k) The milled material of step (j) was collected in a post mixing vessel;
l) The gum solution of step (d) and vegetable oil were added into the milled material of step (k) and stirred till got completely homogenized solution;
m) The final solution of step (l) was stored into the suitable container.

EXAMPLE 2: STABILITY STUDY OF EXAMPLE 1
2.1: Heat stability for 14 days at 54±2? & cold stability 7 days at 0±2?

Parameters Specification (in house) Initial heat stability at 54±2 cold stability at 0±2 degrees centigrade
Flonicamid content percent by mass 19.00 to
21.00 20.25 20.28 20.12
Fipronil content percent by mass 7.60 to
8.80 8.21 8.18 8.20
Flonicamid suspensibility percent mini. 80 98.45 98.43 98.51
Fipronil suspensibility percent mini. 80 99.10 98.90 99.05
pH range (1% aq Suspension) 5.50 to 7.50 7.10 7.05 7.11
Pourability 95% min. 98.50 98.10 97.97
Specific gravity 1.08- 1.18 1.14 1.148 1.141
Viscosity at spindle no. 62,20 rpm 350-800 cps 630 632 630
Particle size (micron) D50<3,D90<10 2.2,5.9 2.3,6.1 2.4,6.5
Persistent foam ml (after 1 minute) max. 60 5 6 5
Table 2: Observations for Heat stability study for 14 days at 54±2? & cold stability study 7 days at 0±2?

2.2: Room Temperature storage stability up to 12 months
Parameters Specification (in house) 1 month 6 month 12 month
Flonicamid content percent by mass 19.00 to 21.00 20.21 20.17 20.19
Fipronil content percent by mass 7.60 to 8.80 8.2 8.22 8.21
Flonicamid suspensibility percent mini. 80 98.12 98.38 98.43
Fipronil suspensibility percent mini. 80 98.92 99.00 98.95
pH range (1% aq Suspension) 5.50 to 7.50 7.05 7.04 7.02
Pourability 95% min. 98.76 98.52 98.25
Specific gravity 1.08- 1.18 1.142 1.138 1.139
Viscosity at spindle no. 62,20 rpm 350-800 cps 627 638 640
Particle size (micron) D50<3,D90<10 2.1, 5.6 2.2,5.9 2.3,6.0
Persistent foam ml (after 1 minute) max. 60 6 5 6
Table 3: Observations for Room Temperature storage stability study up to 12 months

EXAMPLE 3: BIO EFFICACY FIELD TRIAL
Name of Experiment : Bio-efficacy of new formulation of Flonicamid combination with Fipronil against thrips on Cotton crop.
Location : Ahmedabad, Gujarat.
Time of sowing : 4th week of June 2020.
Spray volume &equipment : High volume knap-sack sprayer fitted with Hollow cone nozzle.
Plot size : 500 Sqm
Spacing : 0.9 m × 0.6 m
Treatments : 5 Treatments
Replications : 4 Replications
Crop hybrid : Rasi 659 (Bt cotton)
Soil Type : Black Soil
Spray Schedule : 2 spray at 15 days interval
Spray Volume : 500L/ha.
Irrigated/Rain fed : Irrigated
Season/Year : Kharif 2020
Harvesting Time : 3rd week of November 2020

Treatment No Treatment details Active ingredient
(g.a.i/ha) Formulation: (g/ml/ha) Target pests
T1 Flonicamid 50.00% WG (Market standard, Ulala) 75 150 Thrips
T2 Flonicamid 20% SC+ Fipronil 8% SC (Example 1) 60+24 300
T3 Flonicamid 20% SC+ Fipronil 8% SC (Example 1) 75+30 375
T4 Flonicamid 20% SC+ Fipronil 8% SC (Example 1) 90+36 450
T5 Flonicamid50% WG + Fipronil 5 % SC (Farmers practice) 75+37.5 150+700
Table 4: Observations for bio-efficacy study

OBSERVATIONS PARAMETERS:
1) POPULATION DENSITY OF THRIPS:
Two sprays were given at 10 days interval. The observations on number of thrips were made on 10 randomly selected plants in each treatment on just before spray and 3rd, 7th, and 10 days after spray. Based on these observations, mean insect population 3, 7 and 10 days after spray (DAS) was worked out. The bio-efficacy of applied product and market standards at each spray was recorded and analyzed as efficacy against thrips. The per cent reduction in thrips population over farmer’s practice was worked out for each treatment.

2) COTTON YIELD:
A total of two pickings were made and data on seed cotton yield was summed up for each treatment. The per cent increase in yield was worked out treatment-wise by using the formula:
% Increase in Yield= (yield in treatment) - (yield in farmers practice treatment) X 100
(yield in farmer’s practice treatment

3) PHYTOTOXICITY:
The phyto-toxicity observations were made in all the treatment plots including test chemical and standard market products at 3 doses. Observation was made from all plants from each plot and the total number of leaves of those showing phyto-toxicity, if any, were counted on 3,7 and 10th days after spray and were recorded on wilting, necrosis, vein clearing, Epinasty and hyponasty etc. When there was no phyto-toxicity effect on plant, it was recorded as absolute zero.

RESULTS:
1) POPULATION DENSITY OF THRIPS:
Table 1: Efficacy on THRIPS g.a.i./ha Formulation
ml/g/ha *BSO 3 DAS 7 DAS 10 DAS % Control
T1 Flonicamid50.00% WG (Market Standard) 75 150 5.82 4.47 2.16 2.29 12.71
T2 Flonicamid 20% + Fipronil 8% SC (Example 1) 60+24 300 6.02 3.62 2.22 2.20 16.10
T3 Flonicamid 20% + Fipronil 8% SC (Example 1) 75+30 375 6.33 2.96 1.24 1.16 55.93
T4 Flonicamid 20% + Fipronil 8% SC (Example 1) 90+36 450 6.09 2.84 2.69 2.44 56.27
T5 Flonicamid50% + Fipronil5% SC (Farmer Practice) 75+37.5 150+750 6.51 5.91 2.80 2.62
Table 5: Observation for population density of thrips
* Before Spray Observation (BSO)
* Days After Spray (DAS)

Result:
Treatment T3 - Flonicamid 20% + Fipronil 8% SC from Example at the rate of (75+30) g.a.i./ha has given the highest control of Thrips population (55.93%) as compared to tank mix of Flonicamid 50% + Fipronil 5 % SC (75+37.5) g.a.i./ha used by the Scientist in line with farmer’s practice.

Due to synergistic effect of T3 (Flonicamid 20% + Fipronil 8% SC) at the rate of 75+30 g.a.i./ha has given thrips control almost at par with T4 (Flonicamid 20% + Fipronil 8% SC) at the rate of 90+36g.a.i./ha. In spite of using a higher dose of both the constituents in T4 the degree of control remains at par with T3.

2) COTTON YIELD:
Treatment Formulation g.a.i./ ha Formulation Dose Seed cotton yield (q/ha) Increase in yield over Farmers Practice (%)
(g/ml/ ha)
T1 Flonicamid 50.00% WG (Market standard, Ulala) 75 150 18 -3
T2 Flonicamid 20% + Fipronil 8% SC (Example 1) 60+24 300 17 -8
T3 Flonicamid 20% + Fipronil 8% SC (Example 1 75+30 375 21 14
T4 Flonicamid 20% + Fipronil 8% SC (Example 1) 90+36 450 21 14
T5 Flonicamid50% + Fipronil 5 % SC (Tank mix-Farmers’ practice) 75+37.5 150+750 18.5
Table 6: Observations for seed cotton yield
Result:
Treatment T3 - Flonicamid 20% + Fipronil8% SC from Example 1 at the rate of 75+30g.a.i./ha has given the higher seed cotton yield increase (14%) as compared to tank mix of Flonicamid50 % + Fipronil 5 % SC (75+37.5) g.a.i./ha used by the Scientist in line with farmers’ practice

Due to synergistic effect of T3 (Flonicamid 20% + Fipronil 8% SC) at the rate of 75+30g.a.i./ha has given seed cotton yield at par with T4 (Flonicamid 20% + Fipronil 8% SC) at the rate of 90+36g.a.i./ha. In spite of using a higher dose of both the constituents in T4 the yield remains at par with T3.

3) PHYTOTOXICITY:
No Phyto-toxicity symptoms of whatever form were observed in the highest dose of the formulation of Example 1 in all the Experiment.

,CLAIMS:CLAIMS
We claim;
1) A pesticidal formulation of Flonicamid and Fipronil comprising:
a) 1-90% w/w of Flonicamid,
b) 1-90% w/w of Fipronil,
c) 1-15% w/w of one or more dispersing agent,
d) 0.01-5% of one or more suspending agent,
e) 1-15% w/w of one or more wetting agent,
f) 1-20% w/w of anti-freezing agent,
g) 0.01-5% w/w of anti-foaming agent,
h) 0.01-5% w/w of thickening agent,
i) 0.01-2% of preservative,
j) 1-20% w/w of surfactant and
k) Water.

2) The pesticidal formulation of Flonicamid and Fipronil as claimed in claim 1, wherein said dispersing agent is selected from sodium salt of alkylated naphthalene sulfonate, sodium naphthalene sulfonate formaldehyde condensates, modified styrene Acrylic polymer, Tristyrylphenol ethoxylate phosphate esters, non-ionics such as alkylarylethylene oxide condensates and EO-PO block copolymers, sodium lignosulfonates; sodium naphthalene sulfonate, formaldehyde condensates; tristyrylphenol ethoxylate phosphate esters; aliphatic alcohol ethoxylates; alkyl ethoxylates; EO-PO block copolymers; and graft copolymers or any combination thereof.

3) The pesticidal formulation of Flonicamid and Fipronil as claimed in claim 1, wherein said suspending agent is selected from group consisting of polyalkoxylated butyl ether, carboxymethyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxymethyl cellulose, succinoglycan, polycarboxylate polymer thickener, preferably (preferably slightly) crosslinked polyacrylate, Magnesium aluminium silicate, carrageenan, Silicon Dioxide, colloidal silicon dioxide or combination thereof.

4) The pesticidal formulation of Flonicamid and Fipronil as claimed in claim 1, wherein said wetting agent is selected from group consisting of polyaryl alkoxylated phosphate esters and their potassium salts sodium dioctyl sulfosuccinates, and ethoxylated fatty alcohols, aliphatic alcohol ethoxylates, Trisiloxane ethoxylate, polyoxyethylene sorbitan fatty acid esters, such as polyoxyethylene sorbitan monooleate also known as polysorbate 80, polyoxyethylene-polyoxypropylene copolymers which are poloxamers such as poloxamer 124, 188, 237, 388 and 407, sodium lauryl sulfate, Dodecyl benzene sulphonate; or combination thereof.

5) The pesticidal formulation of Flonicamid and Fipronil as claimed in claim 1, wherein said anti-freezing agent is selected from group consisting of Glycerin, urea diethylene glycol, polypropylene glycol, polyethylene glycol and monoethylene glycol.

6) The pesticidal formulation of Flonicamid and Fipronil as claimed in claim 1, wherein said anti-foaming agent is selected from certain alcohols (cetostearyl alcohol), insoluble oils (castor oil), stearates, polydimethylsiloxane and other silicones derivatives.

7) The pesticidal formulation of Flonicamid and Fipronil as claimed in claim 1, wherein said thickening agent is selected from polysaccharides, agar, corn starch, pre-gelatinized starch, sodium alginate, gum tragacanth, guar gum.

8) The pesticidal formulation of Flonicamid and Fipronil as claimed in claim 1, wherein said preservative is selected from l, 2-benzisothiazol-3-one, 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.
9) The pesticidal formulation of Flonicamid and Fipronil as claimed in claim 1, wherein said surfactant is selected from vegetable oil, 4-(5-dodecyl)benzenesulfonate, docusate (dioctyl sodium sulfosuccinate), alkyl ether phosphates, benzalkaonium chloride (BAC), and perfluorooctanesulfonate (PFOS).

10) A pesticidal formulation of Flonicamid and Fipronil comprising:
a) 1-90% w/w of Flonicamid,
b) 1--90% w/w of Fipronil,
c) 1-15% w/w of combination of modified styrene Acrylic polymer and Alkylated naphthalene sulfonate, sodium salt,
d) 0.01-5% of combination of Polyalkoxylated butyl ether and silicon dioxide,
e) 1-15% w/w of combination of Ethoxylated Fatty Alcohol and Trisiloxane ethoxylate,
f) 1-20% w/w of Polypropylene glycol,
g) 0.01-5% w/w of Polydimethylsiloxane,
h) 0.01-5% w/w of Polysaccharide,
i) 0.01-2% of 1,2-benzisothiazol-3-one,
j) 1-20% w/w of vegetable oil and
k) Water.

11) A process of preparation of the pesticidal formulation of Flonicamid and Fipronil as claimed in claim 1 comprises steps of:
a) Preparing a Gum solution by adding 1, 2-benzisothiazol-3-one to De-Mineralized water;
b) Stirring step (a) solution for 10 min and then adding polysaccharides;
c) Stirring step (b) solution for about 5 hours and heating the jacketed vessel at 45-60?;
d) Allowing step (c) solution to stand for 5 hours before using;
e) Charging De-Mineralized water in another vessel and agitating;
f) Adding and mixing modified styrene Acrylic polymer, Alkylated naphthalene sulfonate, sodium salt, Polyalkoxylated butyl ether, Silicon Dioxide, Ethoxylated Fatty Alcohol, Trisiloxane ethoxylate, Polypropylene glycol, Polydimethylsiloxane into the step (e) solution for half an hour;
g) Adding Flonicamid to step (f) and mixing;
h) Adding Fipronil to step (g) and mixing;
i) Homogenizing step (h) solution under high shear homogenization for 2 hours;
j) Milling / Grinding the material of step (i) through bead milling and achieving required particle size;
k) Collecting the milled material of step (j) in a post mixing vessel;
l) Adding gum solution of step (d) and vegetable oil into the milled material of step (k) and stirring till it gets completely homogenized solution;
m) Storing the final solution of step (l) into the suitable container.