DESC:FIELD OF INVENTION
The present disclosure relates to synergistic insecticidal compositions comprising bioactive amounts of (A) an insecticide Chlorantraniliprole; (B) an insecticide Thiamethoxam; (C) an insecticide Fipronil. The present invention further relates to process of preparing said composition along with at least one inactive excipients and formulation thereof.

BACKGROUND OF THE INVENTION
Pests including insects can have adverse and damaging impacts on agricultural production by affecting crops and food production. In addition, pests can have detrimental effect on environment and human health. Insecticide or pesticides are used widely and very frequently in commercial agriculture and have enabled an enormous increase in crop yield and product quality which is ultimately advantageous to the farmers economically. In order to control pests of plant, various pesticides or combination of pesticides are being used by farmers. Combination of insecticides are used to broaden the spectrum of control of insect, to improve the pest control with synergistic effect, reduce dosage, thereby reducing environmental impact, to broaden the spectrum of control, i.e. chewing and sucking insects including leafhoppers and planthoppers at a time, decrease chances of development and management of resistance and to enhance residual control so lesser the number of sprays for crop protections and minimizing the pesticidal load in ecosystem.
Insecticidal compositions that can be applied at as low a dose as possible and be effective in controlling pest species of insects especially rice stem borer (Chilo suppressalis). Insects are very destructive to crops and can result in significant loss of crop yield and quality, which results in economic loss to the grower and increased cost to the consumer. Combinations of insecticides are typically used to broaden the spectrum of insect control, to minimize the doses of chemicals used, to retard resistance development and to reduce the cost of treatment through additive effect. Although, many combinations of insecticidal agents have been studied, a synergistic effect is rarely attained. Therefore, there is still a need for novel insecticidal composition that exhibits synergistically enhanced action, a broader scope of activity and reduced cost of treatment.

DESCRIPTION OF THE INVENTION
The exemplary mode for carrying out the disclosure is presented in terms of its exemplary embodiments. However, the exemplary embodiments described herein detail for illustrative purposes and are subject to many variations. It is understood that various omissions and substitutions of equivalents are contemplated as circumstances may suggest or render expedient, but are intended to cover the application or implementation without departing from the spirit or scope of the present disclosure.
Unless otherwise specified, all terms used in disclosing the invention, including technical and scientific terms, have the meaning as commonly understood by one of the ordinary skill in the art to which the invention belongs. For further guidance, term definitions may be included to better appreciate the
The terms “a” and “an” herein do not denote a limitation of quantity, but rather denote the presence of at least one of the referenced item.
It should be emphasized that the term “comprises/comprising” when used in this specification is taken to specify the presence of stated features, steps or components but does not preclude the presence or addition of one or more other features, steps, components or groups thereof.
The term "insects" as used herein, includes all organisms in the class "Insects."
The term "Insecticidal" as used herein, refers to the ability of a pesticide 25 to increase mortality or inhibit growth rate of insects.
The term “active ingredient” (a.i.) or “active agent” used herein refers to that component of the composition responsible for control and killing of pests/insects.
The term “formulation” and “composition” as used herein conveys the same meaning and can be used interchangeably. The term "health of a plant" or "plant health" is defined as a condition of the plant and/or its products. As a result of the improved health; yield, plant vigour, quality and tolerance to abiotic or biotic stress is increased.
The terms “weight percent”, “wt-%”, “percent by weight”, “% by weight” and variations thereof, as used herein, refer to the concentration of a substance as the weight of that substance divided by the total weight of the composition .and multiplied by 100. It is understood that, as used here, “percent “, “%” and the like are intended to be synonymous with “weight percent”, “wt. %”, etc.
The term "synergistic", as used herein, refers to the combined action of two or more active agents blended together and administered conjointly that is greater than the sum of their individual effects.
"Bioactive amounts” as mentioned herein means that amount which, when applied for treatment of crops, is sufficient to give effect in such treatment.
Features that are described and/or illustrated with respect to one embodiment may be used in the same way or in a similar way in one or more other embodiments and/or in combination with or instead of the features of the other embodiments.
In accordance with an embodiment of the invention, there is provided a synergistic insecticidal composition comprising (A) an insecticide Chlorantraniliprole; (B) an insecticide Thiamethoxam; and (C) an insecticide Fipronil; and one or more customary formulation adjutants.
Chlorantraniliprole
Chlorantraniliprole is broad-spectrum anthranilic diamide insecticide interrupts the normal muscle contraction of insects, resulting in death. It adheres to plant surfaces and is most effective when consumed by pests. Therefore, it should only be applied when pest insects are present at damaging levels and are actively consuming plant parts.
It has an IUPAC name as 3-Bromo-4'-chloro-1-(3-chloro-2-pyridyl)-2'-methyl-6'-(methylcarbamoyl)pyrazole-5-carboxanilide having chemical structure as:

Thiamethoxam
Thiamethoxam is the first commercial neonicotinoid insecticide from the thianicotinyl subclass. It was discovered in the course of our optimisation program on neonicotinoids started in 1985.it acts by binding to nicotinic acetylcholine receptors. It exhibits exceptional systemic characteristics and provides excellent control of a broad range of commercially important pests, such as aphids, jassids, whiteflies, thrips, rice hoppers, Colorado potato beetle, flea beetles and wireworms, as well as some lepidopteran species. In addition, a strong preventative effect on some virus transmissions has been demonstrated. Thiamethoxam is developed both for foliar/soil applications and as a seed treatment for use in most agricultural crops all over the world.
It has an IUPAC name as 3-[(2-Chloro-1,3-thiazol-5-yl)methyl]-5-methyl-N-nitro-1,3,5-oxadiazinan-4-imine and having the chemical structure as:

Fipronil
Fipronil is a broad use insecticide that belongs to the phenylpyrazole chemical family. Fipronil is used to control ants, beetles, cockroaches, fleas, ticks, termites, mole crickets, thrips, rootworms, weevils, and other insects. Fipronil is a white powder with a moldy odor. Fipronil was first registered for use in the United States in 1996.
It has an IUPAC name as 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-(trifluoromethylsulfinyl)pyrazole-3-carbonitrile and having chemical structure as :

The present disclosure provides a novel synergistic insecticidal combination, which are chemically compatible, affordable and which can control the insects pest in the Rice, chilli, sugarcane, cotton, wheat, cabbage to improve the growth and grain yield without resulting in any environmental hazard and phytotoxicity
In an embodiment of the present disclosure is to provide a novel and synergistic insecticidal composition for controlling Rice Yellow stem borer, leaf folder, Thrips, Diamond black moth, early shoot borer, fruit borer and a composition comprising the same and its utility in improving the yield of food crop.

In an embodiment the formulation of the present disclosure can be in any of the formulations selected from Capsule suspension (CS), Dispersible concentrate (DC), Powder for dry seed treatment (DS), Emulsifiable concentrate (EC), Emulsion, water in oil (EO), Emulsion for foliar spray (ES), Emulsion, oil in water (EW), Flowable suspension/concentrate for foliar spray (FS), Granule/ soil applied (GR), Controlled (Slow or Fast) release granules (CR), Jambo balls or bags (bags in water soluble pouch), Solution for foliar spray (LS), Micro-emulsion (ME), Oil dispersion (OD), Oil miscible flowable concentrate (oil miscible suspension (OF), Oil miscible liquid (OL), Suspension concentrate (SC), Suspo-emulsion (SE), Water soluble granule (SG), Soluble concentrate (SL), Water soluble powder (SP), Water dispersible granule (WG or WDG), Wettable powder (WP).

The composition of the present invention in addition to bioactive amounts of active ingredients further comprises inactive excipients including but not limited to dispersant, anti-freezing agent, anti-foam agent, wetting agent, suspension aid, antimicrobial agent, thickener, quick coating agent or sticking agents (also referred to as “stickers” or “binders”) and buffering agent.

In an embodiment of the present disclosure there is provided a method for preparing active ingredients Insecticidal composition comprising Chlorantraniliprole, Thiamethoxam and Fipronil and its salts.
In an embodiments of the present disclosure provide insecticidal combination and composition comprising said combination that possess an enhanced efficacy over the individual active ingredient compounds, when used in isolation.

The present invention thus provides an insecticidal composition comprising a) Chlorantraniliprole as the first active ingredient b) Thiamethoxam as the second active ingredient and c) Fipronil, as a synergist wherein Chlorantraniliprole is present in an amount ranging from 0.1-20% w/w, Thiamethoxam is present in an amount ranging from 0.1-20% w/w and Fipronil is present in an amount ranging from 0.1 to 35% w/w the insecticidal composition.

In a preferred embodiment, Chlorantraniliprole is present in an amount 0.6%w/w, Thiamethoxam is present in an amount of 1.25%w/w and Fipronil is present in an amount of 1.25% w/w of the insecticidal composition.

In an embodiment, the insecticidal composition of the present invention comprising the said actives exhibits synergistic effect in control of insects in agricultural crops, in Rice.

In an embodiment, the insecticidal composition of the present invention may be applied to a variety of agricultural crops like brinjal, cole crops, cucurbits, cotton, tea, ornamentals, horticultural crops and oil seed crops.

In an embodiment, the insecticidal composition of the present invention further comprises at least one agriculturally acceptable excipient.

In an embodiment, the at least one excipient is selected from the group consisting of at least a dispersing agent, at least a wetting agent, at least a defoamer, at least a biocide, at least a binder, at least a thickener and combinations thereof.

In a preferred embodiment, the insecticidal composition of the present invention is formulated as a granular.

In a more preferred embodiment, the insecticidal composition of the present invention is formulated in the form of a granular comprising a wetting agent, a dispersing agent, a defoaming agent, a biocide, an anti-freeze agent and a thickener.

In an embodiment, the at least a dispersing agent is selected from the group comprising sodium lignosulphonates, sodium naphthalene sulphonate- formaldehyde condensates, aliphatic alcohol ethoxylates, tristyrylphenol ethoxylates and esters, ethylene oxide/propylene oxide block copolymers. In a preferred embodiment, the at least a dispersing agent is sodium lignosulphonate. The at least a dispersing agent weight concentration in said Insecticidal composition is in the range of 0.1-30%w/w

In an embodiment, the at least a wetting agent is selected from the group consisting of blend of alkyl naphthalene sulfonate, sodium salt, castor oil ethoxylate, sodium laurel sulphate, and combinations thereof. In a preferred embodiment, the at least a wetting agent is sodium lignosulphonate and castor oil ethoxylate. The at least a wetting agent weight concentration in said Insecticidal composition is in the range of 0.1-30% w/w.

In an embodiment, the at least an anti-freezing agent is selected from the group comprising monoethylene glycol, diethylene glycol, polypropylene glycol, ethylene alcohols, polyethylene glycols, glycerine, glycerol epichlorohydrin, urea, glycerol, sorbitol or a mixture thereof. In a preferred embodiment the antifreeze agent is glycerol. In an embodiment, the anti-freeze agent is present in an amount ranging from 0.1-15%%w/w.

In an embodiment, the fillers, when present, may be selected from insoluble fillers
and soluble fillers.

By way of example, the fillers may be selected from precipitated silica and
diatomaceous earth kaolin, dibasic ammonium phosphate. . In an embodiment, the anti-freeze agent is present in an amount ranging from 0.1-15%%w/w.

In an embodiment, the binders, when present, may be selected from polyvinylpyrrolidone, lactose, sucrose and the like.

Examples 1
The examples below are given solely for the purpose of illustration and are not to be construed as limitations of the present invention, as many variations thereof are possible without departing from the spirit and scope of the invention.
Example 1: Preparation of Insecticidal composition as Granule(GR)
In an embodiment, the chemical composition of the present insecticidal composition GR is depicted below in Table 1 (a) below:

Table 1 : Composition of the Insecticidal composition
S.no Name of Ingredients Composition % w/w
1. Chlorantraniliprole Active ingredient (based on 95 % w/w ) 0.60 (±3%)

2. Fipronil Active Ingredient (based on 95 % w/w a.i.) 1.25 (±3%)
3. Thiamethoxam Active Ingredient (based on 97 % w/w a.i.) 1.25 (±3%)
4. Polyvinyl Alcohol (PVA) (Binding agent & film forming or coating agent) 2.60
5. Binder sodium lingosulphate 2.50
6. Castor oil Ethoxylate (wetting agent) 3.50
7. Precipitate silica 1.50
8. Glycerol 1.25
9. Silica Sand 16-40 mesh 84.73
10. Colorant polymer 0.75
TOTAL 100.00

Preparation method of Granular formulation:
In our this present invention there is provided a process for the manufacture of the premix Insecticides as finished product , in particular premixed insecticide and preferred formulations coated granules emulsion described above, which comprises a three-steps of process: -
1. Preparation of wet paste with the composition Diluents, colorant and adjuvants: -
Add diluents DiAcetoAcetone (DAA) glycerol, wetting agent , dispersing agent and emulsifiers in a mixing kettle and blend till the homogenous mixture obtained . (Mixture 1)
Make a mixture of Polyvinyl Alcohol (PVA) (Binding agent & film forming or coating agent) with colorant in the ribbon blender. (Mixture 2)
Add slowly Fipronil technical, Chlorantraniliprole and Thiamethoxam technical into mixture 2 thenhomogenize the mixture in the dry medium in a ribbon blender. Mix the above mixture 30 to 60 minutes at room temperature. (Mixture 3)
Micronized the whole mass of mixture 3 in a jet mill on the controlled temperature and air pressure. Control the feed of material by feed controller device and ensure that temperature would not be beyond the temperature of whole system more than 40 degree centigrade.
1. After completing of air grinding in the jet mill, provide the time to homogenize the material as post mixing. Mix it till the homogenous powder obtained, and blend whole mass to 60 to 90 minutes.
2. In the Above mixture add slowly mixture 1, mixed and further blend the mass to 60 to 90 minutes and then analyze the quality parameters of this intermediate.
This is step A
2. Coating of step A on silica quartz granules in a PAN coating Machine: -
1. Take the dry and filtered desired size weighted granules in a PAN coating machine.
2. Weigh the batch quantity from step A and add into above pan coating machine which already charge with blank silica granules.
3. Mix the mass 15 – 20 minutes and get the proper coating and then precipitated silica. Final mixing is about 10- 15 minutes
This is step B
3. Drying of coated granules in a Rotatory dryer:
In this step, the setup the machine having the facility of hot air drying. The hot air generator is produced by HOT air generator. It is continuously drying process as the coated material was charge from charging point and get the material from discharge point. The drying material will to sieve machine.

4. Preparation of Final Product:
1. The coated and dried material is filtered on desired sieve.
2. Homogenize and take the sample for analysis, if the product is found as per specifications to pack into HDPE Bags.

Table 1(a): Quality parameters of GR formulation
Sno Parameter Description
1. Physical Description The material shall be in the form of bluish color granules free from extraneous matter, readily to use as broad casting in the crop field
2. Sieve size of granules Passed minimum 97 % through 16 BSS
Passed maximum 5 % through 36 BSS
Passed maximum 1% through 75 micron
3. pH 1% aqueous solution 5.0 - 8.0
4. Attrition Test Maximum residue 1 %
5. Water runoff test Maximum 5 %
6. Stability at elevated temperature After storage 54 ±20C for 14 days, the determined average active ingredient content must not be lower than 5 % relative to the determined average content found before storage and the formulation shall continue to comply the pH, emulsion stability and re-emulsification as required.
7. Moisture Content % by mass, Max. 1.0
8. Acidity as H2SO4, % by mass, Max. 0.10
9. Alkalinity as NaOH, % by mass, Max. 0.15

Example 2: Field evaluation of the bio efficacy of the present Insecticidal composition.
Experiment Details
Season : Rabi 2022-23
Location of experiment : ICAR-NRRI, Cuttack (Odisha)
Crop : Rice
Variety : TN-1
Plot size : 25 sq. meter
Spacing : Plant to Plant 15cm
Row to Row 20cm
Design : RBD
Replication : 3
Treatments : 9
Date of Transplanting : 16.01.2023
Application (Once) : 20-25 days after transplanting
Stage of application : Emergence of 1st brood of the stem borer moths
Temperature : Avg. 35 degree centigrade
Relative humidity : Avg. 70%
Wind : No wind

Insecticide application method:
Recommended dosage (g/ha) of granular formulation was mixed with sand (50 Kg/ha) and uniformly broadcasted by using hand operated granule applicator or mechanical dispenser or by hand wearing rubber gloves. Kept water impounded for 2-3 days after application.

Table 2 below provides the treatment details in Rice crop. For purposes of convenience, the present composition has been represented by the code “TAS0211”.

Sno Treatment Details Dose a.i/hectare (g) Dose (gm)/ha
T-1 TAS0211 20+40+50 3500
T-2 TAS0211 30+50+60 4500
T-3 TAS0211 50+70+70 6000
T-4 Chlorantraniliprole 0.40 % GR 75 10000
T-5 Chlorantraniliprole 0.50 % + Thiamethoxam 1% GR 30 + 60 6000
T-6 Fipronil 0.3% GR 60 10000
T-7 Thiamethoxam 25 % WG (Spray ) 50 200
T-8 Untreated control - -
T-9 TAS0211 80+100+100 9000
(For phytotoxicity evaluation)

Note: TAS0211 - Chlorantraniliprole 0.6% + Thiamethoxam 1.25% + Fipronil 1.25% GR

EVALUATION OF BIO-EFFICACY IN RICE CROP
a. Stem Borer: Observation on dead hearts/ white ear heads taken at weekly interval after treatment imposition and expressed in % damage reduction over control.
b. Leaf Folder: Observation on number of freshly damaged or folded leaves before and after each application.
c. Effect on natural enemies: Observation on number natural enemies before and after each application.
d. Yield at harvest: Marketable yield per plot recorded and converted to tones per ha.

Table-2.a: Effect of insecticide (TAS0211) treatment on stem borer infestation at different time intervals during vegetative stage
S.no Treatment details Dose /hectare
(g. a. i) Dead heart (%)
7 DAT 14 DAT 21 DAT 28 DAT
T-1 TAS0211 20+40+50 5.47 4.87 4.14 2.72
T-2 TAS0211 30+50+60 3.43 3.46 2.88 1.26
T-3 TAS0211 50+70+70 3.76 3.64 2.97 1.37
T-4 Chlorantraniliprole 0.40 % GR 75 9.29 6.39 6.01 3.25
T-5 Chlorantraniliprole 0.50 % +
Thiamethoxam 1% GR 30 + 60 8.77 9.78 10.50 6.67
T-6 Fipronil 0.3% GR 60 13.23 10.24 12.39 9.66
T-7 Thiamethoxam 25 % WG (Spray ) 50 19.80 20.40 21.68 13.77
T-8 Untreated control - 21.52 22.74 22.43 16.03
S.Em (±) 0.83 1.16 0.72 0.50
CD @ 5 % 2.50 3.51 2.19 1.51

Table 2.a showing that least dead heart percent of rice stem borer observed in T2, TAS0211 @ 30+50+60 gm a.i. per hectare. The treatment also recorded the least count of dead hearts at 7, 14, 21 and 28 days after application during vegetative stage.

Table-2.b: Effect of insecticide(TAS0211) treatment on stem borer infestation at different time intervals during reproductive (panicle initiation) stage
Sno. Treatment details Dose /hectare
(g. a. i) White ear heads count % reduction over control
7 days 14days 7 days 14days
T-1 TAS0211 20+40+50 0.27 0.39 70.00 76.45
T-2 TAS0211 30+50+60 0.15 0.28 83.33 83.43
T-3 TAS0211 50+70+70 0.16 0.31 81.85 81.44
T-4 Chlorantraniliprole 0.40 % GR 75 0.41 0.50 54.07 70.06
T-5 Chlorantraniliprole 0.50 % +
Thiamethoxam 1% GR 30 + 60 0.40 0.80 55.19 52.10
T-6 Fipronil 0.3% GR 60 0.54 0.82 40.00 51.10
T-7 Thiamethoxam 25 % WG (Spray ) 50 0.88 1.49 1.85 10.98
T-8 Untreated control - 0.90 1.67 0.00 0.00
S.Em (±) 0.04 0.06 - -
CD @ 5 % 0.11 0.17 - -

Table 2.b indicating least white ear head counts due to rice stem borer observed in T2, TAS0211 @ 30+50+60 gm a.i. per hectare without any phytotoxicity. The treatment also recorded the highest per cent reduction of white ears at 7 and 14 days observation during reproductive stage.

Table-2.c: Effect of insecticide(TAS0211) treatment on leaf folder infestation at different time intervals

Sno. Treatment details Dose /hectare
(g. a. i) No. of folded leaves
Pre treatment Post treatment
T-1 TAS0211 20+40+50 24.07 2.55
T-2 TAS0211 30+50+60 23.17 1.89
T-3 TAS0211 50+70+70 23.44 2.01
T-4 Chlorantraniliprole 0.40 % GR 75 23.41 4.72
T-5 Chlorantraniliprole 0.50 % +
Thiamethoxam 1% GR 30 + 60 24.29 10.73
T-6 Fipronil 0.3% GR 60 23.64 11.60
T-7 Thiamethoxam 25 % WG (Spray ) 50 24.13 12.95
T-8 Untreated control - 23.27 20.49
S.Em (±) - 0.26
CD @ 5 % NS 0.80
NS- Non significant
Table 2.c showing that least no. of folded leaves due to leaf folder damage was observed in T2, TAS0211 @ 30+50+60 gm a.i. per hectare without any phytotoxicity. All the treatments indicated no significant difference in number of folded leaves before treatment imposition.

Table-2.d: Effect of insecticide(TAS0211) treatment on natural enemy population

Sno Treatment details Dose /hectare
(g. a. i) No. of natural enemies per plot
Dragonflies Spiders
Before After Before After
T-1 TAS0211 20+40+50 4.60 4.48 7.98 8.02
T-2 TAS0211 30+50+60 4.55 4.32 8.03 7.79
T-3 TAS0211 50+70+70 4.23 4.26 7.92 7.86
T-4 Chlorantraniliprole 0.40 % GR 75 4.39 4.15 8.15 7.85
T-5 Chlorantraniliprole 0.50 % +
Thiamethoxam 1% GR 30 + 60 4.21 4.10 7.87 8.07
T-6 Fipronil 0.3% GR 60 4.41 4.37 8.26 7.91
T-7 Thiamethoxam 25 % WG (Spray) 50 4.72 4.33 8.05 8.03
T-8 Untreated control - 4.28 4.25 7.91 7.82
CD @ 5 % NS NS NS NS

Table 2.d: Spider and Dragonflies counts showed that there is no significant difference in natural enemy population count between any of the chemical treatment and the untreated control. Thus, TAS0211 can be considered to be safe on the natural enemies found in rice crop.
Table-2.e: Effect of insecticide (TAS0211) treatment on marketable yield
Sno Treatment details Dose /hectare
(g. a. i) Yield (t/ha.)
T-1 TAS0211 20+40+50 2.94
T-2 TAS0211 30+50+60 3.19
T-3 TAS0211 50+70+70 3.08
T-4 Chlorantraniliprole 0.40 % GR 75 2.33
T-5 Chlorantraniliprole 0.50 % +
Thiamethoxam 1% GR 30 + 60 2.13
T-6 Fipronil 0.3% GR 60 2.08
T-7 Thiamethoxam 25 % WG (Spray ) 50 1.91
T-8 Untreated control - 1.59
S.Em (±) 0.06
CD @ 5 % 4.14

Table 2.e showed that highest yield observed in treatment T2, TAS0211 @ 30+50+60 gm a.i. per hectare, whereas lowest yield was registered in untreated control.

Example 3: Evaluation of phytotoxicity of the present Insecticidal composition
Visual observations were recorded at 1, 3, 5, 7 and 10 days after application (DAA) of tested product. The parameters observed were leaf injury on tip/surface, stunting, necrosis, chlorosis, vein clearing, epinasty, hyponasty and wilting based on 0-10 scale given in below table. A total of 20 plants per plot were observed.

Table 3: Phytotoxicity symptoms scoring and rating for leaf injury on tip/surface
Leaf injury on tips /surface Rating
0% 0
1-10% 1
11-20% 2
21-30% 3
31-40% 4
41-50% 5
51-60% 6
61-70% 7
71-80% 8
81-90% 9
91-100% 10

Phytotoxicity studies
Table-3.a Phytotoxic effect of various treatments on Rice crop after 1 DAA
Treatment number Treatment details Dose /hectare
(g. a. i) 1 DAA
L S N C V E H W
T-1 TAS0211 20+40+50 0 0 0 0 0 0 0 0
T-2 TAS0211 30+50+60 0 0 0 0 0 0 0 0
T-3 TAS0211 50+70+70 0 0 0 0 0 0 0 0
T-4 Chlorantraniliprole 0.40 % GR 75 0 0 0 0 0 0 0 0
T-5 Chlorantraniliprole 0.50 % + Thiamethoxam 1% GR 30 + 60 0 0 0 0 0 0 0 0
T-6 Fipronil 0.3% GR 60 0 0 0 0 0 0 0 0
T-7 Thiamethoxam 25 % WG (Spray ) 50 0 0 0 0 0 0 0 0
T-8 Untreated control - 0 0 0 0 0 0 0 0
T-9 TAS0211 80+100+100 0 0 0 0 0 0 0 0

DAA – Days after application, L- Leaf injury on tips/surface, S- stunting, N-Necrosis, C- Chlorosis, V- Vein clearing, E- Epinasty, H- Hyponasty, W-wilting

Table-3.b Phytotoxic effect of various treatments on Rice crop after 3DAA

Treatment number Treatment details Dose /hectare
(g. a. i) 3 DAA
L S N C V E H W
T-1 TAS0211 20+40+50 0 0 0 0 0 0 0 0
T-2 TAS0211 30+50+60 0 0 0 0 0 0 0 0
T-3 TAS0211 50+70+70 0 0 0 0 0 0 0 0
T-4 Chlorantraniliprole 0.40 % GR 75 0 0 0 0 0 0 0 0
T-5 Chlorantraniliprole 0.50 % + Thiamethoxam 1% GR 30 + 60 0 0 0 0 0 0 0 0
T-6 Fipronil 0.3% GR 60 0 0 0 0 0 0 0 0
T-7 Thiamethoxam 25 % WG (Spray ) 50 0 0 0 0 0 0 0 0
T-8 Untreated control - 0 0 0 0 0 0 0 0
T-9 TAS0211 80+100+100 0 0 0 0 0 0 0 0

DAA – Days after application, L- Leaf injury on tips/surface, S- stunting, N-Necrosis, C- Chlorosis, V- Vein clearing, E- Epinasty, H- Hyponasty, W-wilting

Table-3.c Phytotoxic effect of various treatments on Rice crop after 5 DAA
Sno Treatment details Dose /hectare
(g. a. i) 5 DAA
L S N C V E H W
T-1 TAS0211 20+40+50 0 0 0 0 0 0 0 0
T-2 TAS0211 30+50+60 0 0 0 0 0 0 0 0
T-3 TAS0211 50+70+70 0 0 0 0 0 0 0 0
T-4 Chlorantraniliprole 0.40 % GR 75 0 0 0 0 0 0 0 0
T-5 Chlorantraniliprole 0.50 % + Thiamethoxam 1% GR 30 + 60 0 0 0 0 0 0 0 0
T-6 Fipronil 0.3% GR 60 0 0 0 0 0 0 0 0
T-7 Thiamethoxam 25 % WG (Spray ) 50 0 0 0 0 0 0 0 0
T-8 Untreated control - 0 0 0 0 0 0 0 0
T-9 TAS0211 80+100+100 0 0 0 0 0 0 0 0

DAA – Days after application, L- Leaf injury on tips/surface, S- stunting, N-Necrosis, C- Chlorosis, V- Vein clearing, E- Epinasty, H- Hyponasty, W-wilting

Table-3.d Phytotoxic effect of various treatments on Rice crop after 7 DAA

Sno Treatment details Dose /hectare
(g. a. i) 7DAA
L S N C V E H W
T-1 TAS0211 20+40+50 0 0 0 0 0 0 0 0
T-2 TAS0211 30+50+60 0 0 0 0 0 0 0 0
T-3 TAS0211 50+70+70 0 0 0 0 0 0 0 0
T-4 Chlorantraniliprole 0.40 % GR 75 0 0 0 0 0 0 0 0
T-5 Chlorantraniliprole 0.50 % + Thiamethoxam 1% GR 30 + 60 0 0 0 0 0 0 0 0
T-6 Fipronil 0.3% GR 60 0 0 0 0 0 0 0 0
T-7 Thiamethoxam 25 % WG (Spray ) 50 0 0 0 0 0 0 0 0
T-8 Untreated control - 0 0 0 0 0 0 0 0
T-9 TAS0211 80+100+100 0 0 0 0 0 0 0 0

DAA – Days after application, L- Leaf injury on tips/surface, S- stunting, N-Necrosis, C- Chlorosis, V- Vein clearing, E- Epinasty, H- Hyponasty, W-wilting

Table-3.e Phytotoxic effect of various treatments on Rice crop after 10 DAA

Treatment number Treatment details Dose /hectare
(g. a. i) 10 DAA
L S N C V E H W
T-1 TAS0211 20+40+50 0 0 0 0 0 0 0 0
T-2 TAS0211 30+50+60 0 0 0 0 0 0 0 0
T-3 TAS0211 50+70+70 0 0 0 0 0 0 0 0
T-4 Chlorantraniliprole 0.40 % GR 75 0 0 0 0 0 0 0 0
T-5 Chlorantraniliprole 0.50 % + Thiamethoxam 1% GR 30 + 60 0 0 0 0 0 0 0 0
T-6 Fipronil 0.3% GR 60 0 0 0 0 0 0 0 0
T-7 Thiamethoxam 25 % WG (Spray ) 50 0 0 0 0 0 0 0 0
T-8 Untreated control - 0 0 0 0 0 0 0 0
T-9 TAS0211 80+100+100 0 0 0 0 0 0 0 0

DAA – Days after application, L- Leaf injury on tips/surface, S- stunting, N-Necrosis, C- Chlorosis, V- Vein clearing, E- Epinasty, H- Hyponasty, W-wilting
Results:
Table 3.a, 3.b, 3.c, 3.d and 3.e indicates that application of TAS0211 (trimix of Chlorantraniliprole 0.6% + Thiamethoxam 1.25% + Fipronil 1.25% GR) in all four doses mentioned in the table showed no phytotoxicity. Even the highest dose of TAS0211 i.e. TAS0211 @ 80+100+100 g ai/ha did not record any kind of phytotoxic symptoms like leaf injury on tips, leaf injury on surface, wilting, vein clearing, necrosis, epinasty and hyponasty in rice crop. Thus, the application of TAS0211 can be considered completely safe for rice crop.
,CLAIMS:
1. An insecticidal composition comprising:
a) Chlorantraniliprole in an amount ranging from 0.1-20% w/w,
b) Thiamethoxam in an amount ranging from 0.1-20% w/w; and
c) Fipronil in an amount ranging from 0.1 to 35%w/w.

2. The insecticidal composition as claimed in claim 1, wherein Chlorantraniliprole is present in an amount of 0.6% w/w, Thiamethoxam is present in an amount of 1.25 w/w and Fipronil is present in an amount of 1.25 % w/w.

3. The insecticidal composition as claimed in claim 1, comprising at least one agriculturally acceptable excipient.

4. The insecticidal composition as claimed in claim 1, wherein said insecticidal composition is formulated in a form selected from the group consisting of water-soluble concentrates (SL), emulsifiable concentrates (EC), emulsions (EW), micro-emulsions (ME), Suspension concentrates (SC), oil-based suspension concentrates (OD), flowable suspensions (FS), water-dispersible 15 granules (WG), water-soluble granules (SG), wettable powders (WP), water soluble powders (SP), dry flowables (DF), granules (GR), encapsulated granules (CG), fine granules (FG), macrogranules (GG), aqueous Suspo-emulsions (SE), capsule suspensions (CS), and microgranules (MG).

5. The insecticidal composition as claimed in claim 4, wherein said insecticidal composition is formulated in the form of a Granular (GR).

6. The insecticidal composition as claimed in claim 3, comprising at least a dispersing agent; at least a wetting agent; at least an anti-freeze agent; at least a biocide; at least a defoamer; and at least a thickener.

7. The insecticidal composition as claimed in claim 6, wherein said at least a dispersing agent is present in an amount ranging from 0.1-30% w/w; said at least a wetting agent is present in an amount ranging from 0.1-30% w/w; said at least an anti-freeze agent is present in an amount ranging from 0.1-15% w/w; said at least a binding agent is present in an amount ranging from 0.5-10% w/w; said at least a fillers is present in an amount ranging from 0.1 to 50% w/w.

8. The insecticidal composition as claimed in claim 7, wherein said at least a dispersing agent is selected from the group consisting of sodium lignosulphonates, sodium naphthalene sulphonate- formaldehyde condensates, aliphatic alcohol ethoxylates, tristyrylphenol ethoxylates and esters, ethylene oxide/propylene oxide block copolymers, and combinations thereof;
said at least a wetting agent is selected from the group consisting of blend of alkyl naphthalene sulfonate, sodium salt, sodium laurel sulphate, sodium lignosulphonates and combinations thereof;
said at least an anti-freeze agent is selected from the group consisting of monoethylene glycol, diethylene glycol, polypropylene glycol, glycerol ethylene alcohols, polyethylene glycols, glycerin, epichlorohydrin, urea, glycerol, sorbitol, and mixture thereof;
said at least a binding agent is selected from the group consisting of polyvinylpyrrolidone, lactose, sucrose, and combinations thereof;
said at least thickener is selected from the group consisting of precipitated silica and diatomaceous earth kaolin, dibasic ammonium phosphate.and combinations thereof.

9. A process for preparing a granular formulation of the insecticidal composition as claimed in claim 1, said process comprising:

Add diluents DiAcetoAcetone (DAA) glycerol, wetting agent , dispersing agent and emulsifiers in a mixing kettle and blend till the homogenous mixture obtained . (Mixture 1)
Make a mixture of Polyvinyl Alcohol (PVA) (Binding agent & film forming or coating agent) with colorant in the ribbon blender. (Mixture 2)
Add slowly Fipronil technical, Chlorantraniliprole and Thiamethoxam technical into mixture 2 then homogenize the mixture in the dry medium in a ribbon blender. Mix the above mixture 30 to 60 minutes at room temperature. (Mixture 3)
Micronized the whole mass of mixture 3 in a jet mill on the controlled temperature and air pressure. Control the feed of material by feed controller device and ensure that temperature would not be beyond the temperature of whole system more than 40 degree centigrade.
After completing of air grinding in the jet mill, provide the time to homogenize the material as post mixing. Mix it till the homogenous powder obtained, and blend whole mass to 60 to 90 minutes.
In the Above mixture add slowly mixture 1, mixed and further blend the mass to 60 to 90 minutes and then analyze the quality parameters of this intermediate.