DESC:FIELD OF THE INVENTION
The present invention relates to the field of pesticides. The present invention in particular relates to a synergistic, broad spectrum insecticidal composition comprising Emamectin benzoate, Chlorantraniliprole and Deltamethrin. The present invention further relates to the process of preparation of said composition and uses thereof.
BACKGROUND OF THE INVENTION
The background description includes information that may be useful in understanding the present invention. It is not an admission that any of the information provided herein is prior art or relevant to the presently claimed invention, or that any publication specifically or implicitly referenced is prior art.
Pest infestations pose significant adverse effect on economically important agricultural crops such as cotton, brinjal, okra, tomato, chilli, soybean, chick pea and cabbage. Particularly, cotton an important fiber and cash crop and chilli a spices crop which plays a dominant role in the industrial and agricultural economy are infested by major insects such as sucking insects which includes thrips, aphids, whiteflies and jassids and caterpillars such as helicoverpa, spodoptera and pink bollworm.
To address this problem, researchers are trying to produce an extensive variety of active ingredients and active ingredients formulations effective in the control of insects. Chemical insecticides of many types have been disclosed in the art and a large number are in commercial use. In crop protection, it is desirable in principle to increase specificity and reliability of action of insecticidal active ingredients.
Imidacloprid, emamectin benzoate, ethion, fenpropathrin, fipronil, dimethoate, lambda cyhalothrin, methomyl, spinosad, thiacloprid, diafenthiuron, thiamethoxam, novaluron, lufenuron are compound independently known in the art for their insecticidal potency. They are disclosed in “The Pesticide Manual” 15th Edition, published 2009 by the British Crop Protection Council, and are also commercially available.
WO 2000/002453 A1 generically enables the combination of Phenthoate and Emamectin benzoate emulsifiable concentrates formulation comprising use of surfactants, and an aromatic solvent.
However, certain insect pests are becoming more and more resistant to a number of most widely used insecticides available in the art. Thus, on one hand even more stringent conditions are being placed on the type and use rate of insecticide, while on the other hand approved insecticides are becoming less and less effective over time in insect pests available in the art.
Furthermore, it is very expensive and time consuming to seek and obtain registration of a new insecticide compound, including its proposed use rate. Approval data required must not only include evidence of efficacy at the application rates proposed but also safety of insecticide when applied at the recommended level, also the recommended level of insecticide that may be applied per unit of area is under pressure from governmental, as well as for economic and environmental reasons.
Accordingly, demonstration of synergism by combination of existing insecticide agents, permits use of individual agents of synergistic combination at lower rates than when used alone, and in many instances ameliorates increasing resistance to insecticidal effectiveness.
Thus, there is a great need in the art for environmentally safe, stable, synergistic, broad-spectrum, better efficacious, insecticide composition comprising combination of three active ingredients having different mode of action, showing one or more of advantage such as stability, synergistic effect, faster onset of insecticide action, a broad-spectrum and long-lasting action reduced dosage of active ingredients, reduced application rate of the insecticide thereby rendering such combination environmentally safe, and reduce or delay the development of resistance in pests, which is necessary to obtain acceptable insect pest control and a process for preparing such insecticide composition or formulation comprising the same.
OBJECTS OF THE INVENTION
It is an object of the present invention to provide a novel, stable, synergistic, insecticidal composition comprising Emamectin benzoate, Chlorantraniliprole and Deltamethrin as its ingredients.
It is another object of the present invention to provide an insecticidal composition comprising Emamectin benzoate and Chlorantraniliprole as insecticidal active ingredients and Deltamethrin as a synergist.
It is yet another object of the present invention to provide an insecticidal composition with enhanced bioefficacy at reduced dosage as compared to individual insecticides when used in isolation.
It is yet another object of the present invention to provide an insecticidal composition that result in good enhancement in crop yield.
It is yet another object of the present invention to provide an insecticidal composition that is environmentally safe and non-phytotoxic.
It is yet another object of the present invention to provide an insecticidal composition that has broad spectrum activity and can be used in a wide variety of agricultural crops.

SUMMARY OF THE INVENTION
Accordingly, in one aspect, the present invention provides a novel, stable, synergistic, environmentally safe, broad spectrum, cost effective insecticidal composition comprising Emamectin benzoate as the first active ingredient, Chlorantraniliprole as the second active ingredient and Deltamethrin as the third active ingredient as a synergist.
In another aspect, the present invention provides a novel, stable, synergistic, environment friendly, broad spectrum, cost effective insecticidal composition that is effective in controlling thrips, mite and fruit borer on chilli crop.
In another aspect, the present invention provides a stable formulation comprising said insecticidal composition. In a preferred aspect, said insecticidal composition is formulated as an Emulsion concentrate.
In yet another aspect, the present invention provides a process for preparing said insecticidal composition.

DETAILED DESCRIPTION OF THE INVENTION
Those skilled in the art will be aware that the invention described herein is subject to variations and modifications other than those specifically described. It is to be understood that the invention described herein includes all such variations and modifications. The invention also includes all such steps, features, compositions and compounds referred to or indicated in this specification, individually or collectively, and all combinations of any two or more of said steps or features.
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 teaching of the present invention.
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.
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 "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.
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.
As used herein, the terms "comprises", "comprising", "includes", "including", or any other variation thereof, are intended to cover a non-exclusive inclusion, subject to any limitation explicitly indicated. For example, a composition or a method that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, or method.
As used herein, the term "agrochemically acceptable salts" are typically acid addition salts of inorganic or organic acids, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, malonic acid, toluenesulfonic acid or benzoic acid.
As used herein, the term “additive(s)” or "auxiliary agent(s)" or “agriculturally acceptable carrier(s)” can be used interchangeably and refers to inert substances which are commonly used as diluent, to provide stability or to increase the activity profile of the composition or formulation with or without having agrochemical activity.
Unless otherwise specified, % refers to % weight; and % weight refers to % of the weight of the respective component with respect to the total weight of the composition.
As used herein, the term "effective amount" means the amount of the active substances in the compositions to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The effective amount can vary for the various compositions used in the present invention. An effective amount of the compositions will also vary according to the prevailing conditions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.
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.

Emamectin benzoate chemically known as (4R)-4-deoxy-4-(methylamino)avermectin B1 benzoate (1:1) is an avermectin insecticide. It is a contact insecticide with negligible toxicity to non-target organisms. It allosterically activates glutamate-gated chloride channels (GluCls) causing paralysis in the insects.
Chlorantraniliprole is broad-spectrum anthranilic diamide insecticide interrupts the normal muscle contraction of insects, resulting in death. It adheres to plant 20 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. Its chemically known as 3-Bromo-4'-chloro-1-(3-chloro-2-pyridyl)-2'-methyl-6'-(methylcarbamoyl)pyrazole-5-carboxanilide .
Deltamethrin is the most effective synthetic pyrethroid insecticide for use in agriculture, being photo stable. It is nonsystemic insecticide which acts by contact and ingestion, and exhibiting a broad spectrum control of chewing and sucking insects. It is effective against a wide range of insect pests, which include Lepidoptera, Homoptera; particularly Aphids and Psylla but also some Coccidea and Cicadellinea, Heteroptera, Thysanoptera; selected thrips species, Diptera, Coleoptera and Orthoptera.
Embodiments of the present invention 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) Emamectin Benzoate as the first active ingredient b) Chlorantraniliprole as the second active ingredient and c) Deltamethrin as the third active ingredients. Wherein, Emamectin Benzoate is present in an amount ranging from 0.10-7.5 w/w, Chlorantraniliprole is present in an amount ranging from 0.01- 21% w/w and Deltamethrin is present in an amount ranging from 0.01-11.5% w/w the insecticidal composition.
In a preferred embodiment, Emamectin Benzoate is present in an amount 1.90%w/w, Chlorantraniliprole is present in an amount of 5.0%w/w and Deltamethrin is present in an amount of 1.0%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, particularly insects in Chilli crop, particularly thrips, mite and fruit borer.
In an embodiment, the insecticidal composition of the present invention may be applied to a variety of agricultural crops like brinjal, colecrops, cucurbits, cotton, tea, ornamentals, horticultural crops and oil seed crops.
In a more preferred embodiment, the insecticidal composition of the present invention is formulated in the form of a Emulsion concentrate comprising a Emulsifiers, Buffer, stabilizer, carriers, PH adjusters and diluents.
Suitable emulsifier for use in the formulation includes all substances which normally can be used for this purpose in agrochemical formulations.Examples of the excipient includes substances which can be ionic or non-ionic emulsifier or surfactant. The ionic substances can be selected from cationic surfactants, or anionic surfactants and a combination thereof.
The ionic emulsifier or surfactant can be selected from the group consisting of but not limiting to calcium salt of alkylaryl sulfonates, calcium dodecylbenzene sulfonate, ethoxylated and/or propoxylated di- or tristyrylphenol phosphate, ethoxylated and/or propoxylated di- or tristyrylphenol sulfate, phenyl sulfonate, alkynaphtalenesulphonate ethoxylated and/or propoxylated alcohol phosphate ester, ethoxylated and/or propoxylated alkylaryl phosphate ester, suphosuccinate, salts of polyacrylic acids, salts of lignosulphonic acid, salts of phenylsulphonic or naphthalenesulphonic acids, sulphosuccinic ester salts, taurine derivatives, especially alkyl taurates, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols, phosphoric esters of polyethoxylated phenols or alcohols polycarboxylate and mixtures thereof.
The non-ionic emulsifier or surfactant can be selected from the group consisting of but not limiting to alkoxylated alcohols, ethoxylated alcohols, ethoxylated propoxylated alcohols, alkylphenolethoxylates, alkoxylated tristyrylphenols, tristyryphenol ethoxylate, alkoxylated tributylphenols, alkylaminethoxylates, ethoxylated propoxylated polyaryl phenol, ethoxylated poly adducts of ethylene oxide and propylene oxide, ethoxylated fatty acids, sorbitan esters and their ethoxylates, sorbitol esters, propylene glycol esters of fatty acids and polyglycerol esters, ethoxylated ricinoleic acid triglycerides castor oil ethoxylate and mixtures thereof. The emulsifier is present in an amount of from 1.5% to 13.5 % by weight based on a total weight of the composition.
The pH modifier is selected from sodium silicate, potassium silicate,magnesium silicate, manganese silicate, sodium pyrophosphate, sodium acetate, sodium oxalate, sodium carbonate, sodium bicarbonate, sodium bentonite, sodium acetate, attapulgite, diatomaceous earth, sodium zeolite, trisodium phosphate, trisodium citrate, magnesium carbonate, magnesium sulphate, monoethanol amine, triethanol amine, triethylamine, dibasic esters selected from dimethyl succinate, dimethyl glutarate, dimethyl adipate , ortho phosphoric acid, oxalic acid, citric acid, Fumaric acid, hydrochloric acid and mixtures thereof. The pH modifier is present in an amount of from 0.10% to 5% by weight based on a total weight of the composition.
Suitable inert carrier(s) for use in the composition include, but not limited to, natural ground minerals, such as kaolin or china clay, alumina, talc, chalk, quartz, attapulgite, montmorillonite, and diatomaceous earth, or synthetic ground minerals, such as highly dispersed silicic acid, aluminium oxide, silicates, N-Methyl-2-pyrrolidone and calcium phosphates and calcium hydrogen phosphates, crushed and fractionated natural minerals, such as calcite, marble, pumice, precipitated silica, sepiolite, bentonite, river sand, zeolites, starch, sand, talc, quartz, dolomite, synthetic granules of inorganic and organic ground materials and mixtures thereof. The inert carrier is present in an amount of from 5.0% to 22.5% by weight based on a total weight of the composition.
Suitable solvents for use in the composition are selected from all customaryorganic solvents which dissolve one or more of the active ingredients employed. Preferred solvents include, but not limited to, deionized 5 (DI) water, Nalkyl pyrrolidone, N-methyl-2-pyrrolidone, dimethylformamide (DMF),n-hexanol dimethylsulfoxide (DMSO) and mixtures thereof. The solvent is present in an amount of from 2% to 25% by weight based on a total weight of the composition.
The buffering agent for Emulsion Concentrate (EC) is selected from but no limited to the group consisting of, citric acid, sodium carbonate, sodium bicarbonate, sulphuric acid, hydrochloric acid, sodium hydroxide, potassium hydroxide, acetic acid, sorbic acid, BHT ( Butylated hydroxylated toluene) or mixture thereof. The Buffering agent is present in an amount of from 0.01% to 1.8 % by weight based on a total weight of the composition.
In an embodiment, the insecticidal composition is formulated in a form selected from the group comprising 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 granules (WG), water-soluble granules (SG), wettable powders (WP), water soluble powders (SP), granules (GR), encapsulated granules (CG), fine granules (FG), macrogranules (GG), dry flowables (DF), aqueous Suspo-emulsions (SE), capsule suspensions (CS) and microgranules (MG). In a preferred embodiment, the Insecticidal composition is in the form of suspension concentrates (SC), water-dispersible granule (WDG) and wettable powder (WP).
In a preferred embodiment, the Insecticidal composition of the present invention is formulated as an Emulsion concentrate.
Examples:
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 Emulsion concentrates (EC).
In an embodiment, the chemical composition of the present insecticidal is depicted below in Table 1 (a) below:
Table-1 (a): Composition of the Insecticidal composition
S.no Name of Ingredients
Composition % w/w

1 Emamectin Benzoate Active ingredient (based on 100 % w/w ) 1.90
2 Chlorantraniliprole Active Ingredient (based on 100 % w/w ) 5.0
3 Deltamethrin Active Ingredient (based on 100 % w/w ) 1.0
4 Anionic and non-ionic surfactant 20.00
5 BHT ( Butylated hydroxylated toluene) 0.10
6 Paraffin oil commercial grade 2.00
7 Fumaric Acid commercial grade 0.10
8 N-Methyl-2-pyrrolidone 30.50
9 N Hexanol Commercial 24.20
10 DMF 16.00
TOTAL 100.00
Table-1 (b): Preparation methods of Emulsion concentrate:

1. Mixed charged solvent N, N- dimethyl formamide (DMF) in the mixing kettle and motorised agitation.
2. Add N-Hexanol and N-Methyl-2-pyrrolidone solvents and mixed for 30 to 60 minutes.
3. Add Slowly Chlorantraniliprole, Deltamethrin and Emamectin Technical in the mixing vessel and continue the agitation 60 -120 minutes.
4. Add BHT (Butylated hydroxylated toluene), Paraffin oil and fumaric acid, maintained agitation till 30- 60 minutes.
5. Add Anionic and non-ionic surfactants in this above mixture and run the agitation to whole mass of raw materials.
6. Analysis the batch through representative sample as per prescribed specifications
Table-1(c): Quality parameters of EC formulation
Sno Testing Parameters Specifications of Finished Product
1 Physical Description The material shall be in the form of brown to amber color homogeneous stable emulsified liquid free from extraneous matter, readily mixed with water for the spray
2 Chlorantraniliprole Active Ingredient 4.00- 6.25
3 Deltamethrin Active Ingredient 0.75 – 1.25
4 Emamectin Benzoate Active ingredient 1.425- 2.375
5 Emulsion Stability and re-emulsification The formulation, when diluted at 25 ±50C with CIPAC standard waters A and D , shall comply with the following :
0 h - initial emulsification complete
0.5h-cream, maximum 0 mL
2.0h -cream, maximum 1 mL
24 h – re-emulsification complete
24.5 h – Cream maximum – 2 mL
Free oil maximum – 1 mL
6 pH 1% aqueous solution 5.0 - 8.0
7 Pourability Maximum residue 1 %
8 Persistent foam after 1 minute Maximum 60 mL
9 Stability at 0C After storage at 0 ±0C for 7 days , the volume of solid and / or oily liquid which separates shall not be more than 0.3mL
10 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 .

Example-2: Field evaluation of the bio-efficacy of the present Insecticidal composition.
Details of the experiment:
Location: Sriniketan, Visva-Bharati, Birbhum, West Bengal
Design: Randomized Block Design with 9 treatments including control with 3 replications.
Plot size: 5.0 × 4.0 sq m
Variety : Bullet
Spacing : 80cm X 100 cm

Measured quantity of the chemical was added to required volume of water @ 500L/ha for spraying. The spray tank was filled with ½ the quantity of clean required volume of water and then the measured chemical (according to the dose) was added followed by the rest half quantity of water. The solution was stirred well and thorough coverage was ensured.

Table-2: below provides the treatment details in Chilli crop.
T.no Treatment details Formulation Dose
(ml or g/ha) (ml or g/l)
T1 Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC 281.25 0.56
T2 Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC 375 0.75
T3 Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC 469 0.94
T4 Emamectin benzoate 1.9 % EC 375 0.75
T5 Deltamethrin 02.80 % EC 500 1.0
T6 Chlorantraniliprole 18.50 % SC 150 0.3
T7 Dimethoate 30 % EC 990 1.98
T8 Diafenthiuron 30 % + Pyriproxyfen 8% SC 1000 2.0
T9 Untreated Control - -
*T10 Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC 750 1.5

EVALUATION OF BIO-EFFICACY IN CHILLI CROP
Insect-pest population was recorded from 5 fixed plants/plot, selected randomly for this purpose. The population of thrips was recorded from 5 upper, 5 middle and 5 lower leaves of 5 randomly selected plants and averaged to get number of thrips/plant. Similarly, yellow mite population were recorded. Data was recorded as 1 day before and 5, 10 and 14 days after each spray. All the observations were recorded with the help of a hand lens (10X).
During each plucking, damaged and fresh chilli fruit were recorded and converted to percent damaged and healthy fruits per plant and present cumulative data of all plucking. Percent damaged fruits were calculated using the following formulae.

Percent fruit infestation= (Number of infested fruits)/(Total number of fruits) ? 100

The data thus obtained in different treatments were subjected to analysis of variance by using SPSS version 16.0 and significant differences among treatment means were tested with LSD at p<0.05 after necessary transformation (Gomez and Gomez, 1984). Reduction of pest population in different treatments over control was used as an indicator of insecticidal efficacy which was calculated from the following formula (Flemming & Retnakaran, 1985). Population reduction (%) =

Post-treatment population in treatment Pre-treatment population in untreated control
1- ----------------------------- x ------------------------------- x100
Pre-treatment population in treatment Post-treatment population in untreated control

b) Effect on natural enemies: The major predators namely coccinellid beetle were observed abundantly in the chilli field. For data recording, the predator populations were noted down from 5 plants randomly selected in each plot leaving the border rows just before insecticidal application as well as 5, 10 & 15 days after each spraying.
d) Record on yield: Yield of healthy marketable chilli was recorded during each picking from the selected plants in each plot and latter cumulated to calculate the yield in quintal per hectare. Mean yield estimated in different treatments was subjected to statistical analysis and compared by DMRT (Gomez and Gomez, 1984).
The per cent increase of yield in treatment over control was calculated from the following formula (Vanisree et al., 2013).
Per cent increase of yield in treatment over control =
Yield in treatment – Yield in control
---------------------------------------------- x 100
Yield in control
2. Trial condition: The field experiment was conducted during Rabi-2023-24 having sub-humid and sub-tropical climate at Agricultural farm, Palli Siksha Bhavana, Visva-Bharati, Sriniketan, Birbhum, West Bengal. The field is situated at 23.390N Latitude, 87.420F Longitude and at an average Altitude of 58.90 m above mean sea level in the Lateritic belt of West Bengal.

Table 3: Bio-Efficacy of Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC against chilli thrips
Treatment No. 1st Season Rabi 2023-24
1st Spraying % ROC 2nd Spraying % ROC
Mean no. of Thripsper plant Mean no. of Thripsper plant
PTC 5 DAS 10 DAS 15 DAS PTC 5 DAS 10 DAS 15 DAS
T1 2.63 1.15 1.25 2.00 69.70 2.05 0.90 0.97 1.56 87.67
(1.77) (1.28) (1.32) (1.58) (1.60) (1.18) (1.21) (1.43)
T2 2.51 1.05 1.11 1.94 70.61 1.94 0.81 0.86 1.50 88.14
(1.73) (1.24) (1.27) (1.56) (1.56) (1.15) (1.17) (1.41)
T3 2.36 1.00 1.05 1.90 71.21 1.90 0.81 0.85 1.35 89.33
(1.69) (1.22) (1.24) (1.55) (1.55) (1.14) (1.16) (1.36)
T4 2.32 3.05 3.79 5.01 24.09 5.01 6.59 8.18 9.25 26.88
(1.68) (1.88) (2.07) (2.35) (2.35) (2.66) (2.95) (3.12)
T5 2.51 1.62 1.75 2.76 58.18 2.76 1.78 1.92 3.03 76.05
(1.73) (1.46) (1.50) (1.81) (1.81) (1.51) (1.56) (1.88)
T6 2.25 3.01 3.75 4.98 24.55 4.98 6.66 8.30 9.25 26.88
(1.66) (1.87) (2.06) (2.34) (2.34) (2.68) (2.97) (3.12)
T7 2.15 1.55 1.61 2.21 66.52 2.21 1.59 1.65 2.27 82.06
(1.63) (1.43) (1.45) (1.65) (1.65) (1.45) (1.47) (1.66)
T8 2.34 1.13 1.18 1.98 70.00 1.98 0.96 1.00 1.68 86.72
(1.69) (1.28) (1.30) (1.57) (1.57) (1.21) (1.22) (1.47)
T9 2.51 3.26 4.12 6.60 0.00 5.95 7.73 9.77 12.65 0.00
(1.73) (1.94) (2.15) (2.54) (2.54) (2.87) (3.20) (3.63)
CD (P=0.05) NS 0.05 0.07 0.04 -- 0.04 0.03 0.04 0.06 --
SEm (±) 0.120 0.017 0.023 0.013 0.013 0.010 0.015 0.022
T1: Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC @ 281.25 ml/ha, T2: Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC @ 375 ml/ha, T3: Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC @ 469 ml/ha, T4: Emamectin benzoate 1.9 % EC @ 375 ml/ha, T5: Deltamethrin 02.80 % EC @ 500 ml/ha, T6: Chlorantraniliprole 18.50 % SC @ 150 ml/ha, T7: Dimethoate 30 % EC @ 990 ml/ha, T8: Diafenthiuron 30 % + Pyriproxyfen 8% SC @ 1000 ml/ha, T9: Untreated control.
DAS: Days after spraying; NS: Non-Significant; PTC: Pre treatment count; ROC: Reduction over control
?Figures in parentheses indicate v(x+0.5) transformed value

Table 4: Bio-Efficacy of Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC against chilli mites
Treatment No. 1st Season Rabi 2023-24
1st Spraying % ROC 2nd Spraying % ROC
Mean no. of Mites per plant Mean no. of Mites per plant
PTC 5 DAS 10 DAS 15 DAS PTC 5 DAS 10 DAS 15 DAS
T1 2.10 1.03 1.55 1.85 63.87 1.85 0.91 1.37 1.63 82.13
(1.61) (1.24) (1.43) (1.53) (1.53) (1.19) (1.37) (1.46)
T2 2.36 0.95 1.30 1.56 69.53 1.56 0.67 0.93 1.13 87.61
(1.69) (1.20) (1.34) (1.44) (1.44) (1.08) (1.20) (1.28)
T3 2.02 0.90 1.25 1.51 70.51 1.51 0.63 0.86 1.03 88.71
(1.59) (1.18) (1.32) (1.42) (1.42) (1.06) (1.17) (1.24)
T4 2.31 2.30 3.12 4.25 16.99 4.25 4.23 5.74 7.82 14.25
(1.68) (1.67) (1.90) (2.18) (2.18) (2.18) (2.50) (2.88)
T5 2.05 1.95 2.42 2.58 49.61 2.58 2.45 3.05 3.25 64.36
(1.60) (1.57) (1.71) (1.75) (1.75) (1.72) (1.88) (1.94)
T6 2.15 2.15 3.34 4.12 19.53 4.12 4.12 6.40 7.90 13.38
(1.63) (1.63) (1.96) (2.15) (2.15) (2.15) (2.63) (2.90)
T7 2.40 1.02 1.15 1.45 71.6 1.45 0.84 1.24 1.38 84.87
(1.70) (1.23) (1.28) (1.40) (1.40) (1.06) (1.09) (1.17)
T8 2.15 1.85 1.90 2.00 60.94 2.00 1.72 1.77 1.86 79.61
(1.63) (1.53) (1.55) (1.58) (1.58) (1.49) (1.51) (1.54)
T9 2.25 3.12 4.15 5.12 0.00 5.12 7.10 9.00 9.12 0.00
(1.66) (1.90) (2.16) (2.37) (2.37) (2.76) (3.08) (3.10)
CD (P=0.05) NS 0.04 0.10 0.11 -- 0.11 0.11 0.19 0.21 --
SEm (±) 0.027 0.015 0.033 0.035 0.035 0.038 0.063 0.071
T1: Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC @ 281.25 ml/ha, T2: Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC @ 375 ml/ha, T3: Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC @ 469 ml/ha, T4: Emamectin benzoate 1.9 % EC @ 375 ml/ha, T5: Deltamethrin 02.80 % EC @ 500 ml/ha, T6: Chlorantraniliprole 18.50 % SC @ 150 ml/ha, T7: Dimethoate 30 % EC @ 990 ml/ha, T8: Diafenthiuron 30 % + Pyriproxyfen 8% SC @ 1000 ml/ha, T9: Untreated control.
DAS: Days after spraying; NS: Non-Significant; PTC: Pre treatment count; ROC: Reduction over control
?Figures in parentheses indicate v(x+0.5) transformed value

Table 5: Bio-Efficacy of Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC against fruit borers of chilli

Treatment Details 1st Season
Cumulative data of all plucking % Increases of fresh fruit over control
% Fresh fruit plant-1 % Damaged fruit plant-1
Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC @ 281.25 ml/ha 87.95 12.05 73.38
(69.69) (20.31)
Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC @ 375 ml/ha 89.45 10.55 76.69
(71.05) (18.95)
Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC @ 469 ml/ha 89.75 10.25 77.35
(71.33) (18.67)
Emamectin benzoate 1.9 % EC @ 375 ml/ha 86.75 13.25 70.72
(68.65) (21.35)
Deltamethrin 02.80 % EC @ 500 ml/ha 81.75 18.25 59.68
(64.71) (25.29)
Chlorantraniliprole 18.50 % SC @ 150 ml/ha 87.48 12.52 72.34
(69.28) (20.72)
Dimethoate 30 % EC @ 990 ml/ha 74.76 25.24 44.23
(59.84) (30.16)
Diafenthiuron 30 % + Pyriproxyfen 8% SC @ 1000 ml/ha 58.75 41.25 8.86
(50.04) (39.96)
Untreated control 54.74 45.26 0.00
(47.72) (42.28)
CD (P=0.05) 1.37 1.63 -
SEm (±) 0.457 0.543

Table 6. Bio-efficacy of Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC on yield of chilli crop
Treatments
Rabi-2023-24 % increase yield over control
Yield
(q ha-1)
Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC @ 281.25 ml/ha 55.50 31.83
Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC @ 375 ml/ha 56.00 33.02
Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC @ 469 ml/ha 56.12 33.30
Emamectin benzoate 1.9 % EC @ 375 ml/ha 45.10 7.13
Deltamethrin 02.80 % EC @ 500 ml/ha 48.25 14.61
Chlorantraniliprole 18.50 % SC @ 150 ml/ha 45.21 7.39
Dimethoate 30 % EC @ 990 ml/ha 46.25 9.86
Diafenthiuron 30 % + Pyriproxyfen 8% SC @ 1000 ml/ha 48.95 16.27
Untreated control 42.10 0.00
CD(p=0.05) 2.85 -
SEm (±) 0.95 -

Table 7: Effect of different treatments on NE C. sexmaculata of chilli crop
1st season
1st spray 2nd spray
PTC 5 DAS 10 DAS PTC 5 DAS 10 DAS 15DAS
Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC @ 281.25 ml/ha 2.34 2.16 2.49 2.22 3.63 3.27 3.05
(1.69) (1.63) (1.73) (1.65) (2.03) (1.94) (1.88)
Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC @ 375 ml/ha 2.03 2.22 2.31 2.34 3.54 3.28 3.10
(1.59) (1.65) (1.68) (1.69) (2.01) (1.95) (1.90)
Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC @ 469 ml/ha 2.34 2.34 2.22 2.30 3.57 3.27 3.15
(1.69) (1.69) (1.65) (1.67) (2.02) (1.94) (1.91)
Emamectin benzoate 1.9 % EC @ 375 ml/ha 2.02 2.30 2.26 2.13 3.59 3.31 3.02
(1.59) (1.67) (1.66) (1.62) (2.02) (1.95) (1.88)
Deltamethrin 2.80 % EC @ 500 ml/ha 2.24 2.13 2.27 2.26 2.66 3.32 3.15
(1.66) (1.62) (1.67) (1.66) (1.78) (1.96) (1.91)
Chlorantraniliprole 18.50 % SC @ 150 ml/ha 2.11 2.49 2.61 2.08 3.54 3.26 3.45
(1.62) (1.73) (1.76) (1.61) (2.01) (1.94) (1.99)
Dimethoate 30 % EC @ 990 ml/ha 2.26 2.31 2.44 2.10 3.01 3.07 3.05
(1.66) (1.68) (1.71) (1.61) (1.87) (1.89) (1.88)
Diafenthiuron 30 % + Pyriproxyfen 8% SC @ 1000 ml/ha 2.30 2.22 2.31 2.23 2.90 3.60 3.11
(1.67) (1.65) (1.68) (1.65) (1.84) (2.02) (1.90)
Untreated control 2.31 2.26 2.22 2.25 3.51 3.87 4.85
(1.68) (1.66) (1.65) (1.66) (2.00) (2.09) (2.31)
CD(p=0.05) NS NS NS NS NS NS NS
DAS: Days after spraying; NS: Non-Significant; PTC: Pre treatment count
? Figures in parentheses indicate v(x+0.5) transformed value

Example-3: Evaluation of phytotoxicity of the present Insecticidal composition
The observations on phytotoxicity symptoms (viz., leaf injury, wilting, vein clearing, necrosis, epinasty and hyponasty), if any, on the crop due to application of Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC @ 750 ml/ha were recorded at 1, 3, 5, 7, 10 & 15 days after first spray using the scores shown below:

Scores used for effect of the insecticide on crop health.
Score Percent crop health affected
0 No adverse effect
1 1-10%
2 11-20%
3 21-30%
4 31-40%
5 41-50%
6 51-60%
7 61-70%
8 71-80%
9 81-90%
10 91-100%

.
Table 8. Evaluation of Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC for phytotoxicity on chilli crop (based on 20 leaves sample/ replication)
Treatments Dose
(ml/ha) Leaves injury on tips or surface Wilting Vein clearing Necrosis Epinasty Hyponasty
Untreated control - 0 0 0 0 0 0
Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC @ 375 ml/ha 70 0 0 0 0 0 0
Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC @ 750 ml/ha 140 0 0 0 0 0 0
* Observation were taken at 0, 1, 3, 5, 7, 10 & 15 Days after application in both the season

RESULT
During the study, the crop showed variable levels of infestation of Thrips -Scirtothrips dorsalis, Mites - Polyphagotarsonemus latus and Fruit borers - Helicoverpa armigera and Spodoptera sp.
Effect of treatments on Thrips: Scirtothrips dorsalis and Mites: Polyphagotarsonemus latus: Data presented in Table 3 revealed that, the pre-treatment population of thrips in different treatments did not differ significantly. All the insecticidal treatments significantly reduced the infestation of thrips as compared to untreated control. Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC @ 469 ml/ha was found most efficacious among the treatments and it was on par with its lower dose Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC @ 375 ml/ha. Similarly, mites population before the spraying did not differ significantly in the 1st season, application of Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC @ 469 ml/ha was found most efficacious among the treatments and it was on par with its lower dose Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC @ 375 ml/ha (Table 4).
Effect of treatments on Fruit borers: Helicoverpa armigera and Spodoptera sp: Table 5 revealed that, Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC @ 469 ml/ha was found most efficacious among the treatments and gave the maximum fresh semi ripe chilli fruit and it was on par with Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC @ 375 ml/ha. Percent fruit damage reduction over control was followed as Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC @ 469 ml/ha (77.35) > Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC @ 375 ml/ha (76.69) > Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC @ 281.25 ml/ha (73.38) > Chlorantraniliprole 18.50 % SC @ 150 ml/ha (72.34) > Emamectin benzoate 1.9 % EC @ 375 ml/ha (70.72) > Deltamethrin 02.80 % EC @ 500 ml/ha (59.68), Dimethoate 30 % EC @ 990 ml/ha (44.23), Diafenthiuron 30 % + Pyriproxyfen 8% SC @ 1000 ml/ha (8.86), respectively.
Effect of treatments on natural enemies of chilli ecosystem: During the period of study, natural enemy fauna lady bird beetle (C. septempunctata) was observed. The application of the insecticides was not found any significantly reduction of the lady bird beetle population (Table 7).
Effect of Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC on crop health: Table 7 showed that, no phytotoxic symptoms was observed due to application of Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC @ 750 ml/ha. in chilli crop.
Effect of treatments on Yield: The yield of healthy semi ripe chilli fruits recorded in different treatments is presented in Table 6. All the insecticidal treatments significantly increased the yield as compared to the control (42.10 q/ha). Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC @ 469 ml/ha, gave the maximum yield (56.12 q/ha) and it was found on par with Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC @ 375 ml/ha.
Conclusion: The above results clearly show that, the Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC @ 375 and 469 ml/ha effectively controlled chilli thrips, mites and fruit borers and produced maximum fruit yield of chilli. Two doses of Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC @ 375 and 469 ml/ha was safe to coccinellid natural enemies which were frequently observed on the chilli crop. The chemical even at higher doses Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC @ 750 ml/ha not causes any kind of phytotoxicity to chilli crop. On the basis of bio-efficacy, yield, safety to natural enemies and crop safety, Emamectin benzoate 1.9 % + Chlorantraniliprole 5 % + Deltamethrin 1 % EC @ 375 and 469 ml/ha may be recommended for effective management of sucking pest complex and fruit borer of chilli. ,CLAIMS:
1. An insecticidal composition comprising:
a) Emamectin benzoate in an amount ranging from 0.10 to7.5% w/w,
b) Chlorantraniliprole in an amount ranging from 0.01 to 21% w/w; and
c) Deltamethrin in an amount ranging from 0.01 to 11.5%w/w.
2. The insecticidal composition as claimed in claim 1, wherein Emamectin benzoate is present in an amount of 1.90% w/w, Chlorantraniliprole is present in an amount of 5% w/w and Deltamethrin is present in an amount of 1 % 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 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 Emulsion concentrate (EC).
6. The insecticidal composition as claimed in claim 5, comprising at least a surfactant; at least Emulsifiers, Buffer, stabilizer, carriers, PH adjusters and diluents/solvents.
7. The insecticidal composition as claimed in claim 6, wherein said Emulsifiers are selected form fatty acid esters, fatty alcohols, fatty acid amides or fatty amines with ethylene and/or propylene oxide, alkyl- , alkenyl or polyaryl-substituted phenols with ethylene and/or propylene oxide, fatty esters of polyhydric alcohol esters, Blend (Non-ionic- Alcohol ethoxylates) and Ionic- (Alkylarylsulphonates) .
8. The insecticidal composition as claimed in claim 6, wherein said pH modifier is selected from sodium silicate, potassium silicate,magnesium silicate, manganese silicate, sodium pyrophosphate, sodium acetate, sodium oxalate, sodium carbonate, sodium bicarbonate, sodium bentonite, sodium acetate, attapulgite, diatomaceous earth, sodium zeolite, trisodium phosphate, trisodium citrate, magnesium carbonate, magnesium sulphate, monoethanol amine, triethanol amine, triethylamine, dibasic esters selected from dimethyl succinate, dimethyl glutarate, dimethyl adipate , ortho phosphoric acid, oxalic acid, citric acid, Fumaric acid, hydrochloric acid.
9. The insecticidal composition as claimed in claim 6 , wherein said Buffer is selected from citric acid, sodium carbonate, sodium bicarbonate, sulphuric acid, hydrochloric acid, sodium hydroxide, potassium hydroxide, acetic acid, sorbic acid, BHT (Butylated hydroxylated toluene) .
10. The insecticidal composition as claimed in claim 6, wherein said inert carrier is selected from kaolin or china clay, alumina, talc, chalk, quartz, attapulgite, montmorillonite, and diatomaceous earth, or synthetic ground minerals, such as highly dispersed silicic acid, aluminium oxide, silicates, N-Methyl-2-pyrrolidone and calcium phosphates and calcium hydrogen phosphates, crushed and fractionated natural minerals, such as calcite, marble, pumice, precipitated silica, sepiolite, bentonite, river sand, zeolites, starch, sand, talc, quartz, dolomite, synthetic granules of inorganic and organic ground materials.
11. The insecticidal composition as claimed in claim 6, wherein said solvents is selected from deionized (DI) water, Nalkyl pyrrolidone, N-methyl-2-pyrrolidone, dimethylformamide (DMF),n-hexanol dimethylsulfoxide (DMSO).
12. A method for controlling insects in rice, said method comprising treating chilli crop with an insecticidal composition as claimed in claim 1.
13. A process for preparing an insecticidal composition as claimed in claim 1 as an Emulsion concentrate formulation, said process comprising:
1. Mixed charged solvent N, N- dimethyl formamide (DMF) in the mixing kettle and motorised agitation.
2. Add N-Hexanol and N-Methyl-2-pyrrolidone solvents and mixed for 30 to 60 minutes.
3. Add Slowly Chlorantraniliprole, Deltamethrin and Emamectin Technical in the mixing vessel and continue the agitation 60 -120 minutes.
4. Add BHT (Butylated hydroxylated toluene), Paraffin oil and fumaric acid, maintained agitation till 30- 60 minutes.
5. Add Anionic and non-ionic surfactants in this above mixture and run the agitation to whole mass of raw materials.
6. Analysis the batch through representative sample as per prescribed specifications.