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 Diafenthiuron, Fipronil and Dinotefuran. 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.
Certain mixtures of active compounds are proposed for pest control in the earlier literature. U.S. Patent No.4,104,376 discloses a synergistic formulation for insect control comprised of a combination of phosphorodithioate and formamidine at a ratio of 1 to 0.1 - 1.0, preferably 1 to about 0.2 - 0.5.

U. S. Patent No.4,613,617 discloses synergistic compositions for insect control comprising dione esters and other insecticides, such as pyrethroids, carba- mates and organophosphates.
U.S. Patent No.4,767,773 discloses synergistic compositions for insect control comprising benzoyl ureas and pyrethroids, carbamates, and organophosphates .
U.S. Patent No.5,187,184 discloses that synergistic compositions for insect control comprising adding aryl nitro pyrrole or arylpyrrole- carbonitrile to a compositions of aryl pyrazole carboximide provides superior pest control at lower levels of the combined active ingredients than may be achieved with the aryl nitro pyrrole or aryl pyrrole carbo nitrile or aryl pyrazole 25 carboximide applied alone at equal or higher levels than the total amount of active agent used in the combination treatment.
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 Diafenthiuron, Fipronil and Dinotefuran as its ingredients.
It is another object of the present invention to provide an insecticidal composition comprising Diafenthiuron and Fipronil as insecticidal active ingredients and Dinotefuran 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 Diafenthiuron as the first active ingredient, Fipronil as the second active ingredient and Dinotefuran 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, 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 Suspension 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.
Diafenthiuron is a pesticide, specifically an insecticide. It is a chemical compound which belongs to the thiourea group. Diafenthiuron photochemically transforms into its highly reactive metabolite, carbodiimide, which covalently and irreversibly binds to microsomal glucose-6-phosphate translocase, a part of the adenosine triphosphatase (ATPase) complex. The binding inhibits the function of the ATPase complex due to the modification of a single sulfhydryl/amino phosphate group of the 15 glucose-6-phosphate translocase. Diafenthiuron has shown high efficacy against many important agricultural pests, including mites, aphids, thrips, and whiteflies. Several studies have demonstrated the efficacy of diafenthiuron in controlling various pests affecting a variety of crops.
Fipronil is a broad –spectrum nsectiicde that belongs to the phenylpyrazole chemical family. Fipronil distrupts the insects central nervous system by blocking the ligand –gated ion channel of the GABAA receptor glutamate-gated chloride (GluCl) channels. This causes hyperexcitation of contaminated insects' nerves and muscles. Fipronil specificity towards insects is believed to be due to its greater binding affinity for the GABAA receptors of insects than to those of mammals, and for its action on GluCl channels, which do not exist in mammals.
Dinotefuran is an insecticide of the neonicotinoid class for control of insect pests such as aphids, whiteflies, thrips, leafhoppers, leaf miners, sawflies, mole cricket, white grubs, lace bugs, billbugs, beetles, mealy bugs, and cockroaches on leafy vegetables, in residential and commercial buildings, and for professional turf management. It appears that dinotefuran acts as an agonist of insect nicotinic acetylcholine receptors, but it is postulated that dinotefuran affects the nicotinic acetylcholine; binding in a mode that differs from other neonicotinoid insecticides. Rapid knockdown and death occur within several hours after contact or ingestion of dinotefuran’.
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) Diafenthiuron as the first active ingredient b) Fipronil as the second active ingredient and c) Dinotefuran as the third active ingredients. Wherein, Diafenthiuron is present in an amount ranging from 10.5-30% w/w, Fipronil is present in an amount ranging from 0.3- 18.75% w/w and Dinotefuran is present in an amount ranging from 5.0-20.0 % w/w the insecticidal composition.
In a preferred embodiment, Diafenthiuron is present in an amount 18%w/w, Fipronil is present in an amount of 8%w/w and Dinotefuran is present in an amount of 5 %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 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 Suspension concentrate comprising a Emulsifiers, Biocides, Rheology modifier, antifoam, carriers and diluents.
In an embodiment, anti-foaming agent(s) includes but not limited to, polydimethylsiloxane, magnesium stearate, silicone emulsions (such as e.g. Silikon®SRE, Wacker, Germany or Rhodorsil®, Rhodia, France), long chain alcohols, fatty acids, fatty acid esters, salts of fatty acids, fluoro organic compounds, silicone oils, mineral oils, polyether siloxane copolymer containing fumed silica, silicone defoamers, non-silicone defoamers (such as polyethers, polyacrylates), arylalkyl modified polysiloxanes, polyethylene glycol, glycerin and a suitable mixture thereof. The antifoaming agent is present in an amount of from 0.1% to 5.0% by weight based on a total weight of the composition.
In an embodiment, rheology modifier(s)includes but not limited to, natural and man-made modifiers, such as, for example, natural gums (xanthan gum, gum arabic, gun ghatti, gum karaya, gum tragacanth, guar gum, locust bean gum etc.), attagel, agar, alginic acid, alginate salt, chitin, pectin, casein, dextran, sodium carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydrophilic and hydrophobic silicas, fumed silica, fumed aluminium oxide,colloidal silicon dioxides, hydrogenated castor oils, polyvinyl alcohol, sodium alginate, sodium poly acrylate, welan gum, lignosulfonates, hydroxy methyl cellulose, dextrin, hetero polysaccharides, organic and inorganic clays, montmorillonite, bentonite clays, oxidized waxes, carboxy methylcellulose, carrageen, fucoidan, laminaran, HEUR (hydrophobically modified, ethoxylated urethane), HMPE (hydrophobically modified polyethers), HASE (hydrophobically modified, alkali-swellableemulsion), polyacrylates, polyamides, 2-aminoethyl starch, 2-hydroxy ethyl cellulose, cellulose sulfate salt, polyacrylamide, polyvinyl pyrrolidinones, 20 alkali metal salts of the maleic anhydride copolymers, alkali metal salts of poly(meth)acrylate, starch, Kelzan® (CP Kelco, U.S.A.), Rhodopol® 23 (Rhodia, France), Veegum® (R.T. Vanderbilt, U.S.A.) and Attaclay® (Engelhard Corp., NJ; USA) and a suitable mixture thereof . The Rheology modifier is present in an amount of from 0.05% to 2.0 % by weight based on a total weight of the composition.
In an embodiment, diluents(s) or solvent(s) includes but not limited to, water (Dimineralised water), aromatic hydrocarbons (e.g. toluene, xylene, naphthalene, tetrahydronaphthalene, alkylated naphthalenes or their derivatives), solvent C9, aliphatic hydrocarbons, kerosene, diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aromatic solvents (e.g. solvesso products), paraffins (e.g. mineral fractions), alcohols (e.g. methanol, ethanol, butanol, pentanol, 2-20 ethylhexanol, cyclohexanol, benzyl alcohol), ketones (e.g. cyclohexanone, gamma-butyrolactone), pyrrolidones (e.g. NMP, NOP), DMSO, acetates (glycol diacetate), glycols, fatty acid dimethylamides, fatty acids and fatty acid esters and a suitable mixture thereof. The Diluents is present in an amount of from 2.90% to 9.25 % by weight based on a total weight of the composition.
In an embodiment biocide is selected from the group comprising sodium benzoate, 1,2-benzisothiazoline-3-one, 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, BIT- 20 formaldehyde, potassium sorbate and parahydroxy benzoates or combinations thereof; The Biocides is present in an amount of from 0.10% to 5.0 % by weight based on a total weight of the composition.
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, Polymethyl methacrylate-polyethylene glycol graft copolymer, 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 0.5% to 5.0 % 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 a Suspension 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 Suspension concentrates (SC).
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 Ingredient Composition % w/w

1 Diafenthiuron Active ingredient (based on 100 % w/w ) 18.0

2 Fipronil Active Ingredient (based on 100 % w/w ) 8.0

3 Dinotefuran Active Ingredient (based on 100 % w/w ) 5.0

4 Polymethyl methacrylate-polyethylene glycol graft copolymer- dispersion and wetting agent 4.50

5 Polyoxyethylene alkyl ether 3.50

6 BIT 20- 1,2-Benzisothiozol-3(2H)-one 1.25

7 Xanthan Gum 0.15

8 Silicon defoamer
0.25
9 Demineralized water 59.35

TOTAL 100.00

Table-1 (b): Preparation methods of Suspension concentrate:

1. The half quantity of de-mineralized (D.M) water first charged into high shear mixture homogenizer of rpm 2000- 2500 then add Polymethyl methacrylate-polyethylene glycol graft copolymer- and Polyoxyethylene alkyl ether blend all together for 15- 30 minutes.
2. Add Diafenthiuron, fipronil and Dinotefuran Technical in the above mixed mass under vigorously agitation.
3. Add the remaining quantity of D.M water into mixture.
4. Silicon defoamer and BIT 20- 1,2-Benzisothiozol-3(2H)-one are added and mixed to make homogenous mass of slurry.
5. This homogenous slurry passed through beads mill at lowest temperature. The temperature of beads mill, and slurry should be maintained between 10- 16 degree centigrade, recirculate the mass till get the specified particle size 1- 10 micron.
6. After achieving the particle size xanthan gum is added under mild speed agitation. After homogenous mixing the sample send for quality check.

Table-1(c): Quality parameters of SC formulation

S.NO 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 Diafenthiuron Active Ingredient 13.50- 18.0

3 Fipronil Active Ingredient 6.00- 8.00

4 Dinotefuran ingredient 3.75 -6.25

5 Suspension after dilution into water 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. For phytotoxicity of the chemical, Diafenthiuron 18% + Fipronil 8% + Dinotefuran 5% SC on chili was also laid out separately with 3 treatments replicated 3 times.
Plot size: 5.0 × 4.0 sq m
Variety : Bullet
Targated pest species: Thrips: Scirtothrips dorsalis and Fruit borer :Helicoverpa armigera and Spodoptera litura)

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.
Tr. No Treatment details Formulation Dose Water
(ml/ha) (ml/l)
T1 Diafenthiuron 18% + Fipronil 8% + Dinotefuran 5% SC 656.25 1.31 500 L
T2 Diafenthiuron 18% + Fipronil 8% + Dinotefuran 5% SC 875 1.75 500 L
T3 Diafenthiuron 18% + Fipronil 8% + Dinotefuran 5% SC 1093.75 2.19 500 L
T4 Cyantraniliprole 7.3% w/w + Diafenthiuron 36.4% w/w SC 625 1.25 500 L
T5 Fipronil 18.87 % w/w SC 250 0.5 500 L
T6 Fipronil 5% + Buprofezin 20% SC 1000 2.0 500 L
T7 Flubendiamide 19.92 % + Thiacloprid 19.92 % w/w SC 250 0.5 500 L
T8 Indoxacarb 14.50 % + Acetamiprid 07.70 % w/w SC 500 1.0 500 L
T9 Untreated control - - 500 L

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,2 middle and 5 lower leaves of 5 randomly selected plants and averaged to get number of thrips/plant.Data was recorded as 1 day before and5, 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.

rcent 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.
C) 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
D) 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 1: Bio-Efficacy of Diafenthiuron 18% + Fipronil 8% + Dinotefuran 5% SC against Thrips: Scirtothrips dorsalis in chilli.
Treatment No. 1st Season Rabi 2023-24
1st Spraying 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 2.15 1.15 1.10 1.56 1.56 0.83 0.80 1.13 81.54
(1.63) (1.28) (1.26) (1.44) (1.44) (1.16) (1.14) (1.28)
T2 2.06 1.05 1.03 1.30 1.30 0.66 0.65 0.82 86.60
(1.60) (1.24) (1.24) (1.34) (1.34) (1.08) (1.07) (1.15)
T3 2.31 1.02 1.00 1.25 1.25 0.55 0.54 0.68 88.89
(1.68) (1.23) (1.22) (1.32) (1.32) (1.03) (1.02) (1.08)
T4 2.05 1.07 1.05 1.34 1.34 0.70 0.69 0.88 55.62
(1.60) (1.25) (1.24) (1.36) (1.36) (1.10) (1.09) (1.17)
T5 2.33 1.25 1.30 1.47 1.47 0.85 0.87 0.95 40.48
(1.68) (1.32) (1.34) (1.40) (1.40) (1.16) (1.17) (1.20)
T6 2.04 1.10 1.09 1.42 1.42 0.77 0.76 0.99 23.82
(1.59) (1.26) (1.26) (1.39) (1.39) (1.13) (1.12) (1.22)
T7 2.31 2.30 3.02 4.00 4.00 3.98 5.23 6.00 1.96
(1.68) (1.67) (1.88) (2.12) (2.12) (2.12) (2.39) (2.55)
T8 2.05 1.59 2.00 3.15 3.15 2.44 3.07 4.84 20.92
(1.60) (1.45) (1.58) (1.91) (1.91) (1.72) (1.89) (2.31)
T9 2.41 2.85 3.15 4.52 4.12 4.87 5.39 6.12 0.00
(1.71) (1.83) (1.91) (2.15) (2.15) (2.32) (2.43) (2.57)
CD (P=0.05) NS 0.04 0.03 0.10 0.10 0.12 0.11 0.18 -
SEm (±) 0.011 0.014 0.010 0.034 0.034 0.040 0.036 0.061
T1:Diafenthiuron 18% + Fipronil 8% + Dinotefuran 5% SC @ 656.25 ml/ha, T2:Diafenthiuron 18% + Fipronil 8% + Dinotefuran 5% SC @ 875 ml/ha, T3:Diafenthiuron 18% + Fipronil 8% + Dinotefuran 5% SC @ 1093.75 ml/ha, T4:Cyantraniliprole 7.3% w/w + Diafenthiuron 36.4% w/w SC @ 625 ml/ha, T5:Fipronil 18.87 % w/w SC@ 250 ml/ha, T6:Fipronil 5% + Buprofezin 20% SC@ 1000 ml/ha, T7:Flubendiamide 19.92 % + Thiacloprid 19.92 % w/w SC @ 250 ml/ha, T8:Indoxacarb 14.50 % + Acetamiprid 07.70 % w/w SC @ 500 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 2: Bio-Efficacy of Diafenthiuron 18% + Fipronil 8% + Dinotefuran 5% SC againstfruit borer(S. litura) of chilli
Treatment No. 1st Season Rabi 2023-24
1st Spraying 2nd Spraying % ROC
Mean no. oflarvae/Sqm Mean no. oflarvae/Sqm
PTC 5 DAS 10 DAS 15 DAS PTC 5 DAS 10 DAS 15 DAS
T1 1.02 0.38 0.85 2.51 2.51 0.94 2.09 2.95 32.98
(1.23) (0.94) (1.16) (1.73) (1.73) (1.20) (1.61) (1.86)
T2 1.62 0.30 0.62 1.34 1.34 0.25 0.51 1.11 74.82
(1.46) (0.89) (1.06) (1.36) (1.36) (0.86) (1.01) (1.27)
T3 1.05 0.25 0.52 1.25 1.25 0.30 0.62 1.00 77.28
(1.24) (0.87) (1.01) (1.32) (1.32) (0.89) (1.06) (1.22)
T4 1.25 0.39 0.90 2.45 2.45 0.76 1.76 2.51 42.97
(1.32) (0.94) (1.18) (1.72) (1.72) (1.12) (1.50) (1.73)
T5 1.42 0.30 0.75 1.85 1.85 0.39 0.98 2.41 45.24
(1.39) (0.89) (1.12) (1.53) (1.53) (0.94) (1.22) (1.71)
T6 1.22 0.30 0.71 1.75 1.75 0.43 1.02 2.51 42.97
(1.31) (0.89) (1.10) (1.50) (1.50) (0.96) (1.23) (1.74)
T7 1.35 0.25 0.60 1.32 1.32 0.24 0.59 1.29 70.68
(1.36) (0.87) (1.05) (1.35) (1.35) (0.86) (1.04) (1.34)
T8 1.52 0.24 0.50 1.30 1.30 0.21 0.43 1.11 74.74
(1.42) (0.86) (1.00) (1.34) (1.34) (0.84) (0.96) (1.27)
T9 1.42 1.85 2.02 2.50 2.50 3.26 3.56 4.40 0.00
(1.39) (1.53) (1.59) (1.73) (1.73) (1.94) (2.01) (2.21)
CD (P=0.05) NS 0.04 0.03 0.41 0.41 0.30 0.55 0.63 -
SEm (±) 0.011 0.014 0.010 0.14 0.14 0.10 0.18 0.21
T1:Diafenthiuron 18% + Fipronil 8% + Dinotefuran 5% SC @ 656.25 ml/ha, T2:Diafenthiuron 18% + Fipronil 8% + Dinotefuran 5% SC @ 875 ml/ha, T3:Diafenthiuron 18% + Fipronil 8% + Dinotefuran 5% SC @ 1093.75 ml/ha, T4:Cyantraniliprole 7.3% w/w + Diafenthiuron 36.4% w/w SC @ 625 ml/ha, T5:Fipronil 18.87 % w/w SC@ 250 ml/ha, T6:Fipronil 5% + Buprofezin 20% SC@ 1000 ml/ha, T7:Flubendiamide 19.92 % + Thiacloprid 19.92 % w/w SC @ 250 ml/ha, T8:Indoxacarb 14.50 % + Acetamiprid 07.70 % w/w SC @ 500 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 3: Bio-Efficacy of Diafenthiuron 18% + Fipronil 8% + Dinotefuran 5% SC againstfruit borer(H. armigera) of chilli
Treatment No. 1st Season Rabi 2023-24
1st Spraying 2nd Spraying % ROC
Mean no. oflarvae/Sqm Mean no. oflarvae/Sqm
PTC 5 DAS 10 DAS 15 DAS PTC 5 DAS 10 DAS 15 DAS
T1 1.06 0.40 0.87 2.59 2.59 0.96 2.15 3.03 27.43

(1.25) (0.95) (1.17) (1.76) (1.76) (1.21) (1.63) (1.88)
T2 1.66 0.30 0.64 1.38 1.38 0.25 0.53 1.15 72.57
(1.47) (0.90) (1.07) (1.37) (1.37) (0.87) (1.01) (1.28)
T3 1.09 0.25 0.54 1.29 1.29 0.30 0.64 1.04 75.24
(1.26) (0.87) (1.02) (1.34) (1.34) (0.90) (1.07) (1.24)
T4 1.29 0.41 0.92 2.53 2.53 0.78 1.82 2.59 38.11
(1.34) (0.95) (1.19) (1.74) (1.74) (1.13) (1.52) (1.76)
T5 1.46 0.30 0.77 1.91 1.91 0.41 1.00 2.49 40.53
(1.40) (0.90) (1.13) (1.55) (1.55) (0.95) (1.23) (1.73)
T6 1.26 0.30 0.73 1.81 1.81 0.45 1.06 2.59 38.11
(1.33) (0.90) (1.11) (1.52) (1.52) (0.97) (1.25) (1.76)
T7 1.39 0.25 0.62 1.36 1.36 0.24 0.61 1.33 68.20
(1.37) (0.87) (1.06) (1.36) (1.36) (0.86) (1.05) (1.35)
T8 1.56 0.24 0.52 1.34 1.34 0.21 0.45 1.15 72.57
(1.44) (0.86) (1.01) (1.36) (1.36) (0.84) (0.97) (1.28)
T9 1.46 2.03 2.44 2.79 2.79 3.05 3.81 4.18 0.00
(1.40) (1.59) (1.71) (1.81) (1.81) (1.88) (2.08) (2.16)
CD (P=0.05) NS 0.08 0.15 0.42 0.42 0.31 0.56 0.64 -
SEm (±) 0.011 0.03 0.05 0.14 0.14 0.10 0.19 0.21
T1:Diafenthiuron 18% + Fipronil 8% + Dinotefuran 5% SC @ 656.25 ml/ha, T2:Diafenthiuron 18% + Fipronil 8% + Dinotefuran 5% SC @ 875 ml/ha, T3:Diafenthiuron 18% + Fipronil 8% + Dinotefuran 5% SC @ 1093.75 ml/ha, T4:Cyantraniliprole 7.3% w/w + Diafenthiuron 36.4% w/w SC @ 625 ml/ha, T5:Fipronil 18.87 % w/w SC@ 250 ml/ha, T6:Fipronil 5% + Buprofezin 20% SC@ 1000 ml/ha, T7:Flubendiamide 19.92 % + Thiacloprid 19.92 % w/w SC @ 250 ml/ha, T8:Indoxacarb 14.50 % + Acetamiprid 07.70 % w/w SC @ 500 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: Effect of different treatments on semi ripe chilli fruit
Treatments
23-24 % increase yield over control
Yield
(q ha-1)
Diafenthiuron 12% + Fipronil 8% + Dinotefuran 5% SC @ 492 ml/ha 47.00 13.94
Diafenthiuron 12% + Fipronil 8% + Dinotefuran 5% SC @ 656.25 ml/ha 47.55 15.27
Diafenthiuron 12% + Fipronil 8% + Dinotefuran 5% SC @ 820 ml/ha 48.00 16.36
Diafenthiuron 12% + Fipronil 8% + Dinotefuran 5% SC @ 885.94 ml/ha 48.25 16.97
Cyantraniliprole 7.3% + Diafenthiuron 36.4% SC @ 625 ml/ha 47.25 14.55
Fipronil 18.87 SC @ 250 ml/ha 47.12 14.23
Dinotefuran 15 % EC @ 1000 ml/ha 47.10 14.18
Diafenthiuron 47% + Bifenthrin 9.4% SC @ 625 ml/ha 44.51 7.90
Untreated control 41.25 0.00
CD(p=0.05) 2.80 -

Table 3. Bio-efficacy of of Diafenthiuron 18% + Fipronil 8% + Dinotefuran 5% SC on yield of chilli crop
Treatments
23-24 % increase yield over control
Yield
(q ha-1)
Diafenthiuron 18% + Fipronil 8% + Dinotefuran 5% SC @ 656.25 ml/ha 55.50 31.83
Diafenthiuron 18% + Fipronil 8% + Dinotefuran 5% SC @ 875 ml/ha 56.00 33.02
Diafenthiuron 18% + Fipronil 8% + Dinotefuran 5% SC @ 1093.75 ml/ha 56.12 33.30
Cyantraniliprole 7.3% w/w + Diafenthiuron 36.4% w/w SC @ 625 ml/ha 50.12 19.05
Fipronil 18.87 % w/w SC@ 250 ml/ha 44.20 4.99
Fipronil 5% + Buprofezin 20% SC@ 1000 ml/ha 45.21 7.39
Flubendiamide 19.92 % + Thiacloprid 19.92 % w/w SC @ 250 ml/ha 46.25 9.86
Indoxacarb 14.50 % + Acetamiprid 07.70 % w/w SC @ 500 ml/ha 46.30 9.98
Untreated control 42.10 0.00
CD(p=0.05) 2.81 -
SEm (±) 0.97 -

Table 4: Effect of different treatments on NE C. sexmaculataof chilli crop
1st season
1st spray 2nd spray
PTC 5 DAS 10 DAS PTC 5 DAS 10 DAS 15DAS
Diafenthiuron 18% + Fipronil 8% + Dinotefuran 5% SC @ 656.25 ml/ha 2.28 2.10 2.44 2.16 3.59 3.22 3.00
(1.67) (1.61) (1.71) (1.63) (2.02) (1.93) (1.87)
Diafenthiuron 18% + Fipronil 8% + Dinotefuran 5% SC @ 875 ml/ha 1.97 2.16 2.25 2.28 3.50 3.23 3.05
(1.57) (1.63) (1.66) (1.67) (2.00) (1.93) (1.88)
Diafenthiuron 18% + Fipronil 8% + Dinotefuran 5% SC @ 1093.75 ml/ha 2.28 2.28 2.16 2.24 3.53 3.22 3.10
(1.67) (1.67) (1.63) (1.66) (2.01) (1.93) (1.90)
Cyantraniliprole 7.3% w/w + Diafenthiuron 36.4% w/w SC @ 625 ml/ha 1.96 2.24 2.20 2.07 3.55 3.26 2.97
(1.57) (1.66) (1.64) (1.60) (2.01) (1.94) (1.86)
Fipronil 18.87 % w/w SC@ 250 ml/ha 2.18 2.07 2.21 2.20 2.61 3.27 3.10
(1.64) (1.60) (1.65) (1.64) (1.76) (1.94) (1.90)
Fipronil 5% + Buprofezin 20% SC@ 1000 ml/ha 2.05 2.44 2.56 2.02 3.50 3.21 3.41
(1.60) (1.71) (1.75) (1.59) (2.00) (1.93) (1.98)
Flubendiamide 19.92 % + Thiacloprid 19.92 % w/w SC @ 250 ml/ha 2.20 2.25 2.38 2.04 2.96 3.02 3.00
(1.64) (1.66) (1.70) (1.59) (1.86) (1.88) (1.87)
Indoxacarb 14.50 % + Acetamiprid 07.70 % w/w SC @ 500 ml/ha 2.24 2.16 2.25 2.17 2.85 3.56 3.06
(1.66) (1.63) (1.66) (1.63) (1.83) (2.01) (1.89)
Untreated control 2.25 2.20 2.16 2.19 3.47 3.83 4.82
(1.66) (1.64) (1.63) (1.64) (1.99) (2.08) (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 Diafenthiuron 18% + Fipronil 8% + Dinotefuran 5% SC@ 1325 ml/ha were recorded at 1, 3, 5, 7, 10 and 15 after first spray using the scores shown below:

Scores used for phytotoxicity study
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 5. Evaluation of Diafenthiuron 18% + Fipronil 8% + Dinotefuran 5% SC for phytotoxicity on chilli crop (based on 20 leaves sample/ replication) (1st season)
Treatments Leaves injury on tips or surface Wilting Vein clearing Necrosis Epinasty Hyponasty
Untreated control 0 0 0 0 0 0
Diafenthiuron 18% + Fipronil 8% + Dinotefuran 5% SC @ 875 ml/ha 0 0 0 0 0 0
Diafenthiuron 18% + Fipronil 8% + Dinotefuran 5% SC @ 1750 ml/ha 0 0 0 0 0 0
* Observation were taken at 0, 1, 3, 5, 7, 10 & 15 Days after application in both the season

Results and Conclusion:
During the first season study, the crop showed varied 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): Data presented in Table 1 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. Diafenthiuron 18% + Fipronil 8% + Dinotefuran 5% SC @ 1093.75 ml/ha was found most efficacious among the treatments and it was on par with its lower dose Diafenthiuron 18% + Fipronil 8% + Dinotefuran 5% SC @ 875 ml/ha. While, maximum population of thrips was found in untreated control plot.
Effect of treatments on Fruit borers (Helicoverpa armigera and Spodoptera sp.):Table 2 revealed that, Diafenthiuron 18% + Fipronil 8% + Dinotefuran 5% SC @ 1093.75 ml/ha was found most efficacious among the treatments and gave the maximum fresh semi ripe chilli fruit and it was on par with Diafenthiuron 18% + Fipronil 8% + Dinotefuran 5% SC @ 875 ml/ha.
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 did not find any significant reduction of the lady bird beetle population. (Table 4).
Effect of Diafenthiuron 18% + Fipronil 8% + Dinotefuran 5% SC on crop health:Table 5 showed that, no phytotoxic symptoms was observed due to application of Diafenthiuron 18% + Fipronil 8% + Dinotefuran 5% SC @ 1750 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 3.All the insecticidal treatments significantly increased the yield as compared to the control. Diafenthiuron 18% + Fipronil 8% + Dinotefuran 5% SC @ 1093.75 ml/ha, gave the maximum yield and it was found on par with Diafenthiuron 18% + Fipronil 8% + Dinotefuran 5% SC @ 875 ml/ha.

Conclusion: The above results clearly showed that, the Diafenthiuron 18% + Fipronil 8% + Dinotefuran 5% SC @ 875 and1093.75 ml/ha effectively controlled chilli thrips and fruit borers and produced maximum fruit yield of chilli. Two doses of Diafenthiuron 18% + Fipronil 8% + Dinotefuran 5% SC @ 875 and 1093.75 ml/ha was safe to coccinellid natural enemies which were frequently observed on the chilli crop. The chemical even at higher doses Diafenthiuron 18% + Fipronil 8% + Dinotefuran 5% SC @ 875 and 1750 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, Diafenthiuron 18% + Fipronil 8% + Dinotefuran 5% SC @ 875 and 1093.75 ml/hamay be recommended for effective management of sucking pest complex and fruit borer of chilli.
,CLAIMS:1. An insecticidal composition comprising:
a) Diafenthiuron in an amount ranging from 10.5 to 30% w/w,
b) Fipronil in an amount ranging from 0.3 to 18.75% w/w; and
c) Dinotefuran in an amount ranging from 5.0 to 20%w/w.
2. The insecticidal composition as claimed in claim 1, wherein Diafenthiuron is present in an amount of 18% w/w, Fipronil is present in an amount of 8% w/w and Dinotefuran is present in an amount of 5% 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 Suspension concentrate (SC).
6. The insecticidal composition as claimed in claim 5, comprising at least a Emulsifier; at least Biocides, Rheology modifier, antifoam, carriers, 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, Polymethyl methacrylate-polyethylene glycol graft copolymer, fatty esters of polyhydric alcohol esters, Polyoxyethylene alkyl ether, Blend (Non-ionic- Alcohol ethoxylates) and Ionic- (Alkylarylsulphonates) .
8. The insecticidal composition as claimed in claim 6, wherein said Rheology modifier is selected from natural gums (xanthan gum, gum arabic, gun ghatti, gum karaya, gum tragacanth, guar gum, locust bean gum etc.), attagel, agar, alginic acid, alginate salt, chitin, pectin, casein, dextran, sodium carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydrophilic and hydrophobic silicas, fumed silica, fumed aluminium oxide,colloidal silicon dioxides, hydrogenated castor oils, polyvinyl alcohol, sodium alginate, sodium poly acrylate, welan gum, lignosulfonates, hydroxy methyl cellulose, dextrin, hetero polysaccharides, organic and inorganic clays, montmorillonite, bentonite clays, oxidized waxes, carboxy methylcellulose, carrageen.
9. The insecticidal composition as claimed in claim 6 , wherein said Biocides is selected from sodium benzoate, 1,2-benzisothiazoline-3-one, 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, BIT- 20 formaldehyde, potassium sorbate and parahydroxy benzoates.
9. The insecticidal composition as claimed in claim 6, wherein said antifoaming agent is selected from polydimethylsiloxane, magnesium stearate, silicone emulsions,long chain alcohols, fatty acids, fatty acid esters, salts of fatty acids, fluoro organic compounds, BIT 20- 1,2-Benzisothiozol-3(2H)-one, silicone oils, mineral oils, polyether siloxane copolymer containing fumed silica, silicone defoamers, non-silicone defoamers (such as polyethers, polyacrylates), arylalkyl modified polysiloxanes, polyethylene glycol, glycerin.
10. The insecticidal composition as claimed in claim 6, wherein said Diluents is selected from deionized (DI) water, Dimineralised water Nalkyl pyrrolidone, N-methyl-2-pyrrolidone, dimethylformamide (DMF),n-hexanol dimethylsulfoxide (DMSO).
11. A process for preparing an insecticidal composition as claimed in claim 1 as an Suspension concentrate formulation, said process comprising:
1. The half quantity of de-mineralized (D.M) water first charged into high shear mixture homogenizer of rpm 2000- 2500 and then add Polymethyl methacrylate-polyethylene glycol graft copolymer and Polyoxyethylene alkyl ether blend all together for 15- 30 minutes.
2. Add Diafenthiuron, fipronil and Dinotefuran Technical in the above mixed mass under vigorously agitation.
3. Add the remaining quantity of D.M water into mixture.
4. Silicon defoamer and BIT 20- 1,2-Benzisothiozol-3(2H)-one are added and mixed to make homogenous mass of slurry.
5. This homogenous slurry passed through beads mill at lowest temperature. The temperature of beads mill, and slurry should be maintained between 10- 16 degree centigrade, recirculate the mass till get the specified particle size 1- 10 micron.
6. After achieving the particle size xanthan gum is added under mild speed agitation. After homogenous mixing the sample send for quality check.