DESC:SYNERGISTIC GRANULAR PESTICIDAL COMPOSITION

FIELD OF THE INVENTION
The present invention relates to the field of insecticidal compositions. In particular, the invention relates to a synergistic insecticidal composition comprising of (a) Fipronil, (b) at least one diamide insecticides, (c) at least one neonicotinoid insecticides, and (d) plant growth enhancer, and method for preparation thereof.

BACKGROUND OF THE INVENTION
Loss of yield due to pest damage is a major problem that most farmers face. Approximately, 20 to 40% of global crop production is lost to pests annually. Pesticides are heavily used to manage pests, dangerous insects, and several plant diseases that afflict farm crops.

Various active ingredients are used as solo or binary formulations. However, with extensive and prolonged use of solo or binary formulation, pests develop resistance, more concentrated formulations are required to be applied resulting in various adverse effects on plant health and crop yield. With the onset of resistance to pest (s), despite extensive studies on several insecticidal combinations, a synergistic effect with healthy crop is rarely observed.

CN103651438 disclose a suspending agent composed of 0.1-40% of Chlorantraniliprole, 0.1-40% of Fipronil, 0.5-15% of wetting and dispersing agent, 0-12% of antifreeze agent, 0.1-1.5% of thickener, 0.1-1% of defoaming agent, 0.1-5% of antimicrobial agent, a right amount of pH regulator and the balance of deionized water.

CN103918698 discloses a pesticidal composition containing 10-40 parts of clothianidin and 2-10 parts of fipronil, in parts by weight.

Another important challenge in pest control is the need to lower the active ingredient dose to minimize harmful environmental or toxic effects while ensuring effective pest control. Another issue is the requirement for fungicidal/insecticidal agents that are capable of effectively targeting a wide range of pests. Additionally, there is a need for pest control agents that provide both immediate knock-down activity and long-lasting effectiveness.

While it is indispensable to control pests and insects, it is also desirable to enhance plant health, including various plant improvements related to pest control and other aspects. Plant health improvement includes improved crop characteristics such as emergence, crop yields, enhanced root growth, stress tolerance (e.g. against drought, heat, salt, UV, water, and cold), reduced ethylene production and reception, increase in plant height, leaf size and colour, photosynthetic activity, and more. These improvements reduce the need for inputs like fertilizers or water, promote better germination, and enhance overall plant vigour and productivity.

However, with extensive and prolonged use of known formulations, pests develop resistance, and more concentrated formulations are required, resulting in adverse effects on plant health and crop yield. With the onset of resistance to certain pests, a combination of actives is needed that decreases the chances of resistance and improves the spectrum of pests and diseases controlled.

Therefore, there exists a need for improved insecticidal composition that is effective against pests of different crops and platforms, including sugarcane and paddy, it serves as a useful tool for managing resistance, has a broad spectrum, is environmentally safe, reduced dosage, frequency of application and improves plant health over existing formulations.

OBJECTIVES AND ADVANTAGE OF THE INVENTION
The primary objective of the invention is to provide a synergistic insecticidal composition.

Another objective of the present invention is to provide a synergistic insecticidal composition comprising at least three insecticides and at least one plant growth enhancer.

Yet another objective of the present invention is to provide a simple and economical method for preparing the synergistic composition of the present invention.

Another objective of the present invention is to provide an environment-friendly synergistic insecticidal composition.

Another objective of the present invention is to provide a synergistic insecticidal composition that helps maintain the soil's pH balance.

Another objective of the present invention is to provide an insecticidal composition that enhances soil fertility and better absorption of nutrients.

Yet another objective of the present invention is to provide an insecticidal composition that increases crop yield.

Yet another objective of the present invention is to provide a synergistic insecticidal composition that promotes plant health.

Yet another objective of the present invention is to provide a synergistic insecticidal composition with a low concentration of active ingredients and fewer application cycles.

Another objective and advantage of the present invention is to provide a stable synergistic insecticidal composition.

Some or all these and other objects of the invention can be achieved by way of the invention described hereinafter.

SUMMARY OF THE INVENTION
Accordingly, the present invention provides an insecticidal composition comprising (a) an insecticide Fipronil, (b) at least one diamide insecticides selected from Chlorantraniliprole, Cyclaniliprole and Cyantraniliprole; (c) at least one Neonicotinoid selected from Thiamethoxam and Clothianidin; and (d) plant growth enhancer and one or more customary formulation excipients.

In an aspect of the present invention, the synergistic insecticidal composition comprises of:
a) Fipronil;
b) at least one compound selected from Chlorantraniliprole, Cyclaniliprole and Cyantraniliprole;
c) at least one compound selected from Thiamethoxam and Clothianidin;
d) blend of Ethanol 2,2,2- nitrilotris-, compd. with alpha-(2,4,6-tris(1-phenylethyl)phenyl)- omega-hydroxypoly(oxy-1,2-ethanediyl) phosphate, alkyl phenol polyethanoxy ether, 2-2-oxydiethanol and dihydrogen mono oxide or sodium methyl oleyl taurate;
e) at least one plant growth enhancer;
f) one or more agriculturally acceptable excipients.

In another aspect of the present invention, the synergistic insecticidal composition comprises of:
a) Fipronil in the range of 0.01% to 5% w/w;
b) at least one diamide selected from Chlorantraniliprole, Cyclaniliprole and Cyantraniliprole in the range of 0.01% to 2% w/w;
c) at least one neonicotinoid selected from Thiamethoxam and Clothianidin in the range of 0.01% to 5% w/w;
d) sodium methyl oleyl taurate in the range of 0.01% to 20%;
e) Potassium humate in the range of 1% to 80%; and
f) one or more agriculturally acceptable excipients.

In another aspect of the present invention, the synergistic insecticidal composition comprises of:
a) Fipronil in the range of 0.01% to 5% w/w;
b) at least one diamide selected from Chlorantraniliprole, Cyclaniliprole and Cyantraniliprole in the range of 0.01% to 2% w/w;
c) at least one neonicotinoid selected from Thiamethoxam and Clothianidin in the range of 0.01% to 5% w/w;
d) blend of Ethanol 2,2,2- nitrilotris-, compd. with alpha-(2,4,6-tris(1-phenylethyl)phenyl)- omega-hydroxypoly(oxy-1,2-ethanediyl) phosphate, alkyl phenol polyethanoxy ether, 2-2-oxydiethanol and dihydrogen mono oxide in the range of 0.01% to 4%;
e) zinc in the range of 0.01% to 5%; and
f) one or more agriculturally acceptable excipients.

In another aspect of the present invention, the synergistic insecticidal composition comprises of:
a) Fipronil in the range of 0.01% to 5% w/w;
b) at least one diamide selected from Chlorantraniliprole, Cyclaniliprole and Cyantraniliprole in the range of 0.01% to 2% w/w;
c) at least one neonicotinoid selected from Thiamethoxam and Clothianidin in the range of 0.01% to 5% w/w;
d) sodium methyl oleyl taurate in the range of 0.01% to 20%;
e) Humic acid in the range of 1% to 80%; and
f) one or more agriculturally acceptable excipients.

In yet another embodiment of the present invention, the synergistic insecticidal composition comprises of:
a) Fipronil in the range of 0.01% to 5% w/w;
b) Chlorantraniliprole in the range of 0.01% to 2% w/w;
c) Thiamethoxam in the range of 0.01% to 5% w/w;
d) sodium methyl oleyl taurate in the range of 0.01% to 20%;
e) Potassium humate in the range of 1% to 80%; and
f) one or more agriculturally acceptable excipients.

In another aspect, the synergistic insecticidal composition comprises of:
a) Fipronil in the range of 0.01% to 5% w/w;
b) Chlorantraniliprole in the range of 0.01% to 2% w/w;
c) Clothianidin in the range of 0.01% to 5% w/w;
d) sodium methyl oleyl taurate in the range of 0.01 to 20%;
e) Potassium humate in the range of 1% to 80%; and
f) one or more agriculturally acceptable excipients.

In another aspect, the synergistic insecticidal composition comprises of:
a) Fipronil in the range of 0.01% to 5% w/w;
b) Chlorantraniliprole in the range of 0.01% to 2% w/w;
c) Clothianidin in the range of 0.01% to 5% w/w;
d) blend of Ethanol 2,2,2- nitrilotris-, compd. with alpha-(2,4,6-tris(1-phenylethyl)phenyl)- omega-hydroxypoly(oxy-1,2-ethanediyl) phosphate, alkyl phenol polyethanoxy ether, 2-2-oxydiethanol and dihydrogen mono oxide in the range of 0.01% to 4%;
e) zinc oxide in the range of 0.01% to 5%; and
f) one or more agriculturally acceptable excipients.

In another aspect, the synergistic insecticidal composition comprises of:
a) Fipronil in the range of 0.01% to 5% w/w;
b) Chlorantraniliprole in the range of 0.01% to 2% w/w;
c) Thiamethoxam in the range of 0.01% to 5% w/w;
d) blend of Ethanol 2,2,2- nitrilotris-, compd. with alpha-(2,4,6-tris(1-phenylethyl)phenyl)- omega-hydroxypoly(oxy-1,2-ethanediyl) phosphate, alkyl phenol polyethanoxy ether, 2-2-oxydiethanol and dihydrogen mono oxide in the range of 0.01% to 4%;;
e) zinc oxide in the range of 0.01% to 5%; and
f) one or more agriculturally acceptable excipients.

In another aspects, the present invention provides a method for preparing the synergistic insecticidal composition, comprising the steps of:
a) mixing all actives with a required quantity of dispersing and wetting agents;
b) adding water, monoethylene glycol and the remaining amount of dispersing and wetting agents sequentially;
c) adding aqueous solution of low molecular weight cellulosic ether to the mixture of step b) under continuous stirring;
d) milling the mixture of step c) to obtain an SC formulation having particle size =10 microns;
e) mixing and adding dye and xanthum gum to the SC formulation of Step d);
f) charging river sand into a blender, and uniformly spraying the SC formulation of step e) over the sand under agitation to obtain a homogenous granule;
g) adding and mixing ZnO and silica ppt. to the homogenous granules of step f) and mixing until the granules are dry.

In another aspect of the present invention, the synergistic insecticidal composition controls various pests in field crops.

In another aspect, the synergistic insecticidal composition of the present invention comprises one or more agriculturally acceptable excipients selected from the group consisting of antifreeze, dispersing agents, wetting agents, antifoaming agents, biocides, thickeners, surfactants, and solvents. Additional components may also be included, e.g., protective colloids, adhesives, thickeners, stabilizers, etc. More generally, the active materials may be combined with any solid or liquid additive, which complies with usual formulation techniques.

In another aspect of the present invention, the synergistic insecticidal composition may be formulated as Soil Applied Granules (SAG), Water Dispersible Granules (WDG), ZC formulation (ZC), dustable powder (DP), a gel, a wettable powder (WP), a suspension concentrate, a granule (GR) (such as an emulsifiable granule (EG) or more particularly a water-dispersible granule (WG)), a water-dispersible tablet (WT), jumbo formulation, pellets, dry flowable, encapsulate granules, or controlled release granules (CRG).

DETAILED DESCRIPTION OF THE INVENTION
The definitions provided herein below for the terminologies used in the present disclosure are for illustrative purpose only and in no manner limit, the scope of the present invention disclosed in the present disclosure.

All technical and scientific phrases or terms used here have the same meanings as those that a person who is skilled in the field of study of the current subject matter would understand. Although other process and materials similar, or equivalent, to those described herein may be used in the practice of the present invention, the preferred materials and process are described herein.

It is to be noted that, as used in the specification, the singular forms “a”, “an”, and “the” include plural referents unless the context clearly dictates otherwise. It should also be noted that the term “or” is generally employed in its sense, including “and/or” unless the content clearly dictates otherwise.

The expression of various quantities in terms of “% w/w” or “%” means the percentage by weight relative to the weight of the total solution or composition unless otherwise specified.

The term “active ingredient” (a.i.) or “active agent” or “actives” used herein refers to that component of the composition responsible for control and killing of pests/insects.

The terms “formulation” and “composition”, as used herein, convey the same meaning and may be used interchangeably.

The term “process” and “method” as used herein convey the same meaning and may 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. It is noteworthy that the health of a plant, when applying the composition according to the present invention, is increased independently of the pesticidal properties of the active ingredients used because the increase in health is not based upon the reduced pest pressure but instead on complex physiological and metabolic reactions which result for example in an activation of the plant's own natural defence system. As a result, the health of a plant is increased even in the absence of pest pressure.

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 “insecticide” or “insecticidal” is similar to “pesticides” or “pesticidal” and is used interchangeably in this complete specification and both convey the same meaning.

The term “Neonicotinoid” and “neonics” convey the same meaning and may be used interchangeably in this whole specification.

The terms DF formulation, WDG formulation, WS formulation, WP formulation and SC formulation are the international denominations adopted by the FAO (Food and Agriculture Organization of the United Nations) to designate dry flowable, water-dispersible granules, water-dispersible powder for slurry seed treatment, wettable powder and suspension concentrate, respectively.

The term “plants” refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits. The term “locus” of a plant, as used herein, is intended to embrace the place on which the plants are growing, where the plant propagation materials of the plants are sown or where the plant propagation materials of the plants will be placed into the soil. The term “plant propagation materials” is understood to denote generative parts of a plant, such as seeds, vegetative materials such as cutting or tubers, roots, fruits, bulbs, rhizomes and parts of plants, germinated plants and young plants which are to be transplanted after germination or after emergence from the soil. These young plants may be protected before transplantation by total or partial treatment by immersion.

The “plant growth enhancer” used herein refers to substances that help plants grow larger, healthier, and more productive. They can be used to promote root growth, increase yields, and enhance plant health. Representative “plant growth enhancers” that can be used include but are not limited to micronutrients (such as Iron (Fe), Zinc (Zn), Boron (B), Copper (Cu), Manganese (Mn), Molybdenum (Mo), auxins (Indole-3-acetic acid (IAA), Indole butyric acid (IBA), Naphthalene acetic acid (NAA), 2,4-dichlorophenoxyacetic acid (2,4-D)); Gibberellins, Cytokinins, Abscisic acid (ABA), Strigolactones, Potassium Humate, Humic Acid, Sodium Humate, Potassium Nitrate, Potassium Chloride, Potassium Sulfate or any combination thereof.

The “zinc” relates to any one of the forms Zinc Sulfate Monohydrate (ZnSO4.H2O), Zinc Sulfate Heptahydrate (ZnSO4.7H2O), Zinc Oxysulphate (ZnSO4.xZnO), Zinc Oxide (ZnO), Zinc carbonate (ZnCO3), Zinc Chloride (ZnCl2), Zinc EDTA/Zinc chelate, Zinc Gluconate, Zinc Lactate Gluconate, Zinc Polyflavonoid. The present formulation may optionally use various forms of zinc in nanoparticle form.

Zinc is a vital micronutrient that is essential for the growth and development of plants. It plays a crucial role in various physiological and biochemical processes, including enzyme activation and catalysis, photosynthesis and chlorophyll synthesis, protein synthesis and amino acid metabolism, DNA and RNA synthesis, auxin and hormone regulation, root development and nutrient uptake, stress tolerance and defence mechanisms, flower and seed formation, and protein degradation and recycling.

Khaira disease of rice is a significant problem caused by zinc deficiency, resulting in dusty brown patches on leaves and necrosis. It can lead to substantial yield losses, with up to 25% reduction in rice production. The disease is characterized by interveinal chlorosis and yellow streaks on young leaves, which develop into small brown spots on older leaves that merge and cause leaves to dry out and turn tan. The present invention composition acts synergistically to mitigate the effects of Khaira disease, offering a valuable tool for sustainable agriculture. This composition provides enhanced efficacy and a preventive profile, making it a useful tool for farmers to prevent Khaira disease and ensure higher rice yields. Zinc deficiency can lead to symptoms such as chlorosis of new leaves, necrotic spots, and reduced growth, while toxicity can cause smaller leaf size, chlorosis, and reduced root growth. Maintaining balanced zinc levels through appropriate fertilization and soil amendments is important to ensure optimal plant growth and productivity.

Further, potassium humate is a plant growth enhancer that promotes vigorous root development, better yield, and improved plant quality. It is water-soluble, which increases the quick-acting potassium content in the soil, enhancing its physical characteristics such as colour and moisture-holding capacity. Potassium humate also adds potassium to the soil, facilitating plant utilisation. It has various benefits, including improving soil fertility, water retention, and microbial activities, which enhance plant resilience to stress and disease. Additionally, it can be used as a flowering agent and accelerates seed germination and root development. Similarly, humic acid is a natural and organic substance that is crucial to plant growth and development. It enhances plant nutrient uptake, making essential nutrients more accessible. Humic acid also improves soil structure, water retention, and microbial activity, boosting plant health and productivity. Additionally, it chelates toxins from the soil, protecting plants from harmful substances. Humic acid improves root growth, seed germination, and overall plant metabolism.

According to the present invention, “increased yield” of a plant, in particular, of an agricultural, silvicultural and/ or horticultural plant, means that the yield of a product of the respective plant is increased by a measurable amount over the yield of the same product of the plant produced under the same conditions, but without the application of the composition according to the present invention.

Increased yield may be characterized, among others, by the following improved properties of the plant: increased plant weight, increased plant height, increased biomass such as higher overall fresh weight (FW), increased number of flowers per plant, higher grain yield, more tillers or side shoots (branches), larger leaves, increased shoot growth, increased leaf area index.

Another indicator for the condition of the plant is the "enhanced quality" of a plant and/or its products.

According to the present invention, enhanced quality means that certain plant characteristics, such as the content or composition of certain ingredients, are increased or improved by a measurable or noticeable amount over the same factor of the plant produced under the same conditions but without the application of the mixtures of the present invention. Enhanced quality may be characterized, among others, by following improved properties of the plant or its product: increased nutrient content, increased protein content, increased content of fatty acids, increased metabolite content, increased carotenoid content, increased sugar content, increased amount of essential amino acids, improved nutrient composition, improved protein composition, improved composition of fatty acids, improved metabolite composition, improved carotenoid composition, improved sugar composition, improved amino acids composition, improved or optimal fruit color, improved leaf color, higher storage capacity, higher processability of the harvested products.

In an exemplary embodiment, the active insecticidal compounds used in the present composition may be in the form of base or any salt form or ester form of the active which is known in the art.

In accordance with an exemplary embodiment of the invention, there is provided a synergistic insecticidal composition comprising (a) Fipronil, (b) one or more insecticide(s) selected from the class of diamides or mixture thereof; and (c) another insecticide selected from a class of neonicotinoid insecticide (s) or mixture thereof; and (d) one or more agriculturally acceptable excipients that exhibit unexpected insecticidal activity.

In another exemplary embodiment, the present invention provides a synergistic composition comprising (a) Fipronil, (b) one or more insecticide(s) selected from the class of diamides or mixture thereof; (c) another insecticide selected from a class of neonicotinoid insecticide (s) or mixture thereof; (d) blend of Ethanol 2,2,2- nitrilotris-, compd. with alpha-(2,4,6-tris(1-phenylethyl)phenyl)- omega-hydroxypoly(oxy-1,2-ethanediyl) phosphate, alkyl phenol polyethanoxy ether, 2-2-oxydiethanol and dihydrogen mono oxide; (e) at least one plant growth enhancer; (f) one or more agriculturally acceptable excipients.

In another embodiment, the diamide insecticides are selected from Chlorantraniliprole, Cyclaniliprole and Cyantraniliprole; and the neonicotinoid insecticides are selected from Thiamethoxam and Clothianidin.

In another embodiment, the plant growth enhancers are selected from Zinc, Potassium Humate, Humic Acid, Sodium Humate, Potassium Nitrate, Potassium Chloride, Potassium Sulfate or any combination thereof. Preferably, the plant growth enhancers are selected from Zinc, Potassium Humate, and Humic Acid or a combination thereof.

In another exemplary embodiment, the synergistic composition of the present invention is formulated as Capsule suspension (CS), Dispersible concentrate (DC), Dustable powder (DP), Powder for dry seed treatment (DS), Emulsifiable concentrate (EC), Emulsifiable granule (EG), Emulsion water-in-oil (EO), Emulsifiable powder (EP), Emulsion for seed treatment (ES), Emulsion oil-in-water (EW), Flowable concentrate for seed treatment (FS), Granules (GR), Micro-emulsion (ME), Oil dispersion (OD), Oil miscible flowable concentrate (OF), Oil miscible liquid (OL), Oil dispersible powder (OP), Suspension concentrate (SC), Suspension concentrate for direct application (SD), Suspo-emulsion (SE), Water soluble granule (SG), Soluble concentrate (SL), Spreading oil (SO), Water soluble powder (SP), Water soluble tablet (ST), Ultra-low volume (ULV) suspension, Tablet (TB), Ultra-low volume (ULV) liquid, Water dispersible granules (WG), Wettable powder (WP), Water dispersible powder for slurry seed treatment (WS), Water dispersible tablet (WT), a mixed formulation of CS and SC (ZC) or a mixed formulation of CS and SE (ZE), a mixed formulation of CS and EW (ZW).

In a preferred embodiment, the synergistic composition of the present invention may be formulated as Soil Applied Granules (SAG), Water Dispersible Granules (WDG), ZC formulation (ZC), dustable powder (DP), a gel, a suspension concentrate, a wettable powder (WP), a granule (GR) (such as an emulsifiable granule (EG) or more particularly a water-dispersible granule (WG)), a water-dispersible tablet (WT), jumbo formulation, pellets, dry flowable, encapsulate granules, or controlled release granules (CRG).

The present invention synergistic composition is to be applied by any of below mentioned application method:

Broadcasting provides effective control of the flow of granules such as controlled released granules (CGR) or (CR), Granules (GR) manually. It may be a sand mix or fertilizer mix broadcasting. Broadcasting may be done before or after crop sowing, planting, or transplanting or during land preparation. In sugarcane, broadcasting can be done manually by mixing it with sand or fertilizer and spreading it over cane set, in open furrow before covering it with soil at the time of planting. In rice, broadcasting may be done manually by mixing it with sand or fertilizer after crop transplanting. In groundnuts, broadcasting may be done by broadcasting evenly in the soil surface immediately after sowing.

In an exemplary embodiment, the present invention provides a Water Dispersible Granules (WDG) insecticidal composition comprising of (a) Fipronil in the range of 0.01% to 5%, (b) at least one diamide selected from Chlorantraniliprole, Cyclaniliprole and Cyantraniliprole in the range of 0.01% to 2% and (c) format least one neonicotinoid insecticide (s) selected from Thiamethoxam and Clothianidin in the range of 0.01% to 5% and (d) blend of Ethanol 2,2,2- nitrilotris-, compd. with alpha-(2,4,6-tris(1-phenylethyl)phenyl)- omega-hydroxypoly(oxy-1,2-ethanediyl) phosphate, alkyl phenol polyethanoxy ether, 2-2-oxydiethanol and dihydrogen mono oxide or sodium methyl oleyl taurate; (e) potassium humate in the range of 1% to 80%; and (f) one or more agriculturally acceptable excipients, that exhibit unexpected insecticidal activity.
In an exemplary embodiment, the present invention provides a insecticidal composition comprising of (a) Fipronil in the range of 0.01% to 5%, (b) at least one diamide selected from Chlorantraniliprole, Cyclaniliprole and Cyantraniliprole in the range of 0.01% to 2% and (c) format least one neonicotinoid insecticide (s) selected from Thiamethoxam and Clothianidin in the range of 0.01% to 5%; (d) blend of Ethanol 2,2,2- nitrilotris-, compd. with alpha-(2,4,6-tris(1-phenylethyl)phenyl)- omega-hydroxypoly(oxy-1,2-ethanediyl) phosphate, alkyl phenol polyethanoxy ether, 2-2-oxydiethanol and dihydrogen mono oxide in the range of 0.01 to 4%; (e) zinc in the range of 0.01% to 5% and (f) one or more agriculturally acceptable excipients, that exhibit unexpected insecticidal activity.

In another exemplary embodiment, the present invention provides a method for preparing a WDG formulation, by homogenous blending and agglomerating the solid active ingredient. The formulation comprises 0.01% to 5% Fipronil, 0.01% to 2% Chlorantraniliprole, Cyclaniliprole and/or Cyantraniliprole, 0.01% to 5% Thiamethoxam or/ and Clothianidin in China clay by mixing in a blender, further sufficient amount of wetting and dispersing agent is added to the blender in order to achieve a mix. Followed by adding humic acid in the range of 1% to 80% to the mix with constant stirring until a solid mass is obtained. The obtained solid mass is grinded in a jet-air mill to achieve a uniform composition or milled powdered form. The powder is then mixed with adequate water to extrude the granule formulation, and the mixture is dried for 10 to 20 minutes to produce homogenous granules formulation.

The composition of the present invention comprises inactive excipients including but not limited to dispersant, anti-freezing agent, anti-foam agent, wetting agent, surfactants, dispersants or dispersing agents, suspension aid, antimicrobial agent, thickener, quick coating agent or sticking agents (also referred to as “stickers” or “binders”) and buffering agent, carrier, binder, disintegrant, pH adjuster, preservative and/or coloring agent.

Surfactants that are used as dispersants have the ability to adsorb strongly onto a particle surface and provide a charged or stearic barrier to re-aggregation of particles. A dispersant is a substance which adsorbs onto the surface of particles and helps to preserve the state of dispersion of the particles and prevents them from re-aggregating. Dispersants are added to agrochemical formulations to facilitate dispersion and suspension during manufacture, and to ensure the particles re-disperse into water in a spray tank. They are widely used in wettable powders, suspension concentrates and water-dispersible granules. Surfactants that are used as dispersants have the ability to adsorb strongly onto a particle surface and provide a charged or steric barrier to re-aggregation of particles. The most commonly used surfactants are anionic, non-ionic, or mixtures of the two types. For wettable powder formulations, the most common dispersants are sodium lignosulphonates.

Non-ionic surfactants such as alkyl aryl ethylene oxide condensates and EO-PO block copolymers are sometimes combined with anionic surfactants such as dispersants for suspension concentrates. In recent years, new types of very high molecular weight polymeric surfactants have been developed as dispersants. These have very long hydrophobic backbones and a large number of ethylene oxide chains forming the ‘teeth’ of a ‘comb’ surfactant. These high molecular weight polymers may give very good long-term stability to suspension concentrates because the hydrophobic backbones have many anchoring points onto the particle surfaces. Examples of dispersants used herein include but not limited to sodium lingo sulphonates; poly aryl phenyl ether phosphate, tristyryl phenol ethylated /Acrylic Copolymer/ ethoxylated tristryl phenol sulphate, naphthalene sulfonic acid, sodium salt condensate with formaldehyde, ethoxylated oleyl cetyl alcohol, polyalkelene glycol ether, ethoxylated fatty alcohol; EO-PO block copolymers; and graft copolymers or mixtures thereof.

In one exemplary embodiment of the present invention, surfactants/dispersing agents are present in the range of 0.01 - 5% of the total composition.

Emulsifiers as used herein are selected from a group consisting of calcium hydroxyapatite, potassium dihydrogen phosphate, sodium hydroxide, carbonated apatite, calcium carbonate, sodium bicarbonate, tri calcium phosphate, calcium phosphates, carbonated calcium phosphates, amine monomers, lactate dehydrogenase and magnesium hydroxide, ammonium salts, magnesium salts.

Anti-freezing agent may be selected from the group consisting of polyethylene glycols, mono ethylene glycol, methoxy polyethylene glycols, glycol, propylene glycol, polypropylene glycols, poly butylene glycols, glycerin, ethylene glycol, di ethylene glycol or mixture thereof.

In one exemplary embodiment of the present invention and method, the anti-freezing agent is present in the range of 0.1-6% by wt. of the total composition.

Water-based formulations often cause foam during mixing operations in production. In order to reduce the tendency to foam, anti-foam agents are often added either during the production stage or before filling into bottles. Generally, there are two types of anti-foam agents, namely silicones and non-silicones. Silicones are usually aqueous emulsions of dimethyl polysiloxane while the non-silicone anti-foam agents are water-insoluble oils, such as octanol and nonyl, or silica. In both cases, the function of the anti-foam agent is to displace the surfactant from the air-water interface.

Defoamer/antifoaming agent are used in agrochemical formulations to prevent foaming during mixing and spraying stage and generally added to the composition as foam formation prevents the efficient filling of a container. Antifoaming agents are selected form the group consisting of silicon emulsion based anti-foam agents, siloxane polyalkyleneoxide, trisiloxane ethoxylates and mixtures thereof. Antifoaming agents for the composition of present invention are selected from silicon emulsion based anti-foam agents, siloxane polyalkyleneoxide, trisiloxane ethoxylates and mixtures thereof.

In one exemplary embodiment of the present invention and method, defoamers are present in the range of 0.001-0.2% by wt. of the total composition.

A wetting agent is a substance that, when added to a liquid, increases the spreading or penetration power of the liquid by reducing the interfacial tension between the liquid and the surface on which it is spreading. Wetting agents are used for two main functions in agrochemical formulations: during processing and manufacture to increase the rate of wetting of powders in water to make concentrates for soluble liquids or suspension concentrates, and during mixing of a product with water in a spray tank or other vessel to reduce the wetting time of wettable powders and to improve the penetration of water into water-dispersible granules. Examples of wetting agents used in Granules and water-dispersible granule formulations include but not limited to sodium lauryl sulphate; sodium dioctyl sulpho succinate; tristyrylphenol ethoxylate, non-ionic emulsifier/ mixture of non-ionic surfactants & alkoxylated alcohol/block copolymer, alkyl phenol ethoxylates; and aliphatic alcohol ethoxylates, their salts and mixtures thereof.

In one exemplary embodiment of the present invention and method, wetting agents or/and dispersing agent are present in the range of 0.01 -30% by wt. of the total composition.

In one exemplary embodiment of the present formulation and method, Polar Co-solvents used are selected from the group of Amides, ketones, Alcohol, etc., and are present in the range of 0.01 -10% by wt. of the total composition.

A filler is added to the composition to improve the handling and storage characteristics of the composition. Fillers also add mass and/or volume to the active ingredient in order to facilitate precise measurement of the doses. Suitable fillers that may be used in the composition of the present invention include, but not limited to, silicon dioxide, bentonite clay, China clay, silica, kaolin, talc, starch and diatomaceous earth and mixtures thereof.
In one exemplary embodiment of the present invention and method, fillers are present in the “Quantum Satis” i.e., Q.S quantity.

In another exemplary embodiment of the present invention and method, fillers are present in the range of 0.05- 5% by wt. of the total composition.

An embodiment of the invention provides a synergistic pesticidal composition comprising the following active ingredients in the below mentioned weight percentage range:
Fipronil or its agrochemically acceptable salts

Diamide or its agrochemically acceptable salts

Chlorantraniliprole
Cyclaniliprole
Cyantraniliprole Neonicotinoid or its agrochemically acceptable salts

Thiamethoxam
Clothianidin Plant Growth Enhancers

Zinc,
potassium humate,
Humic Acid
0.01 to 5% 0.01 to 2% 0.01 to 5% 1 to 80%

In an exemplary embodiment, preferred combinations are tabulated herein below. These combinations are only the preferred embodiments of the invention and are not to be construed as limiting:
Fipronil Chlorantraniliprole Thiamethoxam Zinc
Fipronil Chlorantraniliprole Thiamethoxam Potassium humate
Fipronil Chlorantraniliprole Thiamethoxam Humic Acid
Fipronil Chlorantraniliprole Clothianidin Zinc
Fipronil Chlorantraniliprole Clothianidin Potassium humate
Fipronil Chlorantraniliprole Clothianidin Humic Acid
Fipronil Cyantraniliprole Thiamethoxam Zinc
Fipronil Cyantraniliprole Thiamethoxam Potassium humate
Fipronil Cyantraniliprole Thiamethoxam Humic Acid
Fipronil Cyantraniliprole Clothianidin Zinc
Fipronil Cyantraniliprole Clothianidin Potassium humate
Fipronil Cyantraniliprole Clothianidin Humic Acid
Fipronil Cyclaniliprole Clothianidin Zinc
Fipronil Cyclaniliprole Clothianidin Potassium humate
Fipronil Cyclaniliprole Clothianidin Humic Acid
Fipronil Cyclaniliprole Thiamethoxam Zinc
Fipronil Cyclaniliprole Thiamethoxam Potassium humate
Fipronil Cyclaniliprole Thiamethoxam Humic Acid

In another embodiment of the present invention, the synergistic insecticidal composition comprises other phenylpyrazole compounds such as ethiprole and exemplary combinations are tabulated herein below:

Ethiprole Chlorantraniliprole Thiamethoxam Zinc
Ethiprole Chlorantraniliprole Thiamethoxam Potassium humate
Ethiprole Chlorantraniliprole Thiamethoxam Humic Acid
Ethiprole Chlorantraniliprole Clothianidin Zinc
Ethiprole Chlorantraniliprole Clothianidin Potassium humate
Ethiprole Chlorantraniliprole Clothianidin Humic Acid
Ethiprole Cyantraniliprole Thiamethoxam Zinc
Ethiprole Cyantraniliprole Thiamethoxam Potassium humate
Ethiprole Cyantraniliprole Thiamethoxam Humic Acid
Ethiprole Cyantraniliprole Clothianidin Zinc
Ethiprole Cyantraniliprole Clothianidin Potassium humate
Ethiprole Cyantraniliprole Clothianidin Humic Acid
Ethiprole Cyclaniliprole Clothianidin Zinc
Ethiprole Cyclaniliprole Clothianidin Potassium humate
Ethiprole Cyclaniliprole Clothianidin Humic Acid
Ethiprole Cyclaniliprole Thiamethoxam Fipronil
Ethiprole Cyclaniliprole Thiamethoxam Fipronil
Ethiprole Cyclaniliprole Thiamethoxam Fipronil

In another embodiment of the present invention, the synergistic insecticidal composition comprises of:
a) Fipronil in the range of 0.01% to 5% w/w;
b) Chlorantraniliprole in the range of 0.01% to 2% w/w;
c) Thiamethoxam in the range of 0.01% to 5% w/w;
d) sodium methyl oleyl taurate in the range of 0.01 to 20%;
e) Potassium humate in the range of 1% to 80%; and
f) one or more agriculturally acceptable excipients.

In another embodiment of the present invention, the synergistic insecticidal composition comprises of:
a) Fipronil in the range of 0.01% to 5% w/w;
b) Chlorantraniliprole in the range of 0.01% to 2% w/w;
c) Clothianidin in the range of 0.01% to 5% w/w;
d) sodium methyl oleyl taurate in the range of 0.01 to 20%;
e) Potassium humate in the range of 1% to 80%; and
f) one or more agriculturally acceptable excipients.

In another embodiment of the present invention, the synergistic insecticidal composition comprises of:
a) Fipronil in the range of 0.01% to 5% w/w;
b) Chlorantraniliprole in the range of 0.01% to 2% w/w;
c) Clothianidin in the range of 0.01% to 5% w/w;
d) blend of Ethanol 2,2,2- nitrilotris-, compd. with alpha-(2,4,6-tris(1-phenylethyl)phenyl)- omega-hydroxypoly(oxy-1,2-ethanediyl) phosphate, alkyl phenol polyethanoxy ether, 2-2-oxydiethanol and dihydrogen mono oxide;
e) zinc oxide in the range of 0.01% to 5%; and
f) one or more agriculturally acceptable excipients.
In another embodiment of the present invention, the synergistic insecticidal composition comprises of:
a) Fipronil in the range of 0.01% to 5% w/w;
b) Chlorantraniliprole in the range of 0.01% to 2% w/w;
c) Thiamethoxam in the range of 0.01% to 5% w/w;
d) blend of Ethanol 2,2,2- nitrilotris-, compd. with alpha-(2,4,6-tris(1-phenylethyl)phenyl)- omega-hydroxypoly(oxy-1,2-ethanediyl) phosphate, alkyl phenol polyethanoxy ether, 2-2-oxydiethanol and dihydrogen mono oxide;
e) zinc oxide in the range of 0.01% to 5%; and
f) one or more agriculturally acceptable excipients.

In another embodiment of the present invention, the synergistic insecticidal composition comprises of:
a) Fipronil in the range of 0.01% to 5% w/w;
b) Cyantraniliprole in the range of 0.01% to 2% w/w;
c) Thiamethoxam in the range of 0.01% to 5% w/w;
d) sodium methyl oleyl taurate;
e) Potassium humate in the range of 1% to 80%; and
f) one or more agriculturally acceptable excipients.

In another embodiment of the present invention, the synergistic insecticidal composition comprises of:
a) Fipronil in the range of 0.01% to 5% w/w;
b) Cyantraniliprole in the range of 0.01% to 2% w/w;
c) Clothianidin in the range of 0.01% to 5% w/w;
d) sodium methyl oleyl taurate;
e) Potassium humate in the range of 1% to 80%; and
f) one or more agriculturally acceptable excipients.

In another embodiment of the present invention, the synergistic insecticidal composition comprises of:
a) Fipronil in the range of 0.01% to 5% w/w;
b) Cyantraniliprole in the range of 0.01% to 2% w/w;
c) Clothianidin in the range of 0.01% to 5% w/w;
d) blend of Ethanol 2,2,2- nitrilotris-, compd. with alpha-(2,4,6-tris(1-phenylethyl)phenyl)- omega-hydroxypoly(oxy-1,2-ethanediyl) phosphate, alkyl phenol polyethanoxy ether, 2-2-oxydiethanol and dihydrogen mono oxide;
e) zinc oxide in the range of 0.01% to 5%; and
f) one or more agriculturally acceptable excipients.

In another embodiment of the present invention, the synergistic insecticidal composition comprises of:
a) Fipronil in the range of 0.01% to 5% w/w;
b) Cyantraniliprole in the range of 0.01% to 2% w/w;
c) Thiamethoxam in the range of 0.01% to 5% w/w;
d) blend of Ethanol 2,2,2- nitrilotris-, compd. with alpha-(2,4,6-tris(1-phenylethyl)phenyl)- omega-hydroxypoly(oxy-1,2-ethanediyl) phosphate, alkyl phenol polyethanoxy ether, 2-2-oxydiethanol and dihydrogen mono oxide;
e) zinc oxide in the range of 0.01% to 5%; and
f) one or more agriculturally acceptable excipients.

Below are the various examples for preparing different compounds according to the present invention. However, the below examples are not limited and will be further worked on within the scope of the current invention and filed:

Example 1:
Table 1: Granular Formulation

S. No Ingredients Quantity (%w/w)
1. Chlorantraniliprole A.I 0.4%
2. Fipronil A.I 0.6%
3. Clothianidin A.I 1.0%
4. Blend of Ethanol 2,2,2- nitrilotris-, compd. with alpha-(2,4,6-tris(1-phenylethyl)phenyl)- omega-hydroxypoly(oxy-1,2-ethanediyl) phosphate, Alkyl phenol polyethanoxy ether, 2-2-oxydiethanol & Dihydrogen mono oxide 0.154%
5. Sodium lignosulfonate 0.051 %
6. Monoethylene Glycol 0.26 %
7. Aqueous solution of low molecular weight cellulosic ether 0.21%
8. Water 2.0 %
9. Xanthan gum powder 0.003 %
10. Zinc Oxide (ZnO) 2.5 %
11. Ppt. Silica 1.0 %
12. River Sand QS % w/w
13. Resole violet dye 0.25 %
TOTAL 100 gm

Manufacturing process:
Preparing SC formulation
1. Preparing SC formulation by combining all the actives, i.e., Chlorantraniliprole, Fipronil, and Clothianidin, and blend of Ethanol 2,2,2- nitrilotris-, compd. with alpha-(2,4,6-tris(1-phenylethyl)phenyl)- omega-hydroxypoly(oxy-1,2-ethanediyl) phosphate, Alkyl phenol polyethanoxy ether, 2-2-oxydiethanol & Dihydrogen mono oxide along with the required dispersing and wetting agents.
2. Cleaning the entire plant before charging the required materials.
3. Water, monoethylene glycol, dispering, and wetting agents are added.
4. Adding an aqueous solution of low molecular weight cellulosic ether to the above mixture under stirring.
5. Bead milling the whole mass to obtain SC formulation having a particle size =10 microns.
6. Add and mix dye and xanthan gum solution into the SC formulation.
Preparing Granular Formulation
7. Charging base material, i.e., river sand, is put into the blender, and SC formulation is sprayed over river sand and mixed to get a homogenous granule.
8. Followed by adding ZnO and mixing thoroughly.
9. Finally, adding ppt. Silica to dry and mix for 20 minutes.

A suspension concentrate was prepared and charged into the blender, and the SC part was sprayed over river sand. The mixture was then stirred for 30-45 minutes to obtain a homogenous granule. Next, ZnO was added and mixed thoroughly, followed by precipitated silica. The method is effective for crops because it allows silica to contact the crop first, followed by micronutrient zinc, which helps overcome any deficiencies. Finally, the actives in the mixture will positively affect the crop.

Table 2: Quality Parameters of Granular Formulation

S. No Parameters Specification Results
1. Physical State Solid Solid
2. Colour Voilet color Voilet color
3. Odour Odorless Odorless
4. Bulk Density 1.1 – 1.7 1.45
5. Emulsion Stability NA NA
6. pH 1% Aq. Solution 5.0-8.5 7.20
7. Flash Point NA NA
8. Suspensibility % w/w NA NA
9. Spontaneity of Dispersion % w/w NA NA
10. Foaming NA NA

Table 3: Accelerated Storage Stability Data

Parameter 0 Day @ 25°C 14 Days @ 25°C 14 Days AHS @ 54°C
Description Violet color granules Violet color granules Violet color granules
Chlorantraniliprole A.I 0.43 0.43 0.42
Fipronil A.I 0.63 0.63 0.62
Clothianidin A.I 1.08 1.09 1.07
pH 1% Aq. Solution 7.12 7.30 6.98

Example 2:
Table 4: WG Formulation for Broadcasting Application

S. No Ingredients Quantity (%w/w)
1. Chlorantraniliprole A.I 0.3%
2. Fipronil A.I 0.5%
3. Clothianidin A.I 1.0%
4. Sodium Methyl Oleyl Taurate 5.0%
5. Linear Alcohol Derivative (GEROPON L-WET/RP) 3.0%
6. Citric acid 6.0%
7. Potassium Humate 25.0%
8. Hydrated magnesium silicate QS % w/w
Total 100 gm

Manufacturing process:
Blending of Mass and Granulation
1. Charging all ingredients in the required quantity into the Pre-blender and mixing for 20 minutes to homogenize.
2. Milling the entire mass using an air jet mill for particle size reduction, preferably below 50 microns.
3. Transfer the milled mass into a post-mixing vessel and mix for 20 minutes.
4. Add water to the mass and mix for 10 minutes to prepare dough for granulation, followed by cylindrical granulation.
Drying Granules:
5. Transfer the wet granules into the dryer, and dry the granules at a temperature of 50-60?.
6. Sample drawn for quality analysis.

Table 5: Physico-Chemical Properties of the Formulation
S. No Parameters Specification Results
1. Physical State Solid Solid
2. Colour Black color Black color
3. Odour Odorless Odorless
4. pH 1% Aq. Solution 5.0-8.5 7.20
5. Suspensibility % w/w NA NA
6. Dispersion Dispersible Dispersible

Table 6: Stability Data

Parameter 0 Day @ 25°C 14 Days @ 25°C 14 Days AHS @ 54°C
Description Black granules Black granules Black granules
Chlorantraniliprole A.I 0.33 0.32 0.30
Fipronil A.I 0.53 0.52 0.51
Clothianidin A.I 1.01 1.01 1.00
pH 1% Aq. Solution 7.20 7.32 7.48

Table 7: Formulation with High amount of Zinc oxide:
Ingredients Quantity (%w/w)
Chlorantraniliprole A.I 0.4 %
Fipronil A.I 0.6 %
Clothianidin A.I 1.0 %
Blend of Ethanol 2,2,2- nitrilotris-, compd. With alpha-(2,4,6-tris(1-phenylethyl)phenyl)- omega-hydroxypoly(oxy-1,2-ethanediyl) phosphate, Alkyl phenol polyethanoxy ether, 2-2-oxydiethanol & Dihydrogen mono oxide 0.154 %
Sodium Ligno Sulphonate 0.051 %
Monoethylene Glycol 0.26 %
Aqueous solution of low molecular weight cellulosic ether 0.21%
Water 2.0 %
Xanthan gum powder 0.003 %
ZnO 12.5 %
Ppt. Silica 1.0 %
River Sand QS % w/w
Resole violet dye 0.25 %
TOTAL 100 gm

Table 8: Analytical Data

Test Parameter 0 Day @ 25°C
Description Fails as faded appearance of final granules and dust observed
Chlorantraniliprole A. I 0.42
Fipronil A. I 0.63
Clothianidin A. I 1.01
pH 1 % Aq. Solution 7.20

Observation: As the amount of Zinc Oxide increased, dustiness increased in the formulation, which created difficulty in broadcasting, and the colour of the final product faded.

Example 3:

Bio Efficacy
Evaluation of bio-efficacy in sugarcane crop

Field evaluation of the bio efficacy of the present Insecticidal composition against Sugarcane early shoot borer.

Table 9: Experimental Details
Season Rabi
Location Phulabri, Aurangabad
Crop Sugarcane
Age of Crop 0
Temperature Range during Trial 25 to 30?
Variety CO 3102
Single plot size 5.3X6.5 (34.45 m2 )
Date of Transplanting/Sowing 20/3/2023
Number of application 1
Date of application 20/3/2023
Target Pest Early shoot borer
Method of application Broadcasting with sand

Table 10: Treatment Details
S. No. Treatments Active Ingredient (AI) (gm/ha) Dose (Kg/ha)
T1 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Zinc Oxide 2.5% GR 40+60+100+250 10
T2 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Potassium Humate 25% WG 40+60+100+2500 10
T3 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% GR 40+60+100 10
T4 Fipronil 0.3% GR + Chlorantraniliprole 0.4% GR 60+40 20+10
T5 Fipronil 0.3% + Clothianidin 0.5% GR 60+100 20+20
T6 Chlorantraniliprole 0.4% + Clothianidin 0.5% GR 40+100 10+20
T7 Fipronil 0.3% GR 60 20
T8 Chlorantraniliprole 0.4% GR 40 10
T9 Clothianidin 0.5% GR 100 20
T10 Control - -

Methodology

The experiment was conducted under field conditions at Phulabri, Aurangabad, Maharashtra, and on the sugarcane hybrid "CO 3102." The experimental design was laid in a Randomized Block Design (RBD) with three replications for each treatment. Each plot encompassed an area of 34.45 square meters. Pest counts/incidences were recorded post applications at scheduled intervals. Application of insecticides was done at the time of planting sugarcane sets.

Observations:
Pest observations were conducted 30, 45, and 60 days after the treatments were applied. Plant height and leaf width were measured 30 and 45 days after application, while the number of tillers was recorded at 45 days post-application.

Early Shoot Borer: Observation on dead hearts taken at different intervals after treatment imposition and expressed in % damage reduction over control.

Table 11: Effectiveness of different treatments against Sugarcane Early Shoot Borer
S. No. Treatments Dose Kg/ha Effectiveness of different treatments against Sugarcane Early Shoot Borer
Dead heart Percent (%) incidence Percent reduction over Control (%)
30 DAA 45 DAA 60 DAA 30 DAA 45 DAA 60 DAA
T1 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Zinc Oxide 2.5% GR 10 0.29 0.44 1.03 85.04 84.58 76.01
T2 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Potassium Humate 25% WG 10 0.30 0.46 1.06 84.52 84.04 75.17
T3 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% GR 10 0.31 0.47 1.09 84.14 83.64 74.55
T4 Fipronil 0.3% GR + Chlorantraniliprole 0.4% GR 20+10 0.72 1.25 1.97 63.51 56.09 54.00
T5 Fipronil 0.3% + Clothianidin 0.5% GR 20+20 0.65 1.13 2.10 67.04 60.35 50.91
T6 Chlorantraniliprole 0.4% + Clothianidin 0.5% GR 10+20 0.66 1.32 1.99 66.23 53.56 53.56
T7 Fipronil 0.3% GR 20 0.82 1.65 2.47 57.99 42.24 42.24
T8 Chlorantraniliprole 0.4% GR 10 0.81 1.46 2.27 58.67 48.86 46.96
T9 Clothianidin 0.5% GR 20 0.87 1.57 2.43 55.65 45.12 43.09
T10 Control - 1.96 2.85 4.28 0.00 0.00 0.00

The present invention composition, comprising Chlorantraniliprole + Fipronil + Clothianidin + Zinc Oxide and Chlorantraniliprole + Fipronil + Clothianidin + Potassium Humate, provides excellent control against dead hearts incidences caused by early shoot borer compared to other treatments.

Table 12: Effectiveness of different treatments on Sugarcane Plant height
S. No. Treatments Dose Kg/ha Effectiveness of different treatments on sugarcane plant height
Avg. Plant height in (Cm.) Percent increase over control
30 DAA 45 DAA 30 DAA 45 DAA
T1 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Zinc Oxide 2.5% GR 10 73.87 109.67 23.80 16.17
T2 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Potassium Humate 25% WG 10 71.33 106.40 19.55 12.71
T3 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% GR 10 70.33 104.40 17.88 10.59
T4 Fipronil 0.3% GR + Chlorantraniliprole 0.4% GR 20+10 69.07 104.07 15.75 10.24
T5 Fipronil 0.3% + Clothianidin 0.5% GR 20+20 68.60 103.27 14.97 9.39
T6 Chlorantraniliprole 0.4% + Clothianidin 0.5% GR 10+20 67.87 103.73 13.74 9.89
T7 Fipronil 0.3% GR 20 67.00 101.80 12.29 7.84
T8 Chlorantraniliprole 0.4% GR 10 66.47 100.87 11.40 6.85
T9 Clothianidin 0.5% GR 20 66.53 99.40 11.51 5.30
T10 Control - 59.67 94.40 0.00 0.00

The present invention composition, comprising Chlorantraniliprole + Fipronil + Clothianidin + Zinc Oxide and Chlorantraniliprole + Fipronil + Clothianidin + Potassium Humate, promotes maximum increase in the height compared to other treatments.

Table 13: Effectiveness of different insecticides on Sugarcane leaf width
S. No Treatments Dose Kg/ha Effectiveness of different insecticides on sugarcane leaf width
leaf width in (Cm.) Percent increase over control (%)
30 DAA 45 DAA 30 DAA 45 DAA
T1 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Zinc Oxide 2.5% GR 10 3.11 4.09 24.20 16.98
T2 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Potassium Humate 25% WG 10 3.05 3.96 21.81 13.36
T3 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% GR 10 2.93 3.91 17.02 11.83
T4 Fipronil 0.3% GR + Chlorantraniliprole 0.4% GR 20+10 2.90 3.79 15.69 8.59
T5 Fipronil 0.3% + Clothianidin 0.5% GR 20+20 2.88 3.82 14.89 9.35
T6 Chlorantraniliprole 0.4% + Clothianidin 0.5% GR 10+20 2.85 3.79 13.56 8.40
T7 Fipronil 0.3% GR 20 2.77 3.60 10.64 3.05
T8 Chlorantraniliprole 0.4% GR 10 2.74 3.65 9.31 4.39
T9 Clothianidin 0.5% GR 20 2.75 3.66 9.57 4.77
T10 Control - 2.51 3.49 0.00 0.00

The present invention composition, comprising Chlorantraniliprole + Fipronil + Clothianidin + Zinc Oxide and Chlorantraniliprole + Fipronil + Clothianidin + Potassium Humate, promotes maximum increase in the leaf width compared to other treatments.

Table 14: Effectiveness of different treatments on Sugarcane tillers
S. No. Treatments Dose Kg/ha Effectiveness of different treatments on sugarcane tillers
Number of tillers at Percent increase over control (%)
45 DAA 45 DAA
T1 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Zinc Oxide 2.5% GR 10 5.13 32.76
T2 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Potassium Humate 25% WG 10 4.93 27.59
T3 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% GR 10 4.80 24.14
T4 Fipronil 0.3% GR + Chlorantraniliprole 0.4% GR 20+10 4.53 17.24
T5 Fipronil 0.3% + Clothianidin 0.5% GR 20+20 4.60 18.97
T6 Chlorantraniliprole 0.4% + Clothianidin 0.5% GR 10+20 4.67 20.69
T7 Fipronil 0.3% GR 20 4.33 12.07
T8 Chlorantraniliprole 0.4% GR 10 4.27 10.34
T9 Clothianidin 0.5% GR 20 4.20 8.62
T10 Control - 3.87 0.00

The present invention composition, comprising Chlorantraniliprole + Fipronil + Clothianidin + Zinc Oxide and Chlorantraniliprole + Fipronil + Clothianidin + Potassium Humate, produces the maximum number of effective tillers compared to other tested ternary, binary, and solo compositions.

Table 15: Effectiveness of different treatments on Sugarcane yield
S. No. Treatments Dose Kg/ha Effectiveness of different treatments on sugarcane yield
Yield (t/ha) Percent increase over control (%)

T1 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Zinc Oxide 2.5% GR 10 142.49 22.86
T2 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Potassium Humate 25% WG 10 138.14 19.11
T3 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% GR 10 136.47 17.67
T4 Fipronil 0.3% GR + Chlorantraniliprole 0.4% GR 20+10 130.86 12.83
T5 Fipronil 0.3% + Clothianidin 0.5% GR 20+20 129.52 11.68
T6 Chlorantraniliprole 0.4% + Clothianidin 0.5% GR 10+20 130.28 12.33
T7 Fipronil 0.3% GR 20 126.60 9.16
T8 Chlorantraniliprole 0.4% GR 10 126.97 9.47
T9 Clothianidin 0.5% GR 20 125.50 8.21
T10 Control - 115.98 0.00
The yield data shows that the inventive combination of Chlorantraniliprole + Fipronil + Clothianidin + Zinc Oxide and Chlorantraniliprole + Fipronil + Clothianidin + Potassium Humate produces higher yields, approximately > 22% and 19%, respectively, compared to untreated.

Tables 11-15 clearly indicate a significant reduction in the population of early shoot borer in Treatment 1 (T1), which comprised Chlorantraniliprole 0.4% + Fipronil 0.6% +Clothianidin 1%, + Zinc Oxide 2.5% GR. This treatment demonstrated a notable decrease in the early shoot borer population compared to the control. Furthermore, in T1, there was a significant increase in sugarcane height, leaf width, number of tillers and yield.

Table 16: Effect of insecticide treatments on natural enemy population
S. No. Treatment Doses
(Kg/ha) Effect of insecticide treatments on natural enemy population
Spider Chrysoperla carnea
Pre-count 30 DAA 45 DAA 60 DAA Pre-count 30 DAA 45 DAA 60 DAA
T1 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Zinc Oxide 2.5% GR 10 6.67 6.00 7.00 6.33 1.33 1.67 2.00 2.00
T2 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Potassium Humate 25% WG 10 6.33 5.67 5.67 5.67 2.33 1.67 1.00 2.00
T3 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% GR 10 6.00 6.00 6.00 5.67 2.33 1.33 1.67 0.67
T4 Fipronil 0.3% GR + Chlorantraniliprole 0.4% GR 20+10 5.67 6.33 5.67 6.00 1.00 1.67 2.00 1.00
T5 Fipronil 0.3% + Clothianidin 0.5% GR 20+20 6.00 5.00 6.00 5.33 1.33 2.00 1.00 1.67
T6 Chlorantraniliprole 0.4% + Clothianidin 0.5% GR 10+20 6.33 5.67 5.67 5.33 1.67 1.33 1.67 2.33
T7 Fipronil 0.3% GR 20 6.00 6.33 6.00 5.00 2.33 1.33 2.33 2.00
T8 Chlorantraniliprole 0.4% GR 10 5.67 5.33 5.67 6.00 1.33 1.33 0.67 1.33
T9 Clothianidin 0.5% GR 20 6.00 5.33 5.33 5.33 1.33 1.00 1.67 1.33
T10 Control - 6.33 6.00 6.33 5.00 1.00 1.33 1.33 1.67

The present invention compositions, comprising Chlorantraniliprole + Fipronil + Clothianidin + Zinc Oxide and Chlorantraniliprole + Fipronil + Clothianidin + Potassium Humate, are safe on natural enemies in sugarcane ecosystems. No difference in natural enemy population count exists between the present invention treatments and the untreated control. Thus, it is evident that the present invention composition is completely safe for the natural enemy population.

Table 17: 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

Table 18: Phytotoxic effect of various treatments on sugarcane after 15 DAA at recommended dose.
S. No. Treatment details Dose kg/ha 15 DAA
L S N C V E H W
T1 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Zinc Oxide 2.5% GR 10 0 0 0 0 0 0 0 0
T2 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Potassium Humate 25% WG 10 0 0 0 0 0 0 0 0
T3 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% GR 10 0 0 0 0 0 0 0 0
T4 Fipronil 0.3% GR + Chlorantraniliprole 0.4% GR 20+10 0 0 0 0 0 0 0 0
T5 Fipronil 0.3% + Clothianidin 0.5% GR 20+20 0 0 0 0 0 0 0 0
T6 Chlorantraniliprole 0.4% + Clothianidin 0.5% GR 10+20 0 0 0 0 0 0 0 0
T7 Fipronil 0.3% GR 20 0 0 0 0 0 0 0 0
T8 Chlorantraniliprole 0.4% GR 10 0 0 0 0 0 0 0 0
T9 Clothianidin 0.5% GR 20 0 0 0 0 0 0 0 0
T10 Control - 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 19: Phytotoxic effect of various treatments on sugarcane after 15 DAA at double dose (2X)
S. No. Treatment details Dose kg/ha 15 DAA
L S N C V E H W
T1 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Zinc Oxide 2.5% GR 20 0 0 0 0 0 0 0 0
T2 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Potassium Humate 25% WG 20 0 0 0 0 0 0 0 0
T3 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% GR 20 0 0 0 0 0 0 0 0
T4 Fipronil 0.3% GR + Chlorantraniliprole 0.4% GR 40+20 0 0 0 0 0 0 0 0
T5 Fipronil 0.3% + Clothianidin 0.5% GR 40+40 0 0 0 0 0 0 0 0
T6 Chlorantraniliprole 0.4% + Clothianidin 0.5% GR 20+40 0 0 0 0 0 0 0 0
T7 Fipronil 0.3% GR 40 0 0 0 0 0 0 0 0
T8 Chlorantraniliprole 0.4% GR 20 0 0 0 0 0 0 0 0
T9 Clothianidin 0.5% GR 40 0 0 0 0 0 0 0 0
T10 Control - 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 20: Phytotoxic effect of various treatments on Sugarcane after 30 DAA at recommended dose.
S. No. Treatment details Dose kg/ha 30 DAA
L S N C V E H W
T1 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Zinc Oxide 2.5% GR 10 0 0 0 0 0 0 0 0
T2 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Potassium Humate 25% WG 10 0 0 0 0 0 0 0 0
T3 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% GR 10 0 0 0 0 0 0 0 0
T4 Fipronil 0.3% GR + Chlorantraniliprole 0.4% GR 20+10 0 0 0 0 0 0 0 0
T5 Fipronil 0.3% + Clothianidin 0.5% GR 20+20 0 0 0 0 0 0 0 0
T6 Chlorantraniliprole 0.4% + Clothianidin 0.5% GR 10+20 0 0 0 0 0 0 0 0
T7 Fipronil 0.3% GR 20 0 0 0 0 0 0 0 0
T8 Chlorantraniliprole 0.4% GR 10 0 0 0 0 0 0 0 0
T9 Clothianidin 0.5% GR 20 0 0 0 0 0 0 0 0
T10 Control - 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 21: Phytotoxic effect of various treatments on sugarcane after 30 DAA at double dose (2X)
S. No. Treatment details Dose kg/ha 30 DAA
L S N C V E H W
T1 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Zinc Oxide 2.5% GR 20 0 0 0 0 0 0 0 0
T2 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Potassium Humate 25% WG 20 0 0 0 0 0 0 0 0
T3 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% GR 20 0 0 0 0 0 0 0 0
T4 Fipronil 0.3% GR + Chlorantraniliprole 0.4% GR 40+20 0 0 0 0 0 0 0 0
T5 Fipronil 0.3% + Clothianidin 0.5% GR 40+40 0 0 0 0 0 0 0 0
T6 Chlorantraniliprole 0.4% + Clothianidin 0.5% GR 20+40 0 0 0 0 0 0 0 0
T7 Fipronil 0.3% GR 40 0 0 0 0 0 0 0 0
T8 Chlorantraniliprole 0.4% GR 20 0 0 0 0 0 0 0 0
T9 Clothianidin 0.5% GR 40 0 0 0 0 0 0 0 0
T10 Control - 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

Tables 18, 19, 20 and 21 above indicate that application of Chlorantraniliprole + Fipronil + Clothianidin + Zinc Oxide and Chlorantraniliprole + Fipronil + Clothianidin + Potassium Humate in all doses showed no phytotoxicity symptoms like leaf injury on tips, leaf injury on the surface, wilting, vein clearing, necrosis, epinasty and hyponasty in sugarcane crop. Further, as evident from tables 19 and 21, the application of Chlorantraniliprole + Fipronil + Clothianidin + Zinc Oxide and Chlorantraniliprole + Fipronil + Clothianidin + Potassium Humate at even double dose shows no phytotoxicity. Thus, applying the present invention composition may be considered completely safe for Sugarcane crops.

The above tables suggest that among all treatments, the highest percent reduction over control (% ROC) in early shoot borer population was observed with the combination of Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Zinc Oxide 2.5% GR and Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Potassium Humate 25% WG, respectivlely. These treatments were found to be the most effective in reducing early shoot borer population. Moreover, T1 and T2 also resulted in a significant increase in sugarcane height, leaf width, number of tillers and yield. The composition are safe for the natural enemy. No phytotoxicity symptoms were observed on the crop at the recommended application dose during the experiment.

Example 4:
Bio-efficacy in Paddy crop

Stem Borer: Observation on dead hearts taken at different intervals after treatment imposition and expressed in % damage reduction over control.

Field evaluation of the bio efficacy of the present Insecticidal composition against Paddy yellow stem borer (Scirophaga incertulas).

Experimental Details
Table 22
Season Kharif
Location Panchedu, Nellore, Andhra Pradesh
Crop Paddy
Age of Crop 15 days (after transplanting)
Temperature Range during Trial 25-30 °C
Variety MTU 1010
Single plot size 5 x 4 =20 m2
Date of Transplanting/Sowing 17/6/2023
Number of applications 1
Date of application 3/7/2023
Target Pest Stem Borer
Method of application Broadcasting with sand

Table 23
Treatment Details
S. No. Treatments Active Ingredient (AI) (gm/ha) Dose Kg/ha
T1 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Zinc Oxide 2.5% GR 30+45+75+187.5 7.5
T2 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Potassium Humate 25% WG 30+45+75+1875 7.5
T3 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% GR 30+45+75 7.5
T4 Fipronil 0.3% GR + Chlorantraniliprole 0.4% GR 45+30 15+7.5
T5 Fipronil 0.3% + Clothianidin 0.5% GR 45+75 15+15
T6 Chlorantraniliprole 0.4% + Clothianidin 0.5% GR 30+75 7.5+15
T7 Fipronil 0.3% GR 45 15
T8 Chlorantraniliprole 0.4% GR 30 7.5
T9 Clothianidin 0.5% GR 75 15
T10 Control - Nil

Methodology
The experiments were conducted under field conditions at Panchedu, Nellore, Andhra Pradesh, focusing on the paddy hybrid "MTU 1010." The experimental design followed a Randomized Block Design (RBD) with three replications. Each plot covered an area of 20 square meters for precise measurements. Treatments were applied at according to a predefined treatment schedule. This early application was intended to protect the paddy plants from pest infestation right from the start of their growth cycle. Pest counts were meticulously recorded following the application of treatments to assess the effectiveness of each treatment in reducing pest populations.

The crops were observed for pests 10, 20, and 30 days after applying the insecticide. We measured growth characteristics, such as plant height, at 10, 20, and 30 days after the application. We also recorded the number of tillers at these time points to assess the impact of the treatments on plant tillering, which is crucial for determining the overall yield of the paddy crop.

Table 24: Effectiveness of different treatments against Paddy stem borer
S. No. Treatments Dose Kg/Ha Effectiveness of different treatments against Paddy stem borer
Dead heart Percent (%) incidences Percent reduction over Control (%)
10 DAA 20 DAA 30 DAA 10 DAA 20 DAA 30 DAA
T1 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Zinc Oxide 2.5% GR 7.5 0.00 1.03 2.17 100.00 88.12 83.43
T2 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Potassium Humate 25% WG 7.5 0.00 1.21 2.32 100.00 86.05 82.29
T3 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% GR 7.5 0.00 1.37 2.37 100.00 84.18 81.88
T4 Fipronil 0.3% GR + Chlorantraniliprole 0.4% GR 15+7.5 0.00 2.34 4.24 100.00 73.05 67.63
T5 Fipronil 0.3% + Clothianidin 0.5% GR 15+15 0.00 2.39 4.12 100.00 72.47 68.50
T6 Chlorantraniliprole 0.4% + Clothianidin 0.5% GR 7.5+15 1.35 2.24 4.22 56.19 74.24 67.77
T7 Fipronil 0.3% GR 15 1.41 3.31 5.44 54.22 61.87 58.41
T8 Chlorantraniliprole 0.4% GR 7.5 1.41 3.34 5.56 54.22 61.54 57.51
T9 Clothianidin 0.5% GR 15 2.11 3.41 5.41 31.49 60.75 58.70
T10 Control Nil 3.07 8.69 13.09 0.00 0.00 0.00
The present invention composition, comprising Chlorantraniliprole + Fipronil + Clothianidin + Zinc Oxide and Chlorantraniliprole + Fipronil + Clothianidin + Potassium Humate, provides excellent control of dead hearts caused by stem borer compared to other treatments.

Table 25: Effectiveness of different treatments on paddy height

S. No. Treatments Dose Kg/Ha Effectiveness of different treatments on paddy plant height
Plant height at (Cm.) Percent increase over control
10 DAA 20 DAA 30 DAA 10 DAA 20 DAA 30 DAA
T1 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Zinc Oxide 2.5% GR 7.5 34.33 45.94 57.44 5.32 4.03 4.37
T2 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Potassium Humate 25% WG 7.5 34.06 45.87 57.38 4.51 3.86 4.26
T3 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% GR 7.5 33.29 45.29 56.68 2.15 2.57 3.00
T4 Fipronil 0.3% GR + Chlorantraniliprole 0.4% GR 15+7.5 32.93 44.83 56.48 1.04 1.51 2.63
T5 Fipronil 0.3% + Clothianidin 0.5% GR 15+15 33.57 44.57 56.23 2.99 0.94 2.18
T6 Chlorantraniliprole 0.4% + Clothianidin 0.5% GR 7.5+15 33.37 44.59 56.19 2.37 0.98 2.10
T7 Fipronil 0.3% GR 15 32.83 44.42 56.72 0.72 0.59 3.06
T8 Chlorantraniliprole 0.4% GR 7.5 32.97 44.43 55.97 1.15 0.60 1.71
T9 Clothianidin 0.5% GR 15 32.95 44.53 55.68 1.10 0.83 1.18
T10 Control Nil 32.59 44.16 55.03 0.00 0.00 0.00

The present invention composition, comprising Chlorantraniliprole + Fipronil + Clothianidin + Zinc Oxide and Chlorantraniliprole + Fipronil + Clothianidin + Potassium Humate, promotes maximum increase in the height compared to other treatments.

Table 26: Effectiveness of different treatments on paddy tillers
S. No. Treatments Dose Kg/Ha Effectiveness of different treatments on paddy tillers
Number of tillers at Percent increase over control (%)
10 DAA 20 DAA 30 DAA 10 DAA 20 DAA 30 DAA
T1 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Zinc Oxide 2.5% GR 7.5 11.20 13.13 18.67 26.32 21.60 17.15
T2 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Potassium Humate 25% WG 7.5 10.53 12.60 17.73 18.80 16.67 11.30
T3 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% GR 7.5 10.07 12.47 17.27 13.53 15.43 8.37
T4 Fipronil 0.3% GR + Chlorantraniliprole 0.4% GR 15+7.5 9.87 11.87 17.33 11.28 9.88 8.79
T5 Fipronil 0.3% + Clothianidin 0.5% GR 15+15 9.80 11.80 17.40 10.53 9.26 9.21
T6 Chlorantraniliprole 0.4% + Clothianidin 0.5% GR 7.5+15 9.93 11.93 17.27 12.03 10.49 8.37
T7 Fipronil 0.3% GR 15 9.67 11.73 17.20 9.02 8.64 7.95
T8 Chlorantraniliprole 0.4% GR 7.5 9.47 11.53 17.07 6.77 6.79 7.11
T9 Clothianidin 0.5% GR 15 9.13 11.67 16.73 3.01 8.02 5.02
T10 Control Nil 8.87 10.80 15.93 0.00 0.00 0.00

The present invention composition, comprising of Chlorantraniliprole + Fipronil + Clothianidin + Zinc Oxide and Chlorantraniliprole + Fipronil + Clothianidin + Potassium Humate produces maximum number of effective tillers compared to other tested ternary, binary as well as solo compositions.

Table 27: Effectiveness of different treatments on Paddy yield
S. No. Treatments Dose Kg/ha Effectiveness of different treatments on sugarcane yield
Yield (t/ha) Percent increase over control (%)

T1 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Zinc Oxide 2.5% GR 10 7.31 14.24
T2 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Potassium Humate 25% WG 10 7.13 11.46
T3 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% GR 10 7.06 10.24
T4 Fipronil 0.3% GR + Chlorantraniliprole 0.4% GR 20+10 6.92 8.16
T5 Fipronil 0.3% + Clothianidin 0.5% GR 20+20 6.90 7.81
T6 Chlorantraniliprole 0.4% + Clothianidin 0.5% GR 10+20 6.86 7.12
T7 Fipronil 0.3% GR 20 6.76 5.56
T8 Chlorantraniliprole 0.4% GR 10 6.84 6.94
T9 Clothianidin 0.5% GR 20 6.58 2.78
T10 Control - 6.40 0.00
The yield data shows that inventive combination of Chlorantraniliprole + Fipronil + Clothianidin + Zinc Oxide and Chlorantraniliprole + Fipronil + Clothianidin + Potassium Humate produces higher grain yield, which is approximately > 14% and 11%, respectively, compared to untreated.

Table 28: Effect of insecticide treatments on natural enemy population
S. No. Treatment Doses
(Kg/ha) Effect of insecticide treatment on natural enemy population
Dragon Flies Spider
Pre-count 10 DAA 20 DAA 30 DAA Pre-count 10 DAA 20 DAA 30 DAA
T1 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Zinc Oxide 2.5% GR 10 4.33 4.67 4.67 4.00 7.67 7.33 8.00 7.33
T2 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Potassium Humate 25% WG 10 4.67 5.33 4.33 4.00 7.00 6.67 7.00 6.33
T3 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% GR 10 3.33 4.33 3.67 4.33 6.67 7.00 6.67 6.33
T4 Fipronil 0.3% GR + Chlorantraniliprole 0.4% GR 20+10 4.00 4.33 4.67 4.33 7.33 7.33 6.67 7.00
T5 Fipronil 0.3% + Clothianidin 0.5% GR 20+20 3.67 3.67 4.00 4.00 7.33 6.33 7.00 6.33
T6 Chlorantraniliprole 0.4% + Clothianidin 0.5% GR 10+20 3.33 4.67 4.67 4.33 7.33 6.67 6.67 6.33
T7 Fipronil 0.3% GR 20 4.33 4.33 3.33 3.00 7.33 7.33 7.00 6.00
T8 Chlorantraniliprole 0.4% GR 10 3.33 3.67 4.67 4.33 6.33 6.33 6.67 7.00
T9 Clothianidin 0.5% GR 20 3.67 3.67 4.33 3.67 7.00 6.33 6.33 6.33
T10 Control - 4.33 4.33 4.67 4.67 6.67 7.00 7.33 7.33

The present invention compositions, comprising Chlorantraniliprole + Fipronil + Clothianidin + Zinc Oxide and Chlorantraniliprole + Fipronil + Clothianidin + Potassium Humate are safe on natural enemies in paddy ecosystems. There is no difference in natural enemy population count between the present invention treatments and the untreated control.

Evaluation of phytotoxicity of the present Insecticidal combination
Visual observations were recorded at 7, 14 and 21 days after the application (DAA) of the treatments. The parameters observed were leaf injury on tip/surface, stunting, necrosis, chlorosis, vein clearing, epinasty, hyponasty and wilting based on the 0-10 scale given in the below table. A total of 20 plants per plot were observed.

Table 29: Phytotoxic effect of various treatments on Paddy after 7 DAA at recommended dose
S. No. Treatment details Dose Kg/ha 7 DAA

L S N C V E H W
T1 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Zinc Oxide 2.5% GR 7.5 0 0 0 0 0 0 0 0
T2 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Potassium Humate 25% WG 7.5 0 0 0 0 0 0 0 0
T3 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% GR 7.5 0 0 0 0 0 0 0 0
T4 Fipronil 0.3% GR + Chlorantraniliprole 0.4% GR 15+7.5 0 0 0 0 0 0 0 0
T5 Fipronil 0.3% + Clothianidin 0.5% GR 15+15 0 0 0 0 0 0 0 0
T6 Chlorantraniliprole 0.4% + Clothianidin 0.5% GR 7.5+15 0 0 0 0 0 0 0 0
T7 Fipronil 0.3% GR 15 0 0 0 0 0 0 0 0
T8 Chlorantraniliprole 0.4% GR 7.5 0 0 0 0 0 0 0 0
T9 Clothianidin 0.5% GR 15 0 0 0 0 0 0 0 0
T10 Control Nil 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 30: Phytotoxic effect of various treatments on Paddy after 7 DAA at double dose (2X)
S. No. Treatment details Dose kg/ha 7 DAA
L S N C V E H W
T1 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Zinc Oxide 2.5% GR 15 0 0 0 0 0 0 0 0
T2 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Potassium Humate 25% WG 15 0 0 0 0 0 0 0 0
T3 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% GR 15 0 0 0 0 0 0 0 0
T4 Fipronil 0.3% GR + Chlorantraniliprole 0.4% GR 30+15 0 0 0 0 0 0 0 0
T5 Fipronil 0.3% + Clothianidin 0.5% GR 30+30 0 0 0 0 0 0 0 0
T6 Chlorantraniliprole 0.4% + Clothianidin 0.5% GR 15+30 0 0 0 0 0 0 0 0
T7 Fipronil 0.3% GR 30 0 0 0 0 0 0 0 0
T8 Chlorantraniliprole 0.4% GR 15 0 0 0 0 0 0 0 0
T9 Clothianidin 0.5% GR 30 0 0 0 0 0 0 0 0
T10 Control Nil 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 31: Phytotoxic effect of various treatments on Paddy after 14 DAA at recommended dose
S. No. Treatment details Dose Kg/ha 14 DAA
L S N C V E H W
T1 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Zinc Oxide 2.5% GR 7.5 0 0 0 0 0 0 0 0
T2 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Potassium Humate 25% WG 7.5 0 0 0 0 0 0 0 0
T3 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% GR 7.5 0 0 0 0 0 0 0 0
T4 Fipronil 0.3% GR + Chlorantraniliprole 0.4% GR 15+7.5 0 0 0 0 0 0 0 0
T5 Fipronil 0.3% + Clothianidin 0.5% GR 15+15 0 0 0 0 0 0 0 0
T6 Chlorantraniliprole 0.4% + Clothianidin 0.5% GR 7.5+15 0 0 0 0 0 0 0 0
T7 Fipronil 0.3% GR 15 0 0 0 0 0 0 0 0
T8 Chlorantraniliprole 0.4% GR 7.5 0 0 0 0 0 0 0 0
T9 Clothianidin 0.5% GR 15 0 0 0 0 0 0 0 0
T10 Control Nil 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 32: Phytotoxic effect of various treatments on Paddy after 14 DAA at double dose (2X)
S. No. Treatment details Dose kg/ha 14 DAA
L S N C V E H W
T1 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Zinc Oxide 2.5% GR 15 0 0 0 0 0 0 0 0
T2 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Potassium Humate 25% WG 15 0 0 0 0 0 0 0
T3 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% GR 15 0 0 0 0 0 0 0 0
T4 Fipronil 0.3% GR + Chlorantraniliprole 0.4% GR 30+15 0 0 0 0 0 0 0 0
T5 Fipronil 0.3% + Clothianidin 0.5% GR 30+30 0 0 0 0 0 0 0 0
T6 Chlorantraniliprole 0.4% + Clothianidin 0.5% GR 15+30 0 0 0 0 0 0 0 0
T7 Fipronil 0.3% GR 30 0 0 0 0 0 0 0 0
T8 Chlorantraniliprole 0.4% GR 15 0 0 0 0 0 0 0 0
T9 Clothianidin 0.5% GR 30 0 0 0 0 0 0 0 0
T10 Control Nil 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 33: Phytotoxic effect of various treatments on Paddy after 21 DAA at recommended dose
S. No. Treatment details Dose kg/ha 21 DAA
L S N C V E H W
T1 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Zinc Oxide 2.5% GR 7.5 0 0 0 0 0 0 0 0
T2 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Potassium Humate 25% WG 7.5 0 0 0 0 0 0 0 0
T3 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% GR 7.5 0 0 0 0 0 0 0 0
T4 Fipronil 0.3% GR + Chlorantraniliprole 0.4% GR 15+7.5 0 0 0 0 0 0 0 0
T5 Fipronil 0.3% + Clothianidin 0.5% GR 15+15 0 0 0 0 0 0 0 0
T6 Chlorantraniliprole 0.4% + Clothianidin 0.5% GR 7.5+15 0 0 0 0 0 0 0 0
T7 Fipronil 0.3% GR 15 0 0 0 0 0 0 0 0
T8 Chlorantraniliprole 0.4% GR 7.5 0 0 0 0 0 0 0 0
T9 Clothianidin 0.5% GR 15 0 0 0 0 0 0 0 0
T10 Control Nil 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 34: Phytotoxic effect of various treatments on Paddy after 21 DAA at double dose (2X)
S. No. Treatment details Dose kg/ha 21DAA
L S N C V E H W
T1 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Zinc Oxide 2.5% GR 15 0 0 0 0 0 0 0 0
T2 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Potassium Humate 25% WG 15 0 0 0 0 0 0 0 0
T3 Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% GR 15 0 0 0 0 0 0 0 0
T4 Fipronil 0.3% GR + Chlorantraniliprole 0.4% GR 30+15 0 0 0 0 0 0 0 0
T5 Fipronil 0.3% + Clothianidin 0.5% GR 30+30 0 0 0 0 0 0 0 0
T6 Chlorantraniliprole 0.4% + Clothianidin 0.5% GR 15+30 0 0 0 0 0 0 0 0
T7 Fipronil 0.3% GR 30 0 0 0 0 0 0 0 0
T8 Chlorantraniliprole 0.4% GR 15 0 0 0 0 0 0 0 0
T9 Clothianidin 0.5% GR 30 0 0 0 0 0 0 0 0
T10 Control Nil 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

Tables 29, 30, 31, 32, 33 and 34 above indicate that application of Chlorantraniliprole + Fipronil + Clothianidin + Zinc Oxide and Chlorantraniliprole + Fipronil + Clothianidin + Potassium Humate in all doses mentioned in the table showed no phytotoxicity symptoms like leaf injury on tips, leaf injury on surface, wilting, vein clearing, necrosis, epinasty and hyponasty in paddy crop. Thus, applying the treatments (T1 and T2) may be considered completely safe for paddy crops.

The results of the experiment suggest that among all the treatments tested, the combination of Chlorantraniliprole 0.4% + Fipronil 0.6% + Clothianidin 1% + Zinc Oxide 2.5% GR (T1) resulted in the highest percent reduction over control (% ROC) in stem borer population. This combination was the most effective in reducing the stem borer population in paddy. Moreover, T1 also significantly increased paddy height and the number of tillers, indicating improved plant health and productivity. No phytotoxicity symptoms were observed on the crop at the recommended application dose during the experiment, confirming the safety and efficacy of the treatment.

From the foregoing it will be observed that numerous modifications and variations can be effectuated without departing from the true spirit and scope of the novel concepts of the present invention. It is to be understood that no limitations with respect to the specific embodiments illustrated is intended or should be inferred. It should be understood that all such modifications and improvements have been deleted herein for the sake of conciseness and readability but are properly within the scope of the following claims.
,CLAIMS:We Claim:
1. A synergistic insecticidal composition comprising:
a) Fipronil;
b) at least one compound selected from Chlorantraniliprole, Cyclaniliprole and Cyantraniliprole;
c) at least one compound selected from Thiamethoxam and Clothianidin;
d) at least one plant growth enhancer; and
e) one or more agriculturally acceptable excipients.

2. The composition as claimed in claim 1, wherein the fipronil is in the range of 0.01 to 5% by weight of the composition.

3. The composition as claimed in claim 1, wherein the plant growth enhancer is selected from zinc in the range of 0.01 to 5% by weight or potassium humate in the range of 1 to 80% by weight of the composition.

4. The composition as claimed in claim 1, wherein the Chlorantraniliprole, Cyantraniliprole, Cyclaniliprole in the range of 0.01 to 2% by weight of the composition; and Thiamethoxam and Clothianidin in the range of 0.01 to 5% by weight of the composition.

5. The composition as claimed in claim 1, wherein the composition comprises of blend of Ethanol 2,2,2- nitrilotris-, compd. with alpha-(2,4,6-tris(1-phenylethyl)phenyl)- omega-hydroxypoly(oxy-1,2-ethanediyl) phosphate, alkyl phenol polyethanoxy ether, 2-2-oxydiethanol and dihydrogen mono oxide in a range of 0.01 to 4%; or sodium methyl oleyl taurate in a range of 0.01 to 20% by weight of the composition.

6. The composition as claimed in claim 1, wherein the composition is selected from Soil Applied Granules (SAG), Water Dispersible Granules (WDG), ZC formulation (ZC), dustable powder (DP), a gel, a suspension concentrate, a wettable powder (WP), a granule (GR) (such as an emulsifiable granule (EG) or more particularly a water-dispersible granule (WG)), a water-dispersible tablet (WT), jumbo formulation, pellets, dry flowable, encapsulate granules, or controlled release granules (CRG).

7. The composition as claimed in claim 1, wherein the agriculturally acceptable adjuvant is selected from the group comprising of carrier(s), surfactant(s), binder(s), disintegrating agent(s), dispersants or dispersing agent(s), wetting agents, pH modifier(s), thickener(s), biocide(s), preservative(s), anti-freezing agent(s), defoamer(s), solvents, water soluble polymer, and/or stabilizer(s) or a combination thereof.

8. The composition as claimed in claim 1, wherein the composition comprises of:
a) fipronil in the range of 0.01 to 5% by weight of the composition;
b) chlorantraniliprole in the range of 0.01 to 2% by weight of the composition;
c) thiamethoxam in the range of 0.01 to 5% by weight of the composition;
d) blend of Ethanol 2,2,2- nitrilotris-, compd. with alpha-(2,4,6-tris(1-phenylethyl)phenyl)- omega-hydroxypoly(oxy-1,2-ethanediyl) phosphate, alkyl phenol polyethanoxy ether, 2-2-oxydiethanol and dihydrogen mono oxide in the range of 0.01 to 4% by weight of the composition;
e) zinc in the range of 0.01 to 5% by weight of the composition
f) one or more agriculturally acceptable excipients.

9. The composition as claimed in claim 1, wherein the composition comprises of:
a) fipronil in the range of 0.01 to 5% by weight of the composition;
b) chlorantraniliprole in the range of 0.01 to 2% by weight of the composition;
c) Clothianidin in the range of 0.01 to 5% by weight of the composition;
d) blend of Ethanol 2,2,2- nitrilotris-, compd. with alpha-(2,4,6-tris(1-phenylethyl)phenyl)- omega-hydroxypoly(oxy-1,2-ethanediyl) phosphate, alkyl phenol polyethanoxy ether, 2-2-oxydiethanol and dihydrogen mono oxide in the range of in the range of 0.01% to 4%; by weight of the composition;
e) zinc in the range of 0.01 to 5% by weight of the composition
f) one or more agriculturally acceptable excipients.

10. The composition as claimed in claim 1, wherein the composition comprises of:
a) fipronil in the range of 0.01 to 5% by weight of the composition;
b) chlorantraniliprole in the range of 0.01 to 2% by weight of the composition;
c) thiamethoxam in the range of 0.01 to 5% by weight of the composition;
d) sodium methyl oleyl taurate in the range of 0.01 to 20% by weight of the composition;
e) potassium humate in the range of 1 to 80% by weight of the composition
f) one or more agriculturally acceptable excipients.

11. The composition as claimed in claim 1, wherein the composition comprises of:
a) fipronil in the range of 0.01 to 5% by weight of the composition;
b) chlorantraniliprole in the range of 0.01 to 2% by weight of the composition;
c) clothianidin in the range of 0.01 to 5% by weight of the composition;
d) sodium methyl oleyl taurate in the range of 0.01 to 20% by weight of the composition;
e) potassium humate in the range of 1 to 80% by weight of the composition
f) one or more agriculturally acceptable excipients.

12. A method for preparing synergistic insecticidal composition, comprising the steps of:
a) mixing all actives with a required quantity of dispersing and wetting agents;
b) adding water, monoethylene glycol and the remaining amount of dispersing and wetting agents sequentially;
c) adding aqueous solution of low molecular weight cellulosic ether to the mixture of step b) under continuous stirring;
d) milling the mixture of step c) to obtain an SC formulation having particle size =10 microns;
e) mixing and adding dye and xanthum gum to the SC formulation of Step d);
f) charging river sand into a blender, and uniformly spraying the SC formulation of step e) over the sand under agitation to obtain a homogenous granule;
g) adding and mixing ZnO and ppt. silica to the homogenous granules of step f) and mixing unitl the granules are dry.

13. The method as claimed in claim 12, wherein the actives are selected from fipronil, chlorantraniliprole, cyantraniliprole, cyclaniliprole, clothianidin and thiamethoxam.