DESC:FIELD OF THE INVENTION:

The present invention relates to synergistic insecticidal formulation comprising A) Chlorantraniliprole B) at least one insecticide selected from Fipronil, Bifenthrin and Chlorpyrifos C) at least one more insecticide selected from Bifenthrin, Lambda Cyhalothrin, Chlorpyrifos, Cartap Hydrochloride and Thiocyclam Hydrogen Oxalate with one or more inactive excipients. The present invention also relates to process for preparing the said formulation and its use in crops.

BACKGROUND OF THE INVENTION

Chlorantraniliprole was first disclosed WO 03/015518. Chlorantraniliprole is chemically known as 3-bromo-4'-chloro-1-(3-chloro-2-pyridyl)-2'-methyl-6'-(methylcarbamoyl)pyrazole-5-carboxanilide and having chemical structure as below;

Chlorantraniliprole has efficient mechanism which is activated by ryanodine receptor, excessive release of intracellular stores of calcium ions, resulting in the death of the insect paralysis. Chlorantraniliprole is efficient broad-spectrum, for the purpose of Noctuidae phosphorus wing, bore fruit moth, leaf roller Branch, flour moth and other mouth ColeopteraCurculionidae, Chrysomelidae, DipteraAgromyzidae etc. are good control effect.

Fipronil is an insecticide of the phenylpyrazoles class and an active ingredient of one of the popular ectoparasiticide veterinary products, Frontline. Frontline is commonly used on dogs and cats to kill fleas, and all stages of ticks (brown dog ticks, American dog ticks, lone star ticks) which may carry Lyme disease, and mites. Fipronil is also formulated as insect bait for roaches, ants, and termites; as a spray for pets; and as a granular form on turf and golf courses.

Bifenthrin is a pyrethroid insecticide. Pyrethroids are synthetic compounds made to mimic the pyrethrins that are refined from chemicals found in chrysanthemum flowers. Bifenthrin is a broad-spectrum insecticide that works by interfering with a nerve cell's ability to send a normal signal by jamming open tiny gates on the cell that need to open and close rapidly to carry the message. Bifenthrin is used in agriculture and residential settings, both indoors and outdoors.

Chlorpyrifos is a broad spectrum insecticide, a chemical used to kill a wide variety of insects. It was introduced in 1965. While originally used primarily to kill mosquitoes in the immature, larval stage of development, chlorpyrifos is no longer registered for this use. Chlorpyrifos is effective in controlling a variety of insects, including cutworms, corn rootworms, cockroaches, grubs, flea beetles, flies, termites, fire ants, and lice. It is used as an insecticide on grain, cotton, field, fruit, nut and vegetable crops, and well as on lawns and ornamental plants. Chlorpyrifos is available in emulsifiable concentrate, dust, flowable, pellet, spray, granular and wettable powder formulations. Chlorpyrifos acts on pests primarily as a contact poison, with some action as a stomach poison. It is a nonsystemic contact chemical, meaning that it is acts only where it comes into direct contact with plant tissues, and is not transported to other plant parts. Chlorpyrifos is one of a class of insecticides referred to as organophosphates. These chemicals act by interfering with the activities of cholinesterase, an enzyme that is essential for the proper working of the nervous systems of both humans and insects. Please refer to the Toxicology Information Brief on cholinesterase-inhibition for a more detailed description of this topic.

Lambda cyhalothrin is a synthetic pyrethroid insecticide and acaricide used to control a wide range of pests in a variety of applications. Pests controlled include aphids, Colorado beetles and butterfly larvae. Crops on which it may be applied include cotton, cereals, hops, ornamentals, potatoes, vegetables or others. Lambda cyhalothrin is available as an emulsifiable concentrate, wettable powder or ULV liquid and is commonly mixed with buprofezin, pirimicarb, dimethoate or tetramethrin. It is compatible with most other insecticides and fungicides.

Cartap is a pesticide that was first introduced into the market in Japan in 1967. Its commercial names include Padan, Kritap, AG-Tap, Thiobel, and Vegetox. Its basic chemical structure is S, S-[2-(dimethylamino)-1, 3-propanediyl] dicarbamothioate. It is commonly used as a hydrochloride (C7H15N3O2S3HCl). Cartap is essentially a contact and stomach poison. It is used for the control of chewing and sucking pests and results in insect paralysis. It has been categorized as a high-effectiveness, low-toxicity, and low-residue pesticide used in rice and sugarcane fields.

Thiocyclam hydrogen oxalate is very effective against the rice striped borer (Chilo suppressalis),the yellow stemborer (Tryporyza incertulas),the rice leaf folder (Chaphalocrocis medinalis) and the rice thrip (Baliothrips biformis). Results of root-zone application showed that thiocyclam hydrogen oxalate is also a good systemic insecticide, when used at a rate of1.5 kg ai/ha.It is very effective in controlling rice borers and thrips by roof-zone application. In view of the fact that thiocyclam hydrogen oxalate belongs to a novel class of insecticides including cartap, and "dimehypo" which presumably acts by the interruption of the nerve impulse transmission at the synapses by blocking the acetylcholine receptors, it is a promising compound for the control of rice insects resistant to organochlorine, organophosphorus and caroamate insecticides.

CN103109823A relates to novel composition butene-fipronil and chlorantraniliprole pesticide composition. The butene-fipronil and chlorantraniliprole pesticide composition comprises the components of butene-fipronil and chlorantraniliprole serving as active ingredients, as well as the balance of a pesticide adjuvant, wherein the weight ratio of the butene-fipronil and the chlorantraniliprole is (1:20)-(20:1), and the sum of the weight of the butene-fipronil and the chlorantraniliprole accounts for 0.1-80% of the weight of the composition.

CN104273157A relates to an efficient insecticide composition for killing agricultural pests. The efficient insecticide composition comprises the following components in parts by weight: 30 parts of thiacloprid, 25 parts of chlorantraniliprole and 35 parts of bifenthrin. The efficient insecticide composition disclosed by the invention has a remarkable synergetic effect, is capable of reducing the consumption of active ingredients, lowering the use cost, delaying the generation of pest resistance to insecticides, and effectively reducing the environment pollution and pesticide residue, and has a remarkable effect of killing pests such as plutella xylostella, beet armyworm, rice leaf folder, cotton bollworm, pink worms, spider mites and monochamus alternatus hope; meanwhile, the damage to the environment can be reduced.

CN102113516A discloses an insect killing compound containing chlorantraniliprole, which is prepared by two effective ingredients A and B. The ingredient A is chlorantraniliprole, the ingredient B is one of high-efficiency cypermethrin, trifluoro-cypermethrin, dursban, profenofos, dipterex, diafenthiuron, chlorfenapyr, emamectin benzoate, pleocidin, tebufenozide, hexaf lumuron, chlorfenapyr, pyridaben, acetamiprid, isoprocarb, dimehypo and cartap, and the composed mass ratio of the effective ingredient A to the ingredient B is 1:60-60:1. The accumulated mass percent of the two ingredients A and B accounts 1%-85% of the total mass of the compound. In the invention, the blending of the two active ingredients is utilized, so that the effect is improved obviously, the dosage of effective ingredients is reduced, and the drug resistance of insects and mites on the chlorantraniliprole is delayed.

CN 200910069468 relates to novel composition comprising chlorantraniliprole with synergistic effective dose, abamectin or emamectin benzoate, and one of cyhalothrin, dursban, diazinon, acetamiprid, cypermethrin, alpha cypermethrin, thiamethoxam, thiacloprid, fenvalerate, propargite, diafenthiuron, benfuracarb, azocyclotin, buprofezin, ethofenprox, phonamiphos, fipronil, flufenoxuron, monosultap, dimehypo, imidacloprid, flufenoxuron, chlorfluazuron, pleocidin and tebufenozide, wherein the mass percentage of the three compositions is that: the chlorantraniliprole is 1 to 35 percent, the abamectin or the emamectin benzoate is 1 to 10 percent, and any one of the insecticides is 1 to 50 percent. The invention discloses a process for processing the compositions and application of the compositions in preparing insecticides for controlling agricultural, forestry and gardening insect pests.

However still there is a need for a synergistic insecticidal formulation which overcomes some of the existing problems and can be prepared easily without much complex manufacturing process.

Inventors of the present invention have surprisingly found that the insecticidal formulation comprising synergistically effective amounts A) Chlorantraniliprole B) at least one insecticide selected from Fipronil, Bifenthrin and Chlorpyrifos C) at least one more insecticide selected from Bifenthrin, Lambda Cyhalothrin, Chlorpyrifos, Cartap Hydrochloride and Thiocyclam Hydrogen Oxalate with one or more inactive excipients described herein in can provide solution to the above mentioned problems. Further the present invention increase efficacy against target insect-pests, broaden the activity means to control more than one insect-pests at a time, reduce the total loading of insecticides in to the environment, provide safety to the applicators and crop ecosystem and last but not least delay or to manage resistance development.

SUMMARY OF THE INVENTION

It is an aspect of the present invention is to provide, with a view to effective resistance management and effective control of harmful insects, at application rates which are as low as possible, compositions which, at a reduced total amount of active compounds applied, have improved activity against the harmful pests and a broadened activity spectrum, in particular for certain indications.

We have accordingly found that this object is achieved by the present synergistic insecticidal formulation comprising A) Chlorantraniliprole B) at least one insecticide selected from Fipronil, Bifenthrin and Chlorpyrifos C) at least one more insecticide selected from Bifenthrin, Lambda Cyhalothrin, Chlorpyrifos, Cartap Hydrochloride and Thiocyclam Hydrogen Oxalate with one or more inactive excipients, wherein at anytime two insecticides are present along with Chlorantraniliprole.

Accordingly, as per another aspect, the present invention provides a method of preparing the synergistic insecticidal formulation comprising A) Chlorantraniliprole B) at least one insecticide selected from Fipronil, Bifenthrin and Chlorpyrifos C) at least one more insecticide selected from Bifenthrin, Lambda Cyhalothrin, Chlorpyrifos, Cartap Hydrochloride and Thiocyclam Hydrogen Oxalate with one or more inactive excipients, wherein at any time two insecticides are present along with Chlorantraniliprole.

Accordingly, in a yet another aspect, the present invention provides a method of protecting a plant propagation material, a plant, parts of a plant and/or plant organs that grow at a later point in time against pathogenic damage or pest damage by applying to the plant propagation material an insecticidal formulation defined in the first aspect.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides solution to all the problems mentioned above by providing the insecticidal formulation.

The present invention provides synergistic insecticidal formulation comprising A) Chlorantraniliprole B) at least one insecticide selected from Fipronil, Bifenthrin and Chlorpyrifos C) at least one more insecticide selected from Bifenthrin, Lambda Cyhalothrin, Chlorpyrifos, Cartap Hydrochloride and Thiocyclam Hydrogen Oxalate with one or more inactive excipients, wherein at any time two insecticides are present along with Chlorantraniliprole.

"Effective amounts” as mentioned herein means that amount which, when applied treatment of crops, is sufficient to effect such treatment.

The term “formulation” and “composition” as used herein conveys the same meaning and can be used interchangeably.

The formulation or composition of the present invention can be in various physical forms, for example in the form of a GR (Granules, Soil Applied Granules), CR Granules (Controlled/Sustained Release Granules), MS (Microsphere/Microcapsule Granules, SG (Soluble Granules), WG or WDG (Water Dispersible Granules), WP (Wettable Powder), SC (Suspension Concentrate), FS (Flowable Suspsension), CS (Capsule Suspension), SE (Suspo Emulsion), ZE (A mixed formulation of CS and SE), ZW (A mixed formulation of CS and EW) and OD (Oil Dispersion).

As per one embodiment, synergistic insecticidal formulation comprising A) Chlorantraniliprole B) at least one insecticide selected from Fipronil, Bifenthrin and Chlorpyrifos C) at least one more insecticide selected from Bifenthrin, Lambda Cyhalothrin, Chlorpyrifos, Cartap Hydrochloride and Thiocyclam Hydrogen Oxalate with one or more inactive excipients, wherein at any time two insecticides are present along with Chlorantraniliprole:

Compound A Compound B Compound C
Chlorantraniliprole Fipronil
Bifenthrin
Chlorpyrifos Bifenthrin
Lambda Cyhalothrin
Chlorpyrifos
Cartap Hydrochloride
Thiocyclam Hydrogen Oxalate
Preferred combination are as follows:
Chlorantraniliprole Fipronil Bifenthrin
Chlorantraniliprole Fipronil Lambda cyhalotrhin
Chlorantraniliprole Fipronil Chlorpyrifos
Chlorantraniliprole Fipronil Cartap Hydrochloride
Chlorantraniliprole Fipronil Thiocyclam Hydrogen Oxalate
Chlorantraniliprole Bifenthrin Chlorpyrifos
Chlorantraniliprole Bifenthrin Cartap Hydrochloride
Chlorantraniliprole Bifenthrin Thiocyclam Hydrogen Oxalate
Chlorantraniliprole Chlorpyrifos Lambda cyhalotrhin
Chlorantraniliprole Chlorpyrifos Cartap Hydrochloride
Chlorantraniliprole Chlorpyrifos Thiocyclam Hydrogen Oxalate
0.1-20% 0.1-30% 0.1-50%

According to a specific embodiment, the application rates of Chlorantraniliprole are from 5 g/ha to 80 g/ha. According to a specific embodiment, the application rates of Fipronil are from 10 g/ha to 100 g/ha. According to a specific embodiment, the application rates of Bifenthrin are from 10 g/ha to 100 g/ha. According to a specific embodiment, the application rates of Lambda cyhalothrin are from 5 g/ha to 100 g/ha. According to a specific embodiment, the application rates of Chlorpyrifos are from 100 g/ha to 1000 g/ha. According to a specific embodiment, the application rates of Cartap hydrochloride are from 100 g/ha to 750 g/ha. According to a specific embodiment, the application rates of Thiocyclam Hydrogen Oxalate are from 100 g/ha to 750 g/ha.

In another embodiment of the present invention of synergistic insecticidal formulation is effective for control of Insect-pests in the crops selected from GMO (Genetically Modified Organism) and Non GMO varieties of Cotton (Gossypium spp.), Jute (Corchorus oliotorus), Paddy (Oryza sativa), Wheat (Triticum aestavum), Barley (Hordeum vulgare), Maize (Zea mays), Sorghum (Sorghum bicolor), Ragi (Eleusine coracana), Pearl millet (Pennisetum glaucum), Sugarcane (Saccharum officinarum) , Sugarbeet (Beta vulgaris), Soybean (Glycin max), Peanut (Arachis hypogaea), Sunflower (Helianthus annuus) , Mustard (Brassica juncea), Rape seed (Brassica napus), Linseed (Linum usitatissimum), Sesame (Sesamum indicum), Castor (Ricinus communis), Green gram (Vigna radiata), Black gram (Vigna mungo), Chickpea (Cicer aritinum), Cowpea (Vigna unguiculata), Redgram (Cajanus cajan), Frenchbean (Phaseolus vulgaris), Indian bean (Lablab purpureus), Horse gram (Macrotyloma uniflorum), Field pea (Pisum sativum), Cluster bean (Cyamopsis tetragonoloba), Lentils (Lens culinaris), Brinjal (Solanum melongena), Cabbage (Brassica oleracea var. capitata), Cauliflower (Brassica oleracea var. botrytis), Okra (Abelmoschus esculentus) , Onion (Allium cepa L.), Tomato (Solanum lycopersicun) , Potato (Solanum tuberosum) , Sweet potato (Ipomoea batatas), Chilly (Capsicum annum), Garlic (Allium sativum), Cucumber (Cucumis sativus), Muskmelons (Cucumis melo), Watermelon (Citrullus lanatus), Bottle gourd (Lagenaria siceraria), Bitter gourd (Momordica charantia), Radish (Raphanus sativus), Carrot (Dacus carota subsp. sativus), Turnip (Brassica rapa subsp rapa), Apple (Melus domestica), Banana (Musa spp.), Citrus groups (Citrus spp.), Grape (Vitis vinifera), Guava (Psidium guajava), Litchi (Litchi chinensis), Mango (Mangifera indica), Papaya (Carica papaya), Pineapple (Ananas comosus), Pomegranate (Punica granatum) , Sapota (Manilkara zapota), Tea (Camellia sinensis), Coffea (Coffea Arabica), Turmeric (Curcuma longa), Ginger (Zingiber officinale), Cumin (Cuminum cyminum), Fenugreek (Trigonella foenum-graecum), Fennel (Foeniculum vulgare), Coriander (Coriandrum sativum), Ajwain (Trachyspermum ammi), Psyllium (Plantago ovate), Black Pepper (Piper nigrum), Stevia (Stevia rebaudiana), Safed musli (Chlorophytum tuberosum), Drum stick (Moringa oleifera), Coconut (Coco nucifera), Mentha ( Mentha spp.), Rose (Rosa spp.), Jasmine (Jasminum spp.), Marigold ( Tagetes spp.), Common daisy (Bellis perennis), Dahlia (Dahlia hortnesis), Gerbera ( Gerbera jamesonii), Carnation (Dianthus caryophyllus).

In one embodiment of the present invention, the insecticidal formulation of present invention controls pests and insects listed below;

Insects from the order of the Lepidoptera, for example Agrotis ypsilon, Chilo infuscatellus, Chilo partellus, Chilo suppressalis, Cnaphalocrocis medinalis, Cydia pomonella, Earias vittella, Earias insulana, Helicoverpa armigera, Leucinodes orbonalis, Maruca testulalis, Mythimna separata, Pectinophora gossypiella, Phyllocnistis citrella, Pieris bras-sicae, Plutella xylostella, Scirpophaga incertulas, Sesamia inferens, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Tryporyza novella, Tuta absoluta and Zeiraphera Canadensis. Beetles (Coleoptera), for example Diabrotica longicornis, Diabrotica semipunctata, Diabrotica punctata, Diabrotica speciosa, Diabrotica virgifera, Dicladispa armigera, Epila-chna varivestis, Holotrichia bicolor, Holotrichia consanguinea, Leptinotarsa decemlineata, flies (Diptera), e.g. Atherigona orientalis, Dacus cucurbi-tae, Liriomyza trifolii, Melanagromyza obtuse, thrips (Thysanoptera), e.g. Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Scirtothrips dorsalis, Thrips oryzae, Thrips palmi and Thrips tabaci, termites (Isoptera), e.g. Calotermes flavicollis, Coptotermes formosanus, Heterotermes aureus, Leucotermes flavipes, Microtermes obesi, Odontotermes obesus, Reticulitermes flavipes, Termes natalensis. true bugs (Hemiptera), e.g. Amrasca biguttula biguttula, Amrasca devastans, Amritodus atkinsoni, Aphis gossypii, Aphis crassivora, Bemisia argentifolii, Bemisia tabaci, Dysdercus cingulatus, Empoasca fabae, Idioscopus spp. My-zus persicae, Nilaparvata lugens, Nephotettix virescens, Nephotettix nigropictus, Planococcus spp., Pseudococcus spp., Pyrilla perpusilla, Sogatella furcifera, Trialeurodes vaporariorum, Toxoptera aurantiia, Psylla spp., Rhopalosiphum spp., Sitobion spp.

The insecticidal formulation according to the present invention can be applied to any and all developmental stages of pests, such as egg, larva, pupa, and adult. The pests may be controlled by contacting the target pest, its food supply, habitat, breeding ground or its locus with an effective amount of the formulation of present invention.

The inventive formulation of present invention comprising the mixtures are highly effective in controlling insect pests, in GMO (Genetically Modified Organism) and Non GMO varieties of Cotton (Gossypium spp.), Paddy (Oryza sativa), Wheat (Triticum aestavum), Maize (Zea mays), Sugarcane (Saccharum officinarum) , Sugarbeet (Beta vulgaris), Soybean (Glycin max), Peanut (Arachis hypogaea), Green gram (Vigna radiata), Black gram (Vigna mungo), Chickpea (Cicer aritinum), Redgram (Cajanus cajan), Brinjal (Solanum melongena), Cabbage (Brassica oleracea var. capitata), Cauliflower (Brassica oleracea var. botrytis), Okra (Abelmoschus esculentus) , Onion (Allium cepa L.), Tomato (Solanum lycopersicun) , Potato (Solanum tuberosum) , Chilly (Capsicum annum), Garlic (Allium sativum), Cucumber (Cucumis sativus), Muskmelons (Cucumis melo), Watermelon (Citrullus lanatus), Bottle gourd (Lagenaria siceraria), Apple (Melus domestica), Banana (Musa spp.), Citrus groups (Citrus spp.), Grape (Vitis vinifera), Guava (Psidium guajava), Litchi (Litchi chinensis), Mango (Mangifera indica), Papaya (Carica papaya), Pineapple (Ananas comosus), Pomegranate (Punica granatum) , Tea (Camellia sinensis), Coffea (Coffea Arabica), Turmeric (Curcuma longa), Ginger (Zingiber officinale), Cumin (Cuminum cyminum).

Method of Applications:
The formulation of present invention can be applied by any of the below mentioned method;
Broadcasting of Granules, Controlled Release Granules (CR), Slow release and Fast release Microsphere/Microcapsule Granules (MS) by manual (by hand), by hand or power operated granules spreader, by machine operated soil granules applicators. It can be a sand mix or fertilizer mix broadcasting. Broadcasting can be done before or after crop sowing, planting or transplanting or at the time of land preparation. In sugarcane, broadcasting can be done manually by mixing it with sand or fertilizer and by spreading over cane sett, in open furrow before covering it with soil at the time of planting. In rice, broadcasting can be done manually by mixing it with sand or fertilizer after transplanting the crop.

Seed treatment to seeds, plant propagating materials
Foliar application / spraying
Soil drenching
Through drip irrigation
Nursery bed application

Mixing in to soil or other plant growing media in protected cultivations, green houses, net houses, poly houses.

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 vigor, quality and tolerance to abiotic or biotic stress are increased. Noteworthy, the health of a plant when applying the method according to the 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 defense system. As a result, the health of a plant is increased even in the absence of pest pressure. Accordingly, in an especially preferred embodiment of the method according to the invention, the health of a plant is increased both in the presence and absence of biotic or abiotic stress factors. The above identified indicators for the health condition of a plant may be interdependent or they may result from each other. An increase in plant vigor may for example result in an increased yield and/or tolerance to abiotic or biotic stress. One indicator for the condition of the plant is the yield. "Yield" is to be understood as any plant product of economic value that is produced by the plant such as grains, fruits in the proper sense, vegetables, nuts, grains, seeds, wood (e.g. in the case of silviculture plants) or even flowers (e.g. in the case of gardening plants, ornamentals). The plant products may in addition be further utilized and/or processed after harvesting.

In an especially preferred embodiment of the invention, the yield of the treated plant is increased.

In another preferred embodiment of the invention, the yield of the plants treated according to the method of the invention, is increased synergistically.

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 mixture according to the invention.

Increased yield can be characterized, among others, by the following improved proper-ties 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 protein content, increased oil content, increased starch content, increased pigment content, increased leaf are index.

A further indicator for the condition of the plant is the plant vigor. The plant vigor becomes manifest in several aspects such as the general visual appearance. In another especially preferred embodiment of the invention, the plant vigor of the treated plant is increased. In another preferred embodiment of the invention, the plant vigor of the plants treated according to the method of the invention, is increased synergistically. Improved plant vigor can be characterized, among others, by the following improved properties of the plant: improved vitality of the plant, improved plant growth, improved plant development, improved visual appearance, improved plant stand (less plant verse/lodging), improved emergence, enhanced root growth and/or more developed root system, enhanced nodulation, in particular rhizobial nodulation, bigger leaf blade, bigger size, increased plant weight, increased plant height, increased tiller number, increased number of side shoots, increased number of flowers per plant, increased shoot growth, increased root growth (extensive root system), increased yield when grown on poor soils or unfavorable climate, enhanced photosynthetic activity (e.g. based on increased stomatal conductance and/or increased C02 assimilation rate), increased stomatal conductance, increased C02 assimilation rate, enhanced pigment content (e.g. chlorophyll content), earlier flowering, earlier fruiting, earlier and improved germination, earlier grain maturity, improved self-defence mechanisms, improved stress tolerance and resistance of the plants against biotic and abiotic stress factors such as fungi, bacteria, viruses, insects, heat stress, cold stress, drought stress, UV stress and/or salt stress, less non-productive tillers, less dead basal leaves, less input needed (such as fertilizers or water), greener leaves, complete maturation under shortened vegetation periods, less fertilizers needed, less seeds needed, easier harvesting, faster and more uniform ripening, longer shelf-life, longer panicles, delay of senescence, stronger and/or more productive tillers, better extractability of ingredients, improved quality of seeds (for being seeded in the following seasons for seed production), better nitrogen uptake, improved reproduction, reduced production of ethylene and/or the inhibition of its reception by the plant.

The improvement of the plant vigor according to the present invention particularly means that the improvement of any one or several or all of the above mentioned plant characteristics are improved independently of the pesticidal action of the mixture or active ingredients (components).

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

In an especially preferred embodiment of the invention, the quality of the treated plant is increased.

In another preferred embodiment of the invention, the quality of the plants treated according to the method of the invention, is increased synergistically.

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 can 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 process ability of the harvested products.

Another indicator for the condition of the plant is the plant's tolerance or resistance to biotic and/or abiotic stress factors. Biotic and abiotic stress, especially over longer terms, can have harmful effects on plants. Biotic stress is caused by living organisms while abiotic stress is caused for example by environmental extremes. According to the present invention, "enhanced tolerance or resistance to biotic and/or abiotic stress factors" means (1) that certain negative factors caused by biotic and/or abiotic stress are diminished in a measurable or noticeable amount as compared to plants exposed to the same conditions, but without being treated with a mixture according to the invention and (2) that the negative effects are not diminished by a direct action of the mixture according to the invention on the stress factors, e.g. by its fungicidal or insecticidal action which directly destroys the microorganisms or pests, but rather by a stimulation of the plants' own defensive reactions against said stress factors.

One or more inactive excipient is selected from including but not limited to dispersant, anti-freezing agent, anti-foam agent, wetting agent, suspension aid, anti-microbial agent, thickener, quick coating agent or sticking agents (also referred to as “stickers” or “binders”) and buffering 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. 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. For suspension concentrates, very good adsorption and stabilization are obtained using polyelectrolytes, such as sodium naphthalene sulphonate formaldehyde condensates. Tristyrylphenolethoxylate phosphate esters are also used. Nonionics such as alkylarylethylene oxide condensates and EO-PO block copolymers are sometimes combined with anionics 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 can 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 lignosulphonates; sodium naphthalene sulphonate formaldehyde condensates; tristyrylphenolethoxylate phosphate esters; aliphatic alcohol ethoxylates; alky ethoxylates; EO-PO block copolymers; and graft copolymers or mixtures thereof.

Anti-freezing agent as used herein can be selected from the group consisting of polyethylene glycols, methoxypolyethylene glycols, polypropylene glycols, polybutylene glycols, glycerin and ethylene glycol.

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 nonanol, or silica. In both cases, the function of the anti-foam agent is to displace the surfactant from the air-water interface.

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 wettable powder, suspension concentrate, and water-dispersible granule formulations include but not limited to sodium lauryl sulphate; sodium dioctylsulphosuccinate; alkyl phenol ethoxylates; and aliphatic alcohol ethoxylates and the salts thereof which are standard in agricultureor mixtures thereof.

Suspension aid in the present description denotes a natural or synthetic, organic or inorganic material with which the active substance is combined in order to facilitate its application to the plant, to the seeds or to the soil. This carrier is hence generally inert, and it must be agriculturally acceptable, in particular to the plant being treated. The carrier may be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, and the like or mixtures thereof) or liquid (water, alcohols, ketones, petroleum fractions, aromatic or paraffinic hydrocarbons, chlorinated hydrocarbons, liquefied gases, and the like or mixtures thereof).

Biocides / Microorganisms cause spoilage of formulated products. Therefore anti-microbial agents are used to eliminate or reduce their effect. Examples of such agents include, but are not limited to: propionic acid and its sodium salt; sorbic acid and its sodium or potassium salts; benzoic acid and its sodium salt; p-hydroxy benzoic acid sodium salt; methyl p-hydroxy benzoate; and biocide such as sodium benzoate, 1,2-benzisothiazoline-3-one, 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, potassium sorbate, parahydroxy benzoates or mixtures thereof.

Thickeners or gelling agents are used mainly in the formulation of suspension concentrates, emulsions and suspo-emulsions to modify the rheology or flow properties of the liquid and to prevent separation and settling of the dispersed particles or droplets. Thickening, gelling, and anti-settling agents generally fall into two categories, namely water-insoluble particulates and water-soluble polymers. It is possible to produce suspension concentrate formulations using clays and silicas. Examples of these types of materials, include, but are limited to, montmorillonite, bentonite; magnesium aluminum silicate; and attapulgite. Water-soluble polysaccharides have been used as thickening-gelling agents for many years. The types of polysaccharides most commonly used are natural extracts of seeds and seaweeds are synthetic derivatives of cellulose or mixtures thereof. Examples of these types of materials include, but are not limited to, guar gum; locust bean gum; carrageenam; xanthan gum; alginates; methyl cellulose; sodium carboxymethyl cellulose (SCMC); hydroxyethyl cellulose (HEC) or mixtures thereof. Other types of anti-settling agents are based on modified starches, polyacrylates, polyvinyl alcohol and polyethylene oxide or mixtures.

The quick coating agent can be a conventionally available sticker, for example polyesters, polyamides, poly- carbonates, polyurea and polyurethanes, acrylate polymers and copolymers, styrene copolymers, butadiene copolymers, polysaccharides such as starch and cellulose derivatives, vinylalcohol, vinylacetate and vinylpyrrolidone polymers and copolymers, polyethers, epoxy, phenolic and melamine resins, polyolefins and define copolymersand mixtures thereof. Examples of preferred polymers are acrylate polymers such as poly(methacrylate), poly(ethyl methacrylate), poly(methylmethacrylate), acrylate copoylmers and styrene-acrylic copolymers as defined herein below, poly(styrene-co maleic anhydride), cellulosic polymers such as ethyl cellulose, cellulose acetate, cellulose acetatebutyrate, acetylated mono, di, and triglycerides, poly(vinylpyrrolidone), vinyl acetate polymers and copolymers, poly(alkylene glycol), styrene butadiene copolymers, poly(orthoesters), alkyd resins, and mixtures of two or more of these. Polymers that are biodegradable are also useful in the present invention. As used herein, a polymer is biodegradable if is not water soluble, but is degraded over a period of several weeks when placed in an application environment. Examples of biodegradable polymers that are useful in the present invention include biodegradable polyesters, starch, polylactic acid starch blends, polylactic acid, poly(lactic acid-glycolic acid) copolymers, polydioxanone, cellulose esters, ethyl cellulose, cellulose acetate butyrate, starch esters, starch esteraliphatic polyester blends, modified corn starch, polycaprolactone, poly(namylmethacrylate), wood rosin, polyanhydrides, polyvinylalcohol, polyhydroxybutyratevalerate, biodegradable aliphatic polyesters, and polyhydroxybutyrate or mixtures thereof.

Buffering agent as used herein is selected from group consisting of calcium hydroxyapatite, Potassium Dihydrogen Phosphate, Sodium Hydroxide, carbonated apatite, calcium carbonate, sodium bicarbonate, tricalcium phosphate, calcium phosphates, carbonated calcium phosphates, amine monomers, lactate dehydrogenase and magnesium hydroxide.

The solvent for the formulation of the present invention may include water, water-soluble alcohols and dihydroxy alcohol ethers. The water-soluble alcohol which can be used in the present invention may be lower alcohols or water-soluble macromolecular alcohols. The term "lower alcohol", as used herein, represents an alcohol having 1-4 carbon atoms, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, etc. Macromolecular alcohol is not limited, as long as it may be dissolved in water in a suitable amount range, polyethylene glycol, sorbitol, glucitol, etc. The examples of suitable dihydroxy alcohol ethers used in the present invention may be dihydroxy alcohol alkyl ethers or dihydroxy alcohol aryl ethers. The examples of dihydroxy alcohol alkyl ether include ethylene glycol methyl ether, diethylene glycol methyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol ethyl ether, propylene glycol ethyl ether, dipropylene glycol ethyl ether, etc. The examples of dihydroxy alcohol aryl ethers include ethylene glycol phenyl ether, diethylene glycol phenyl ether, propylene glycol phenyl ether, dipropylene glycol phenyl ether, and the like. Any of the above mentioned solvent can be used either alone or in combination thereof.

Inactive excipients used in SC (Suspension Concentrate (= flow able concentrate) formulation: Dispersing agent: Acrylic graft copolymer, Alkylated naphthalene sulfonate, sodium salt, Sodium salt of naphthalene sulfonate condensate, Sodium Lignosulfonate etc., Dispersing agent cum Emulsifier: Polyalkoxy alkyl ether, Ethylene oxide/propylene oxide block copolymer etc,, Dispersing agent & Wetting agent: Polyarylphenyl ether phosphate, Ethoxylated Fatty Alcohol etc., Wetting agent & Spreader: Trisiloxane ethoxylate etc., Wetting agent & Emulsifier: Sodium dioctyl sulfosuccinate etc., Antifoaming agent: Silicone antifoam emulsion, Dimethylsiloxane, Polydimethyl siloxane etc., Rheology Modifier,Thickner: Polysaccharide etc., Anti freezing Agent: Glycol (Monoethylene glycol, Diethylene glycol, Polypropylene glycol, Polyethylene glycol), Glycerin etc., Biocide/Preservative: 1,2-benzisothiazolin-3(2H)-one, sodium salt, Sodium benzoate, 2-bromo-2-nitropropane-1,3-diol, Formaldehyde, Sodium o-phenylphenate, 5-chloro-2-methyl-4-isothiazolin-3-one & 2-methyl-4-isothiazolin-3-one etc., Suspending aid: Aluminum Magnesium Silicate etc., Suspending and Anticaking agent: Silicone dioxide etc., Spreader: Organo modified Trisiloxane etc., Sticker and Penetrant: Poly glycerol ester etc., Deposition aid: Polyether etc.

Inactive excipients used in SE (Suspo emulsion) formulation: Solvent: n-Octanol etc., Wetting and emulsifier: Octyl Phenol Ethoxylate, Polyoxyethylene (8) nonyl phenol, Sodium dioctyl sulfosuccinate etc., Dispersing agent: Acrylic graft copolymer etc., Dispersing agent & Emulsifier: Polyalkoxy alkyl ether, Ethylene oxide/propylene oxide block copolymer, Sodium salt of naphthalene sulfonate condensate etc., Dispersing and wetting agent: Polyarylphenyl ether phosphate etc., Co-dispersant/Wetting agent: Ethoxylated Fatty Alcohol etc., Spreading and Wetting agent: Trisiloxane ethoxylate etc., Antifoam: Silicone antifoam emulsion etc., Suspending aid and anticaking agent: Silicone dioxide etc., Rheology Modifier, Thickner: Polysaccharide etc., Anti-freezing Agent: Glycol (Monoethylene glycol, Diethylene glycol, Polypropylene glycol, Polyethylene glycol) etc., Biocide/Preservative: 1,2-benzisothiazolin-3-one, Sodium benzoate, 2-bromo-2-nitropropane-1,3-diol, Formaldehyde etc.,

Inactive excipients used in WG (Water Dispersible Granule) formulation: Dispersing agents: Sodium salt of naphthalene sulfonate condensate, Modified polyacrylate copolymer, Sodium polycarboxylate, Sodium Ligno sulfonate, Alkyl naphthalene sulfonate condensate-sodium salt, Alcohol block co-polymer etc;, Wetting agents: Blend of naphthalene sulfonate condensate & phenol sulfonate condensate, blend of naphthalene sulfonate condensate, Sodium dodecylbenzene sulfonate, Sodium lauryl sulfate, Blend of alkyl naphthalene sulfonate and anionic wetting agent, Sodium n-butyl naphthalene sulfonate, Sodium isopropyl naphthalene sulfonate, Blend of sodium alkyl aryl sulfonate etc., suspending agents: silicon dioxide etc, anticaking agents: Urea formaldehyde resin / Urea-methanol etc, defoaming agents: silicone antifoam emulsion etc, binders: corn starch, Polyvinylpyrrolidone etc, fillers: lactose, china clay/kaolin, titanium dioxide, talcum powder, diatomaceous earth humic acid (sodium salt or potassium salt), fulvic acid, protein hydrolysate, amino acid, seaweed extract, microbial extract, plant extract, vitamin B, chitin, chitosan etc, wetting, dispersing agent, stabilizer, sanitizers and defoaming agent: fatty amine ethoxylate etc., stabilizer, emulsifier and dispersing agent: polyacrylate co-polymer, polyacrylate polymer sodium salt etc.

Example 1: Granules formulation of chlorantraniliprole 0.6% + fipronil 0.6% + bifenthrin 0.5%:

Chemical composition % (w/w)
chlorantraniliprole a.i. 0.60
fipronil a.i. 0.60
bifenthrin a.i. 0.50
Polyaryl phenol ethoxylate & calcium dodecyl benzene solphonate Blend 1.00
Phosphoric acid 0.05
Azo Dye 0.05
Diacetone alcohol 2.00
China Clay 3.00
River Sand q.s.
TOTAL 100.00

Manufacturing process of Granules (GR)
Step 1 Charged required quantity of carrier into the booth mixture with help of bucket elevator, then add other raw material (as technical, solvent, Surfactant, stabilizer, and binder) into the booth mixture and at this point add filler and allow mixing for another 20 minutes for homogenization.
Step 2 After completion of raw material addition and proper mixing, stop booth mixture for sampling.
Step 3 Sample is sent for QC approval and approved material is unloaded in 25 Kg HDPE wooven bags.

Example 2: Granules formulation of chlorantraniliprole 0.6% + fipronil 0.6% + thiocyclam hydrogen oxalate 3%:

Chemical composition % (w/w)
chlorantraniliprole a.i. 0.60
fipronil a.i. 0.60
thiocyclam hydrogen oxalate 3.00
Polyaryl phenol ethoxylate & calcium dodecyl benzene solphonate Blend 1.00
Phosphoric acid 0.05
Azo Dye 0.05
Diacetone alcohol 2.00
China Clay 3.00
River Sand q.s.
TOTAL 100.00

Procedure: as per Example 1

Example 3: Granules formulation of chlorantraniliprole 0.6%+bifenthrin 1%+thiocyclam hydrogen oxalate 3%:

Chemical composition % (w/w)
chlorantraniliprole a.i. 0.60
bifenthrin a.i. 1.00
thiocyclam hydrogen oxalate a.i. 3.00
Polyaryl phenol ethoxylate & calcium dodecyl benzene solphonate Blend 1.00
Phosphoric acid 0.05
Azo Dye 0.05
Diacetone alcohol 2.00
China Clay 3.00
River Sand q.s.
TOTAL 100.00

Procedure: as per Example 1

Example 4: Zeon Concentrate (ZC) formulation of Chlorantraniliprole 6.25%+Fipronil 12.5%+Lambda cyhalothrin 2.5%

Chemical Composition Percent (% w/w)
chlorantraniliprole a.i. 6.25
fipronil a.i. 12.50
lambda cyhalothrin a.i. 2.50
Acralic graft polymer 2.50
Fatty alcohol Ethoxylated 1.50
MonoEthyleneGlycol 2.50
Sodium salt of naphthalene sulfonate condensate 0.50
1, 2- benzisothiazolin-3-one 0.10
Toluene Diisocynate 0.08
Polymethyl polyphenyl Isocynate 0.01
Mixture of heavy Aromatic Hydrocarbons 1.50
Silicon Dioxide 0.30
Polyaryl phenol ethoxylate 0.15
Calcium dodecyl benzene sulfonate 0.15
Modified styrene acrylic polymer 0.15
Xanthan powder 0.15
Silicone Antifoam 0.50
Water q.s.
Total 100.00

Manufacturing process of Zeon Concentrate (ZC)

Part 1 Capsule suspension
Step 1 Oil Phase : Charge the Chlopyrifos technical to the reactor and mix thoroughly and heat the vessel at 50-55 °C. Afterwards charge the PMPI and TDI to vessel and mix thoroughly for 10-15 minutes.
Step 2 Aqueous Phase: Take required quantity of water Add required quantity of Wetting agent, dispersing agent and homogenize the contents for 1 hours. (Maintain Temp 50-55 °C)
Step 3 Now mix the oil phase slowly in aqueous phase then stir for another 1 hours till required particle size is achieved.
Step 4 Add Amine to this formulation and stop the high shear agitator, and start bulk agitation and heat the contents of the reactor to 50-55°C for 1-2 hours for polymerization step and cooking.
Step 5 Now, cool the vessel to 40°C or below.
Step 6 Finally add required quantity of 2% of xanthum gum solution to this formulation
Step 7 Final product is sent for QC approval.
Part 2 Suspension Concentrate
Step 1 Charge required quantity of DM water need to be taken in designated vessel for Suspension concentrate production.
Step 2 Add required quantity of Wetting agent, antifreeze, dispersing agent & suspending agents and homogenize the contents for 1 hour using high shear homogenizer.
Step 3 Then add technical and other remaining adjuvants excluding ‘thickener’ are added to it and homogenized to get uniform slurry ready for grinding.
Step 4 Before grinding half the quantity of antifoam was added and then material was subjected to grinding in Dyno mill till desired particle size is achieved.
Step 5 After grinding material is transferred in CS Vessel.
Step 6 Final product is sent for QC approval.
Part 3 Mixing CS + SC
Step 1 After getting approval from QC department SC part is added in CS Vessel and homogenized for 30 minutes.
Step 2 Finally remaining 2% Xanthum Gum is added to it and homogenized for 20 minutes.
Step 3 Now Final Formulation is sent for quality check.
Step 4 After approval material is packed in required pack sizes.

Example 5: Zeon Concentrate (ZC) formulation of Chlorantraniliprole 2.5%+ Bifenthrin 4%+Chlorpyrifos 25%

Chemical Composition Percent (% w/w)
chlorantraniliprole a.i. 2.50
bifenthrin a.i. 4.00
chlorpyrifos a.i. 25.00
Sodium dioctyl sulphosuccinate 2.00
Modified styrene acrylic polymer 5.00
1, 2- benzisothiazolin-3-one 0.20
Toluene Diisocynate 0.40
Polymethyl polyphenyl Isocynate 0.80
Silicon Dioxide 0.50
Ethylene oxide/propylene oxide block copolymer 0.30
Xanthan powder 0.15
Polyamines 0.10
Silicone Antifoam 0.50
Polyethylene glycol 2.50
Water q.s.
Total 100.00

Procedure: as per Example 4

Example 6: Zeon Concentrate (ZC) formulation of Chlorantraniliprole 2.5%+ Chlorpyrifos 25%+Lambda cyhalothrin 1%

Chemical Composition Percent (% w/w)
chlorantraniliprole a.i. 2.50
chlorpyrifos a.i. 25.00
lambda cyhalothrin a.i. 1.00
Sodium dioctyl sulphosuccinate 2.00
Modified styrene acrylic polymer 5.00
1, 2- benzisothiazolin-3-one 0.20
Toluene Diisocynate 0.40
Polymethyl polyphenyl Isocynate 0.80
Silicon Dioxide 0.50
Ethylene oxide/propylene oxide block copolymer 0.30
Xanthan powder 0.15
Polyamines 0.10
Silicone Antifoam 0.50
Polyethylene glycol 2.50
Water q.s.
Total 100.00

Procedure: as per Example 4

Example 6 to 15 Most Preferred formulations

a.i.3 active ingredients in % Formulation Strength (%) Formulation Type Application Rate (g per hectare) g.a.i per hectare
a.i.1 a.i.2 a.i.3 a.i.1 a.i.2 a.i.3
a.i.1 a.i.2a Bifenthrin 0.6 0.6 0.5 1.7 Granule 10000 60.00 60.00 50.00
a.i.1 a.i.2a Lambda Cyhalothrin 6.25 12.5 2.5 21.25 ZC 400 25.00 50.00 10.00
a.i.1 a.i.2a Chlorpyrifos 2.5 5 25 32.5 ZC 1000 25.00 50.00 250.00
a.i.1 a.i.2a Cartap HCl 0.6 0.6 3.75 4.95 Granule 10000 60.00 60.00 375.00
a.i.1 a.i.2a Thiocyclam Hydrogen Oxalate 0.6 0.6 3 4.2 Granule 10000 60.00 60.00 300.00
a.i.1 a.i.2b Chlorpyrifos 2.5 4 25 31.5 ZC 1000 25.00 40.00 250.00
a.i.1 a.i.2b Cartap HCl 0.6 1 3.75 5.35 Granule 10000 60.00 100.00 375.00
a.i.1 a.i.2b Thiocyclam Hydrogen Oxalate 0.6 1 3 4.6 Granule 10000 60.00 100.00 300.00
a.i.1 a.i.2c Lambda Cyhalothrin 2.5 25 1 28.5 ZC 1000 25.00 250.00 10.00
[a.i.1: Chlorantraniliprole ; a.i.2a=Fipronil; a.i.2b=Bifenthrin; a.i.2c=Chlorpyrifoss]

Biological Examples:
Field experiments of inventive synergistic mixtures of
chlorantraniliprole+fipronil+bifenthrin,
chlorantraniliprole+fipronil+cartap hydrochloride,
chlorantraniliprole+fipronil+thiocyclam hydrogen oxalate,
chlorantraniliprole+Bifenthrin+Thiocyclam hydrogen oxalate
on sugarcane crop evaluate bio-efficacy against different insect-pests damaging the crops.
A synergistic effect exists wherever the action of a combination of active ingredient is greater than the sum of the action of each of the components alone. Therefore a synergistically effective amount or an effective amount of a synergistic composition or combination is an amount that exhibits greater pesticidal activity than the sum of the pesticidal activities of the individual components.
In the field of agriculture, it is often understood that the term “synergy” is as defined by Colby S.R. in an article entitled “ Calculation of the synergistic and antagonistic responses of herbicide combinations” published in the journal Weeds, 1967, 15, p.20-22, incorporated herein by reference in its entirety. The action expected for a given combination of two active components can be calculated as follows:

The synergistic herbicidal action of the inventive mixtures can be demonstrated by the experiments below.

FIELD BIO-EFFICACY STUDIES:
EXPERIMENT 1: Control of Sugarcane insect-pests.
Crop & Variety : Sugarcane, Co-0238
Location : Faridpur, Dist. Barielly, Uttar Pradesh
Treatments : 8 (Set 1), 18 (Set 2)
Plot size : 40 sq. mt. (8 m x 5 m)
Spacing : 90 cm row to row
Planting material : 3 budded setts, 4 setts per meter
Date of sowing : 17 March 2017
Date of Application : At the time of planting, 17 March 2017
Method of Application: In furrow application, over the setts and then cover up with soil
Date of Harvesting : 17 March 2018
Fertilizer : 100 kg per ha. DAP (diammonium phosphate) as basal dose at plating.
Agronomic Practices : Fertilizer, irrigation, inter culturing, earthing up and weeding done as per
the crop requirement.
Observation Methods:
Germination (%):
The germination (%) was recorded after 45 days of planting using following formula.
Number of emerging shoots
Percent germination of Buds = ----------------------------------------- X 100
Total number of buds planted
Shoot count:
The number of shoots were counted from 1 mrl (meter row length) from randomly selected 5 spot per plot.

The percent increase in shoot over untreated control were calculated by below formula.

Number of shoots in treatment
Percent increase over untreated control = 100 X ------------------------------------------------ - 100
Number of shoots in untreated control

Early shoot borer (Chilo infuscatellus) incidence (%):

Fifty shoots per plot were selected randomly and presence of characteristic “dead heart”
(damaged shoots) were recorded to calculate per cent shoot damage by early shoot borer.

Damaged shoots
Percent shoot damage = -------------------------------------------------- X 100
Total number of shoots observed (50)

Plant damage by Termite (Odontotermes spp. And Microtermes spp.) (%):

Ten plants at random from each plot were observed to record the plant damage due to termites at 60 and 120 days after sowing (planting)

Damaged plants
Percent plant damage = ------------------------------------------- X 100
Total number of plants observed

Table 1: Synergism in efficacy against early shoot borer (Chilo infuscatellus) control in sugarcane
(Set 1)
Treatment Details Formulation (kg or ml per h) Active Ingredient (g/h) % Early shoot borer control Observed % Early shoot borer control Expected Colby Ratio o/e
45 DAS 60 DAS 45 DAS 60 DAS 45 DAS 60 DAS
Chlorantraniliprole 0.6%+Fipronil 0.6%+Bifenthrin 0.5% Granule 10 kg 60+60+50 98.8 97.8 92.47 85.89 1.07 1.14
Chlorantraniliprole 0.6% Granule +Fipronil 0.6% Granule (tank mix) 10 kg+10 kg 60+60 87.6 77.8 88.24 79.84 0.99 0.97
Chlorantraniliprole 0.6% Granule +Bifenthrin 10% EC (tank mix) 10 kg+500 ml 60+50 80.2 72.4 82.08 74.80 0.98 0.97
Fipronil 0.6% Granule +Bifenthrin 10% EC (tank mix) 10 kg+500 ml 60+50 72.4 56.2 73.12 60.80 0.99 0.92
Chlorantraniliprole 0.6% Granule 10 kg 60 72.0 64.0
Fipronil 0.6% Granule 10 kg 60 58.0 44.0
Bifenthrin 10% EC 500 ml 50 36.0 30.0
Unweeded control 0 0 0.0 0.0
kg- killogram, h-hectare, UTC- Untreated Check, DAS- Days After Sowing

The field trials data (table 1) shows that synergistic activities of chlorantraniliprole+ fipronil+ bifenthrin has been observed in terms of efficacy against early shoot borer infesting sugarcane crop.

Table 2: Treatment details
Treatment Number Composition Application Rate/Hectare
Formulation (kg) gram active
1 Chlorantraniliprole 0.6%+Fipronil 0.6%+Bifenthrin 0.5% Granule 10 kg 60+60+50
2 Chlorantraniliprole 0.6%+Fipronil 0.6%+Cartap Hydrochloride 3.75% Granule 10 kg 60+60+375
3 Chlorantraniliprole 0.6%+Fipronil 0.6%+Thiocyclam Hydrogen Oxalate 3% Granule 10 kg 60+60+300
4 Chlorantraniliprole 0.6%+Bifenthrin 1%+Thiocyclam Hydrogen Oxalate 3% Granule 10 kg 60+100+300
5 Chlorantraniliprole 0.6%+Fipronil 0.6% Granule 10 kg 60+60
6 Chlorantraniliprole 0.6%+Bifenthrin 1% Granule 10 kg 60+100
7 Chlorantraniliprole 0.6%+Cartap Hydrochloride 3.75% Granule 10 kg 60+375
8 Chlorantraniliprole 0.6%+Thiocyclam Hydrogen Oxalate 3% Granule 10 kg 60+300
9 Fipronil 0.6%+Bifenthrin 0.5% Granule 10 kg 60+50
10 Fipronil 0.6%+Cartap Hydrochloride 3.75% Granule 10 kg 60+375
11 Fipronil 0.6%+Thiocyclam Hydrogen Oxalate 3% Granule 10 kg 60+300
12 Bifenthrin 1%+Thiocyclam Hydrogen Oxalate 3% Granule 10 kg 100+300
13 Chlorantraniliprole 0.6% Granule 10 kg 60
14 Fipronil 0.6% Granule 10 kg 60
15 Bifenthrin 1% Granule 10 kg 100
16 Cartap Hydrochloride 3.75% Granule 10 kg 375
17 Thiocyclam Hydrogen Oxalate 3% Granule 10 kg 300
18 Untreated control 0 0
kg- killogram, h-hectare, DAS- Days After Sowing

Table 3: Efficacy of inventive synergistic ready mix against insect-pest of sugarcane crop
Treatment Number Germination (%) No. of shoots per mrl % Increase of shoots over Untreated Control Early shoot borer incidence (%) % Plant Damage by Termite
45 DAS 45 DAS 45 DAS 60 DAS 60 DAS 120 DAS
1 100.0 23.6 90.3 0.00 0.00 0.00
2 100.0 24.0 93.5 0.00 0.00 0.00
3 100.0 24.4 96.8 0.00 0.00 0.00
4 100.0 23.6 90.3 0.00 0.00 0.00
5 100.0 19.8 59.7 0.84 0.96 1.10
6 100.0 18.6 50.0 1.12 1.42 2.36
7 99.2 18.8 51.6 1.06 1.92 2.68
8 99.4 19.2 54.8 0.92 2.24 3.18
9 98.4 17.8 43.5 1.68 0.82 0.98
10 95.2 18.2 46.8 1.24 1.16 1.76
11 92.4 18.6 50.0 1.30 1.10 1.62
12 95.6 17.6 41.9 1.84 2.56 4.26
13 98.2 15.0 21.0 2.86 3.18 4.62
14 90.2 15.4 24.2 2.96 1.26 2.10
15 96.4 13.6 9.7 3.86 2.68 4.16
16 88.4 14.2 14.5 3.42 3.26 5.42
17 90.2 14.8 19.4 3.24 3.12 5.18
18 88.6 12.4 0.0 4.86 4.88 8.62
DAS- Days After Sowing, mrl-meter row length

The field trial results presented in table 3 shows synergistic activity between three active ingredients of:
chlorantraniliprole+fipronil+bifenthrin,
chlorantraniliprole+fipronil+cartap hydrochloride,
chlorantraniliprole+fipronil+thiocyclam hydrogen oxalate,
chlorantraniliprole+ bifenthrin+thiocyclam hydrogen oxalate by giving excellent germination (100%), about >90 % increase in shoots cane over control, excellent protection against early shoot borer (no incidence), excellent protection against termite with longer residual control (up to 120 days). The visible characters were observed were increase in number of roots (root mass), more number of secondary and tertiary roots, dark green color of leaf, increased leaf blades width, leaf shinning, stem girth, plant/ shoot height and no lodging compared to other treatments.
,CLAIMS:CLAIMS We claim; [CLAIM 1]. An synergistic insecticidal composition comprising A) Chlorantraniliprole; B) one insecticide selected from Fipronil, Bifenthrin and Chlorpyrifos C) further one more insecticide selected from Bifenthrin, Lambda Cyhalothrin, Chlorpyrifos, Cartap Hydrochloride and Thiocyclam Hydrogen Oxalate and salts thereof; and one or more other inactive excipients. [CLAIM 2]. The synergistic composition as claimed in claim 1 wherein the component (A) Chlorantraniliprole is in ratio of 0.1-20%, component (B) insecticide selected from Fipronil, Bifenthrin and Chlorpyrifos is in ratio of 0.1-30% and component (C) further one more insecticide selected from Bifenthrin, Lambda Cyhalothrin, Chlorpyrifos, Cartap Hydrochloride and Thiocyclam Hydrogen Oxalate and salts thereof is in ratio of 0.1 to 50%. [CLAIM 3]. The synergistic composition as claimed in claim 1, wherein inactive excipients are selected from the group consisting of dispersant, anti-freezing agent, anti-foam agent, wetting agent, suspension aid, anti-microbial agent, thickener, quick coating agent or sticking agents (also referred to as “stickers” or “binders”) and buffering agent. [CLAIM 4]. The synergistic composition as claimed in claim 1-3, wherein the formulations comprises of Granules (GR) or Zeon Concentrate (ZC) formulation. [CLAIM 5]. The formulation comprising the synergistic composition as claimed in claim 4, wherein the Granules (GR) formulation comprises:
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a) component (A) Chlorantraniliprole is in ratio of 0.1-20%, component (B) insecticide selected from Fipronil, Bifenthrin and Chlorpyrifos is in ratio of 0.1-30% and component (C) further one more insecticide selected from Bifenthrin, Lambda Cyhalothrin, Chlorpyrifos, Cartap Hydrochloride and Thiocyclam Hydrogen Oxalate and salts thereof is in ratio of 0.1 to 50%; b) polyaryl phenol ethoxylate & calcium dodecyl benzene solphonate Blend; c) phosphoric acid; d) azo dye; e) diacetone alcohol; f) china clay; g) river sand. [CLAIM 6]. The formulation comprising the synergistic composition as claimed in claim 4, wherein the Zeon Concentrate (ZC) formulation comprises: a) component (A) Chlorantraniliprole is in ratio of 0.1-20%, component (B) insecticide selected from Fipronil, Bifenthrin and Chlorpyrifos is in ratio of 0.1-30% and component (C) further one more insecticide selected from Bifenthrin, Lambda Cyhalothrin, Chlorpyrifos, Cartap Hydrochloride and Thiocyclam Hydrogen Oxalate and salts thereof is in ratio of 0.1 to 50%; b) Acralic graft polymer; c) Fatty alcohol Ethoxylated; d) MonoEthyleneGlycol; e) Sodium salt of naphthalene sulfonate condensate; f) 1, 2- benzisothiazolin-3-one; g) Toluene Diisocynate; h) Polymethyl polyphenyl Isocynate; i) Mixture of heavy Aromatic Hydrocarbons;
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j) Silicon Dioxide; k) Polyaryl phenol ethoxylate; l) Modified styrene acrylic polymer; m) Xanthan powder; n) Silicone Antifoam. [CLAIM 7]. The formulation comprising the synergistic composition as claimed in claim 4, wherein the Zeon Concentrate (ZC) formulation comprises: a) component (A) Chlorantraniliprole is in ratio of 0.1-20%, component (B) insecticide selected from Fipronil, Bifenthrin and Chlorpyrifos is in ratio of 0.1-30% and component (C) further one more insecticide selected from Bifenthrin, Lambda Cyhalothrin, Chlorpyrifos, Cartap Hydrochloride and Thiocyclam Hydrogen Oxalate and salts thereof is in ratio of 0.1 to 50%; b) Sodium dioctyl sulphosuccinate; c) Modified styrene acrylic polymer; d) 1, 2- benzisothiazolin-3-one; e) Toluene Diisocynate; f) Polymethyl polyphenyl Isocynate; g) Silicon Dioxide; h) Ethylene oxide/propylene oxide block copolymer; i) Xanthan powder; j) Polyamines; k) Silicone Antifoam; l) Polyethylene glycol. [CLAIM 8]. The synergistic composition as claimed in any of the preceding claims, wherein the said composition is to be used to manage or control Insect-pests in the crops selected from GMO (Genetically Modified Organism) and Non GMO varieties of Cotton (Gossypium spp.), Paddy (Oryza sativa), Wheat (Triticum aestavum), Maize (Zea
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mays), Sugarcane (Saccharum officinarum) , Sugarbeet (Beta vulgaris), Soybean (Glycin max), Peanut (Arachis hypogaea), Green gram (Vigna radiata), Black gram (Vigna mungo), Chickpea (Cicer aritinum), Redgram (Cajanus cajan), Brinjal (Solanum melongena), Cabbage (Brassica oleracea var. capitata), Cauliflower (Brassica oleracea var. botrytis), Okra (Abelmoschus esculentus) , Onion (Allium cepa L.), Tomato (Solanum lycopersicun) , Potato (Solanum tuberosum) , Chilly (Capsicum annum), Garlic (Allium sativum), Cucumber (Cucumis sativus), Muskmelons (Cucumis melo), Watermelon (Citrullus lanatus), Bottle gourd (Lagenaria siceraria), Apple (Melus domestica), Banana (Musa spp.), Citrus groups (Citrus spp.), Grape (Vitis vinifera), Guava (Psidium guajava), Litchi (Litchi chinensis), Mango (Mangifera indica), Papaya (Carica papaya), Pineapple (Ananas comosus), Pomegranate (Punica granatum) , Tea (Camellia sinensis), Coffea (Coffea Arabica), Turmeric (Curcuma longa), Ginger (Zingiber officinale), Cumin (Cuminum cyminum). [CLAIM 9]. The synergistic composition as claimed in any of the preceding claims, wherein the said composition control pests and insects from the order of the Lepidoptera, for example Agrotis ypsilon, Chilo infuscatellus, Chilo partellus, Chilo suppressalis, Cnaphalocrocis medinalis, Cydia pomonella, Earias vittella, Earias insulana, Helicoverpa armigera, Leucinodes orbonalis, Maruca testulalis, Mythimna separata, Pectinophora gossypiella, Phyllocnistis citrella, Pieris bras-sicae, Plutella xylostella, Scirpophaga incertulas, Sesamia inferens, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Tryporyza novella, Tuta absoluta and Zeiraphera Canadensis. Beetles (Coleoptera), for example Diabrotica longicornis, Diabrotica semipunctata, Diabrotica punctata, Diabrotica speciosa, Diabrotica virgifera, Dicladispa armigera, Epila-chna varivestis, Holotrichia bicolor, Holotrichia consanguinea, Leptinotarsa decemlineata, flies (Diptera), e.g. Atherigona orientalis, Dacus cucurbi-tae, Liriomyza
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trifolii, Melanagromyza obtuse, thrips (Thysanoptera), e.g. Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Scirtothrips dorsalis, Thrips oryzae, Thrips palmi and Thrips tabaci, termites (Isoptera), e.g. Calotermes flavicollis, Coptotermes formosanus, Heterotermes aureus, Leucotermes flavipes, Microtermes obesi, Odontotermes obesus, Reticulitermes flavipes, Termes natalensis. true bugs (Hemiptera), e.g. Amrasca biguttula biguttula, Amrasca devastans, Amritodus atkinsoni, Aphis gossypii, Aphis crassivora, Bemisia argentifolii, Bemisia tabaci, Dysdercus cingulatus, Empoasca fabae, Idioscopus spp. My-zus persicae, Nilaparvata lugens, Nephotettix virescens, Nephotettix nigropictus, Planococcus spp., Pseudococcus spp., Pyrilla perpusilla, Sogatella furcifera, Trialeurodes vaporariorum, Toxoptera aurantiia, Psylla spp., Rhopalosiphum spp., Sitobion spp.