DESC:
FIELD OF THE INVENTION
The present invention relates to synergistic insecticidal mixtures of Chlorantraniliprole, Methoxyfenozide and Biostimulant selected from Fulvic acid or Amino acid. The present invention more particularly relates to insecticidal compositions and a method of preparation thereof.

BACKGROUND OF THE INVENTION
Chlorantraniliprole is an insecticide with chemical name 5-bromo-N-[4-chloro-2-methyl-6-(methylcarbamoyl) phenyl]-2-(3-chloropyridin-2-yl) pyrazole-3-carboxamide.

Methoxyfenozide is a carbohydrazide and is a low toxicity insecticides with chemical name N'-tert-Butyl-N'-(3,5-dimethylbenzoyl)-3-methoxy-2-methylbenzohydrazide.

Pesticide composition comprising chlorantraniliprole and diacylhydrazine insecticide (methoxyfenozide) is known in CN104782630A.

The present inventors have surprisingly developed an insecticidal composition comprising Chlorantraniliprole, Methoxyfenozide, and Biostimulant selected from Fulvic acid, or Amino acid which increase the yield and plant vigour of the treated plant.

Advantages of the present invention
• Increase in yield of treated plants (cereals, pulses, oilseeds, fibre crop, sugar crops, leafy vegetables, tuber crops, fruit crops, flowers, ornamentals etc.)
• Increase in yield due to protection against insect pests.
• Increase in yield due to plant health and increase in reproductive parts of plant.
• Increase in yield due to more number of tillers, more branches and sub branches, more number of flowers, and more number of fruits.
• Increase plant vigor.
• Increase tolerance to insect-pests damage.
• Increase tolerance to the weather stress, moisture stress.
• Prevents lodging in susceptible plants (lodging due to biotic and abiotic factors, like heavy rains, winds, insects and diseases damage.
• Improves quality (means visual appearance, color, size, shape etc.) in grains, fruits, fiber, flowers, tuber, bulb, rhizomes, straw, leaves and other plant parts and plant products.
• Improves keeping quality of produce, increase post harvest life, storage life, protection from post harvest diseases.
• Decreases the synthetic nitrogeneous fertilizer requirement by crops treated with present invention.
• Decreases the dropping of buds, flowers, fruits, leaves etc.in crop treated with present invention.

OBJECTS OF THE INVENTION
It is an object of the present invention to provide an insecticidal composition comprising comprising Chlorantraniliprole, Methoxyfenozide and Biostimulant selected from Fulvic acid or Amino acid.

It is another object of the present invention to provide an insecticidal composition comprising comprising Chlorantraniliprole, Methoxyfenozide and Biostimulant selected from Fulvic acid or Amino acid which improve the yield and plant vigour of the treated plant.

SUMMARY OF THE INVENTION
According to an aspect of the present invention there is provided a synergistic insecticidal composition comprising:

I) Chlorantraniliprole in the range from 0.1 to 20% by weight of the composition;
II) Methoxyfenozide in the range from 0.1 to 30% by weight of the composition; and
III) Biostimulant in the range from 0.1 to 50% by weight of the composition wherein the said biostimulant is selected from Fulvic acid or Amino acid.

DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to insecticidal mixtures of Chlorantraniliprole, Methoxyfenozide and Biostimulant selected from Fulvic acid or Amino acid.

In an embodiment of the present invention there is provided a insecticidal composition of comprising:

I) Chlorantraniliprole in the range from 0.1 to 20% by weight of the composition;
II) Methoxyfenozide in the range from 0.1 to 30% by weight of the composition;
III) Biostimulant in the range from 0.1 to 50% by weight of the composition wherein the said biostimulant selected from Fulvic acid or Amino acid; and
IV) One or more inactive excipients.

In another embodiment of the present invention there is provided an insecticidal composition comprising Chlorantraniliprole Methoxyfenozide and Biostimulant selected from Fulvic acid or Amino acid with the following mass percentage of the composition:

Sr. No. Raw material Concentration range (w/w %)
i Chlorantraniliprole 0.1 to 20
ii Methoxyfenozide 0.1 to 30
iii Biostimulant 0.1 to 50

Biostimulant is selected from Fulvic acid, or Amino acid such as Glycine, Proline, Hydroxyproline, Glutamic acid, Alanine, Arginine, Phenylalanine.

The insecticidal composition of the present invention may be formulated in the forms given below:

Capsule suspension (CS), Dispersible concentrate (DC), Powder for dry seed treatment (DS), Emulsifiable concentrate (EC), Emulsion, water in oil (EO), Emulsion for seed treatment (ES), Emulsion, oil in water (EW), Flowable suspension/concentrate for seed treatment (FS), Granule/ soil applied (GR), Controlled (Slow or Fast) release granules (CR)Solution for seed treatment (LS), Micro-emulsion (ME), Oil dispersion (OD), Oil miscible flowable concentrate (oil miscible suspension (OF), Oil miscible liquid (OL), Suspension concentrate (= flowable concentrate) (SC), Suspo-emulsion (SE), Water soluble granule (SG), Soluble concentrate (SL), Water soluble powder (SP), Water dispersible granule (WG or WDG), Wettable powder (WP), Water dispersible powder for slurry treatment (WS), A mixed formulation of CS en SC (ZC), A mixed formulation of CS en SE (ZE), A mixed formulation of CS en EW (ZW).

In a preffered embodiment of the present invention the composition may be formulated as Suspension concentrate (SC).

In another embodiment the composition of the present invention further comprises inactive excipients.

The list of inactive excipients for SC formulation are as follows:

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 Ligno sulfonate.
Dispersing agent cum Emulsifier: Polyalkoxy alkyl ether, Ethylene oxide/propylene oxide block copolymer.
Dispersing agent & Wetting agent: Polyarylphenyl ether phosphate, Ethoxylated Fatty Alcohol etc., Ethylene oxide/propylene oxide block copolymer, Polyarylphenyl ether phosphate, Sodium dioctyl sulfosuccinate, sodium lauryl sulfate and sodium dodecyl benzene sulfonate, alkyldiphenylsulfonates, sodium isopropyl naphthalene sulfonate,Alkylnaphthalene sulfonate etc., Acrylic graft copolymer, Alkylated naphthalene sulfonate, sodium salt, Sodium salt of naphthalene sulfonate condensate, Sodium Ligno sulfonate,Sodium ploycarboxylate,EO/PO based copolymer, Phenol sulfonate, Sodium Methyl Oleoyl Taurate,
Wetting agent & Spreader: Trisiloxane ethoxylate.
Wetting agent & Emulsifier: Sodium dioctyl sulfosuccinate.
Antifoaming agent: Silicone antifoam emulsion, Dimethylsiloxane, Polydimethyl siloxane etc., Vegetable oil based antifoam, tallow based fatty acids, polyalkyleneoxide modified polydimethylsiloxane.
Rheology Modifier and Thickner: Polysaccharide.
Anti freezing Agent: Glycol (Monoethylene glycol, Diethylene glycol, Polypropylene glycol, Polyethylene glycol), Glycerin, Urea, Magnesium sulfate Heptahydrate, Sodium Chloride.
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.
Suspending and Anticaking agent: Silicone dioxide etc.,
Spreader: Organo modified Trisiloxane etc.,
Sticker and Penetrant: Poly glycerol ester etc.,
Deposition aid: Polyether etc.
Suspensind agent: Aluminum Magnesium Silicate, Bentonite clay, Silica, Attapulgite clay,
Thickners: Xanthan gum, PVK, carboxymethylcelluloses, or polyvinyl alcohols.

In another embodiment of the present invention there is provided a method of preparing a stable, non phytotoxic formulation of the present invention.

The method of application of the insecticidal composition of the present invention includes foliar spray, Seed treatment or treatment to planting materials, soil application.

The lists of crops which can be protected by the insecticidal composition of the present invention are GMO (Genetically Modified Organism) and Non GMO varieties of Cotton (Gossypium spp.), Paddy (Oryza sativa), Wheat (Triticum aestavum), Barley (Hordeum vulgare), Maize (Zea mays), Sorghum (Sorghum bicolor), 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), 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)

The insecticidal composition of the present invention can be used to control the Insects from the order of the Lepidoptera, for example cutworm Agrotis ypsilon, sugarcane shoot borer Chilo infuscatellus, sugarcane stalk borer Chilo partellus, sugarcane internode borer Chilo sacchariphagus, paddy/rice stem borer, Chilo suppressalis, rice leaffolder Cnaphalocrocis medinalis, apple colding moth Cydia pomonella, okra fruit borer Earias vittella, Earias insulana, Tomato fruit borer Helicoverpa armigera, tobacco budworm Helicoverpa virescens, corn earworm Helicoverpa zea, cabbage webworm Hellula undalis, Brinjal fruit and shoot borer Leucinodes orbonalis, bean pod borer Maruca vitrata, Maruca testulalis, armyworm Mythimna separata, cotton pinkbollworm Pectinophora gossypiella, citrus leafminer Phyllocnistis citrella, cabbage butterfly Pieris bras-sicae, diamond backmoth Plutella xylostella, paddy stem borer Scirpophaga excerptallis, Scirpophaga incertulas, Scirpophaga innotata, wheat stem borer Sesamia inferens, Sitotroga cerealella, Spilosoma obliqua, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Trichoplusia ni, Tryporyza novella, Tuta absoluta.

Beetles (Coleoptera), for example Anthonomus grandis, Bruchus lentis, Diabrotica semipunctata, Diabrotica virgifera, Dicladispa armigera, Epila-chna varivestis, Holotrichia bicolor, Holotrichia consanguinea, Holotrichia serrata, Leptinotarsa decemlineata, Phyllotreta chrysocephala, Popillia japonica.

Flies, mosquitoes (Diptera), e.g. Atherigona orientalis, Calliphora vicina, Dacus cucurbi-tae, Liriomyza trifolii, Melanagromyza obtuse.

Thrips (Thysanoptera), e.g. Dichromothrips ssp, Frankliniella occidentalis, 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. Cotton leafhopper Amrasca biguttula biguttula, Amrasca devastans, Mango hopper Amritodus atkinsoni, Idioscopus spp., cotton aphid Aphis gossypii, groundnut aphid Aphis crassivora, whitefly Bemisia argentifolii, Bemisia tabaci, cabbage aphid Brevicoryne brassicae, red gram bug Clavigralla gibbosa, leaf hopper Empoasca fabae, Lygus pratensis, Macrosiphum avenae, Myzus persicae, Nilaparvata lugens, Nephotettix virescens, Nephotettix nigropictus, Planococcus spp., Pseudococcus spp., Pyrilla perpusilla, Rhopalosiphum maidis, Saccharicoccus sacchari, Sitobion avenae, Sogatella furcifera, Trialeurodes vaporariorum, Toxoptera aurantiia, Psylla spp., Rhopalosiphum spp.

Arachnoidea, such as arachnids (Acarina/ plant mites), e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma variegatum, Ambryomma maculatum, Boophilus microplus, Eriophyidae spp. such as Aculus schlechtendali, Phyllocoptrata oleivora and Eriophyes sheldoni; Tarsonemidae spp. such as Phytonemus pallidus and Polyphagotarsonemus latus; Tenuipalpidae spp. such as Brevipalpus phoenicis; Tetra-nychidae spp. such as Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panony-chus citri, and Oligonychus pratensis; Araneida, e.g. Latrodectus mactans, and Loxos-celes reclusa.

The insecticidal composition of the present invention can be applied to any and all developmental stages of pests, such as egg, nymph, larva, pupa and adult. The pests may be controlled by contacting the target pest, its food supply, habitat, breeding ground or its locus with a pesticidally effective amount of the inventive mixtures or of compositions comprising the mixtures.

The insecticidal composition of the present invention is uses to improve the plant health.

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 insecticidal composition of the present invention is increased independently of the insecticidal 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 present 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.

The insecticidal composition of the present invention is used to increase plant logitivity (plant life)

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

In another preferred embodiment of the present invention, the yield of the plants treated according to the insecticidal composition of the present 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 insecticidal composition of the present invention.

Increased yield can 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 protein content, increased oil content, increased starch content, increased pigment content, increased leaf are index.

According to the present invention, the yield is increased by at least 4 %, preferable by 5 to 10%, more preferable by 10 to 20%, or even 20 to 30% compared to the untreated control plants or plants treated with pesticides in a way different from the method of the present invention. In general, the yield increase may even be higher.

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 present invention, the plant vigor of the treated plant is increased. In another preferred embodiment of the present invention, the plant vigor of the plants treated with insecticidal composition of the present 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 CO2 assimilation rate), increased stomatal conductance, increased CO2 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 present invention, the quality of the treated plant is increased.

In another preferred embodiment of the present invention, the quality of the plants treated with the insecticidal composition of the present 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 insecticidal composition 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 processability 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 insecticidal composition of the present invention and (2.) that the negative effects are not diminished by a direct action of the insecticidal composition of the present 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.

Manufacturing Process:
SC (Suspension Concentrate):

Step 1: Gum Solution should be made 12-18 hour prior to use. Take required quantity of water, biocide, and defoamer and homogenise, then slowly add gum powder to it and stir till complete dissolution.
Step 2: Charge required quantity of DM water need to be taken in designated vessel for Suspension concentrate production.
Step 3: Add required quantity of Wetting agent, antifreeze, dispersing agent & suspending agents and homogenise the contents for 45 – 60 minutes using high shear homogeniser.
Step 4: Then add technical and other remaining adjuvants excluding ‘thickener’ are added to it and homogenised to get uniform slurry ready for grinding.
Step 5: 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 6: Half quantity of the antifoam was added after grinding process completes and before sampling for in process analysis.
Step 7: Finally add gum solution to this formulation and send to QC for quality check.

EXAMPLES

The present invention will now be explained in detail by reference to the following formulation examples and a test example, which should not be construed as limiting the scope of the present invention.

Formulation recipe
1. Suspension concentrate (SC) formulation of Methoxyfenozide 20%+Chlorantraniliprole 5%+Fulvic Acid 2.5%
Chemical composition % (w/w) range of % (w/w)
Methoxyfenozide a.i. 20.00 15 to 25
Chlorantraniliprole a.i. 5.00 2.5 to 10
Fulvic acid 2.50 1 to 5
Wetting agent 3.50 3.50
Dispersing agent I 4.50 4.50
Dispersing agent II 0.50 0.50
Suspending agent 0.50 0.50
Antifoaming agent 0.30 0.30
Preservative 0.20 0.20
Antifreezing agent 5.00 5.00
Thickner 0.15 0.15
Diluent Water q.s. q.s.
Total 100.00 100.00

Storage stability of suspension concentrate (SC) of Methoxyfenozide 20%+Chlorantraniliprole 5%+Fulvic Acid 2.5%
Laboratory storage stability for 14 days
Parameters specification (in house) initial heat stability study at 54±2 0C cold storage stability at 0±2 0C
Methoxyfenozide content percent by mass 19.0 to 21.0 20.3 20.20 20.3
Chlorantraniliprole content percent by mass 4.75 to 5.5 5.25 5.2 5.25
Fulvic acid content percent by mass 2.375 to 2.750 2.51 2.5 2.51
Methoxyfenozide suspensibility percent min. 80 96.14 95.15 96.03
Chlorantraniliprole suspensibility percent min. 80 97.16 97.10 96.80
Fulvic acid suspesnibility precent min. 80 97.15 97.12 96.80
pH range (1% aq. Suspension) 5.5 to 7.5 6.5 6.55 6.5
Pourability 95% min. 97.4 97.2 97.5
Specific gravity 1.05-1.10 1.08 1.08 1.08
Viscosity at spindle no. 62, 20 rpm 350-800 cps 510 518 520
Particle size (micron) D50<3, D90<10 2.2,8.6 2.4,8.8 2.5,8.9
Persistent foam ml (after 1 minute) max. 60 nil 3 nil
Room temperature storage stability up to 12 months
Parameters specification (in house) 1 month 6 month 12 month
Methoxyfenozide content percent by mass 19.0 to 21.0 20.3 20.30 20.20
Chlorantraniliprole content percent by mass 4.75 to 5.5 5.25 5.25 5.2
Fulvic acid content percent by mass 2.375 to 2.750 2.51 2.51 2.5
Methoxyfenozide suspensibility percent min. 80 96.17 95.13 95.32
Chlorantraniliprole suspensibility percent min. 80 97.16 96.10 96.20
Fulvic acid suspesnibility precent min. 80 97.13 96.14 96.20
pH range (1% aq. Suspension) 5.5 to 7.5 6.5 6.5 6.5
Pourability 95% min. 97.4 97.4 97.3
Specific gravity 1.05-1.10 1.08 1.08 1.08
Viscosity at spindle no. 62, 20 rpm 350-800 cps 515 520 523
Particle size (micron) D50<3, D90<10 2.2,8.6 2.2,8.6 2.2,8.7
Persistent foam ml (after 1 minute) max. 60 nil nil 2

2. Suspension concentrate (SC) formulation of Methoxyfenozide 20%+Chlorantraniliprole 5%+Amino Acid 2.5%
Chemical composition % (w/w) range of % (w/w)
Methoxyfenozide a.i. 20.00 15 to 25
Chlorantraniliprole a.i. 5.00 2.5 to 10
Amino acid 2.50 1 to 5
Wetting agent 3.50 3.50
Dispersing agent 4.50 4.50
Dispersing agent 0.50 0.50
Suspending agent 0.50 0.50
Antifoaming agent 0.30 0.30
Preservative 0.20 0.20
Antifreezing agent 5.00 5.00
Thickner 0.15 0.15
Diluent Water q.s. q.s.
Total 100.00 100.00

Storage stability of suspension concentrate of Methoxyfenozide 20%+Chlorantraniliprole 5%+Amino Acid 2.5%
Laboratory storage stability for 14 days
Parameters specification (in house) initial heat stability study at 54±2 0C cold storage stability at 0±2 0C
Methoxyfenozide content percent by mass 19.0 to 21.0 20.3 20.20 20.3
Chlorantraniliprole content percent by mass 4.75 to 5.5 5.25 5.2 5.25
Amino acid content percent by mass 2.375 to 2.750 2.51 2.5 2.51
Methoxyfenozide suspensibility percent min. 80 96.14 95.15 96.03
Chlorantraniliprole suspensibility percent min. 80 97.16 97.10 96.80
Amino acid suspesnibility precent min. 80 96.14 95.12 96.05
pH range (1% aq. Suspension) 5.5 to 7.5 6.5 6.52 6.5
Pourability 95% min. 97.4 97.2 96.5
Specific gravity 1.05-1.10 1.08 1.08 1.08
Viscosity at spindle no. 62, 20 rpm 350-800 cps 525 513 520
Particle size (micron) D50<3, D90<10 2.2,8.6 2.4,8.8 2.5,8.9
Persistent foam ml (after 1 minute) max. 60 nil 2 nil
Room temperature storage stability up to 12 months
Parameters specification (in house) 1 month 6 month 12 month
Methoxyfenozide content percent by mass 19.0 to 21.0 20.3 20.30 20.20
Chlorantraniliprole content percent by mass 4.75 to 5.5 5.25 5.25 5.2
Amino acid content percent by mass 2.375 to 2.750 2.51 2.51 2.5
Methoxyfenozide suspensibility percent min. 80 96.17 95.13 95.32
Chlorantraniliprole suspensibility percent min. 80 97.16 96.10 96.20
Amino acid suspesnibility precent min. 80 96.17 95.13 95.32
pH range (1% aq. Suspension) 5.5 to 7.5 6.5 6.5 6.5
Pourability 95% min. 97.4 97.4 97.3
Specific gravity 1.05-1.10 1.08 1.08 1.08
Viscosity at spindle no. 62, 20 rpm 350-800 cps 525 518 523
Particle size (micron) D50<3, D90<10 2.2,8.6 2.2,8.6 2.2,8.7
Persistent foam ml (after 1 minute) max. 60 nil nil 1

Amino acid use in the above experiments are selected as “mixture of amino acids, (atleast two) selected from Glycine, Proline, Hydroxyproline, Glutamic acid, Alanine, Arginine, or Phenylalanine.

Biological Examples:
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 insecticidal action of the inventive mixtures can be demonstrated by the experiments below.

FIELD BIO-EFFICACY STUDIES:

EXPERIMENT 1: Control of Chilli insect-pests and yield
Crop & Variety : Chilli, Rekha
Location : Umreth, Dist. Anand, Gujarat
Plot size : 30 sq. mt. (6m x 5m)
Spacing : 100 cm row to row, 30 cm plant to plant
Treatment Number : Twelve
Replication : Three
Crop stage : 75 days
Method of Application : Foliar spray with hand operated knapsack sprayer
Spray volume : 500 liter per hectare
Agronomic Practices : Fertilizer, irrigation, inter culturing, earthing up and weeding done as per the crop requirement.

Observation Methods:
Larval control:
Count the number of live larvae of fruit borer (Helicoverpa armigera, Spodoptera litura, Spodoptera exigua) per plant. Record the live larvae from 10 plants per plot at before spray, 3, 7, 10 and 15 DAA (Days after application). Calculate the % Larval control (Observed value) as below formula

The calculated value of % larval control was worked out by using Colby’s formula given above.

Yield (Green fruit Yield) and other agronomic character:
The chilli green fruit yield data (gram per plot) was collected by weighing the freshly picked green fruit from entire plot. The other yield attributing characters like number of fruits per plant, number of flowers per plant and number of twigs per plant were also recorded from 10 randomly selected plants per plot.

Table 1: Treatment Details
Treatments details Formulation (g or ml/h) Rate (g.a.i/h)

T1-Methoxyfenozide 20%+Chlorantraniliprole 5%+Fulvic acid 2.5% SC 500 100+25+12.5
T2-Methoxyfenozide 20%+Chlorantraniliprole 5%+Amino acid 2.5% SC 500 100+25+12.5
T3-Methoxyfenozide 20%+Chlorantraniliprole 5% SC 500 100+25
T4-Methoxyfenozide 20%+Fulvic acid 2.5% SC 500 100+12.5
T5-Methoxyfenozide 20%+Amino acid 2.5% SC 500 100+12.5
T6-Chlorantraniliprole 5%+Fulvic acid 2.5% SC 500 25+12.5
T7-Chlorantraniliprole 5%+Amino acid 2.5% SC 500 25+12.5
T8-Methoxyfenozide 20% SC 500 100
T9-Chlorantraniliprole 5% SC 500 25
T10-Fulvic acid 2.5% SC 500 12.5
T11-Amino acid 2.5% SC 500 12.5
T12-Untreated Check (Water spray) 0 0

Table 2: Synergism in efficacy against fruit borer larval control in Chilli crop
Treatment Details % Fruit borer larval Control (Observed Value) % Fruit borer larval Control (Calculated Value) Colby's Ratio (Observed Value/Calculated Value)
3 DAA 7 DAA 10 DAA 15 DAA 3 DAA 7 DAA 10 DAA 15 DAA 3 DAA 7 DAA 10 DAA 15 DAA
T1 100.0 100.0 99.2 92.6 91.28 84.33 73.84 56.24 1.10 1.19 1.34 1.65
T2 100.0 100.0 98.8 93.1 91.14 84.20 73.76 55.97 1.10 1.19 1.34 1.66
T3 89.8 82.6 72.8 54.6 90.28 83.57 73.19 55.62 0.99 0.99 0.99 0.98
T4 65.0 53.2 38.5 18.2 66.95 54.97 40.27 20.73 0.97 0.97 0.96 0.88
T5 62.4 52.6 37.2 18.8 66.44 54.59 40.09 20.24 0.94 0.96 0.93 0.93
T6 74.1 64.8 55.4 43.2 76.29 66.80 57.25 45.57 0.97 0.97 0.97 0.95
T7 74.5 63.8 56.2 42.8 75.92 66.52 57.12 45.24 0.98 0.96 0.98 0.95
T8 63.2 52.8 38.8 19.6
T9 73.6 65.2 56.2 44.8
T10 10.2 4.6 2.4 1.4
T11 8.8 3.8 2.1 0.8
T12 0.0 0.0 0.0 0.0
DAA- Days After Application
The field trials data (table 2) shows that synergistic activities of methoxyfenozide+chlorantraniliprole+fulvic acid (T1) and methoxyfenozide+chlorantraniliprole+amino acid (T2) has been observed in terms of efficacy against fruit borer larval control in chilli crop.

Table 3: Yield and yield attributing characters of chilli crop
Treatment Details Twigs/ Plant % Increase over T3 Flowers/ Plant % Increase over T3 Fruits/ Plant % Increase over T3 Yield (g/plant) % Increase over T3

T1 31.2 60.8 118.4 31.8 87.2 22.5 948.6 56.2
T2 31.4 61.9 116.6 29.8 86.8 21.9 925.8 52.5
T3 19.4 89.8 71.2 607.2
T4 18.4 94.6 68.4 606.8
T5 17.8 96.2 67.4 596.2
T6 18.2 98.4 69.2 595.7
T7 16.7 97.5 70.4 602.4
T8 15.8 78.6 56.2 428.8
T9 15.2 79.6 55.8 468.6
T10 14.2 92.4 46.4 268.7
T11 13.6 91.2 44.8 246.5
T12 12.6 74.6 39.6 226.8

The field trial results presented in table 3 shows synergistic activity between three active ingredient of methoxyfenozide+chlorantraniliprole+fulvic acid (T1) and methoxyfenozide+chlorantraniliprole+amino acid (T2) has been observed by giving more number of twigs per plant, more number of flower per plant and number of green chilli fruits per plant. The green chilli fruit yield has been obtained from the treatment of methoxyfenozide+chlorantraniliprole+fulvic acid (T1) and methoxyfenozide+chlorantraniliprole+amino acid (T2).

The inventive synergistic mixture of methoxyfenozide+chlorantraniliprole+fulvic acid and methoxyfenozide+chlorantraniliprole+amino acid shows excellent synergistic control of fruit borer and also giving highest number of twigs, flower, green frui ts per plant and green chilli fruit yield compared to their solo and all other prior art treatments.

EXPERIMENT 2: Control of diamond back moth (Plutella xylostella) in cabbage crop.
Details of Experiment: Laboratory bio assay
a) Test Insects : Diamond backmoth (DBM) Plutella xylostella (3rd Instar)
b) Experiment design : Randomized Block Design
c) Replication : Four
d) Treatments : Twelve
e) Number of larvae per replication : 16 (One HIS tray with 16 cells)
a) Evaluation Method :
Cabbage leaves collected from the farm (unsprayed plant) and cut in to 2x2 sq.cm.size. Such 48 cut pieces of cotton leaves, dip in desired solution of insecticides as per the details given. After dipping, it placed on tissue paper and allow to dry for 15 minutes. Each treated cut piece of cotton leave, placed in to each cell of HIS tray (16 cell stay) with moist filter paper. The 3rd instar larvae from laboratory reared culture were released. One larvae in each cell and it covered with plastic lead with ventilation hole. Such 3 HIS tray were taken as 3 replication per treatment. These Trays should be kept in incubator at 30 degree C temperature and 14: 10 hrs L:D. Evaluation at 96 hrs after release for % mortality (dead + moribund) and % feeding. Larval mortality was calculated as below:

Number of dead larvae in treatment (out of 16)
% Larval mortality = ----------------------------------------------------------- X 100
Number of larvae treated (16)

If any larval mortality observed in untreated tray, the % corrected larval mortality should be calculated by below mention formula:

Henderson-Tilton's formula

Corrected % = (1 - n in Co before treatment * n in T after treatment

n in Co after treatment * n in T before treatment
) * 100
Where: n = Insect population, T = treated, Co = control
Table 4: Synergistic larval control of diamond backmoth (Plutella xylostella) in cabbage crop
Treatment details % Larval Control
Observed Value Calculated Value Ratio (Obs/Cal. Value)
Methoxyfenozide 20%+Chlorantraniliprole 5%+Fulvic acid 2.5% SC, 1 ml/l water 100.0 90.14 1.11
Methoxyfenozide 20%+Chlorantraniliprole 5%+Amino acid 2.5% SC, 1 ml/l water 100.0 90.02 1.11
Methoxyfenozide 20%+Chlorantraniliprole 5% SC, 1 ml/l water 86.4 88.15 0.98
Methoxyfenozide 20%+Fulvic acid 2.5% SC, 1 ml/l water 72.6 73.71 0.98
Methoxyfenozide 20%+Amino acid 2.5% SC, 1 ml/l water 71.8 73.39 0.98
Chlorantraniliprole 5%+Fulvic acid 2.5% SC, 1 ml/l water 66.8 68.80 0.97
Chlorantraniliprole 5%+Amino acid 2.5% SC, 1 ml/l water 66.2 68.43 0.97
Methoxyfenozide 20% SC, 1 ml/l water 68.4
Chlorantraniliprole 5% SC, 1 ml/l water 62.5
Fulvic acid 2.5% SC, 1 ml/l water 16.8
Amino acid 2.5% SC, 1 ml/l water 15.8

The laboratory bioassay of feeding test on diamond backmoth (Plutella xylostella) shows that methoxyfenozide +chlorantraniliprole+fulvic acid and methoxyfenozide+chlorantraniliprole+amino acid shows synergism in terms of larval control compared to the other prior art treatments.
,CLAIMS:
1. A synergistic insecticidal composition comprising:
I) Chlorantraniliprole in the range from 0.1 to 20% by weight of the composition;
II) Methoxyfenozide in the range from 0.1 to 30% by weight of the composition; and
III) Biostimulant in the range from 0.1 to 50% by weight of the composition wherein the said biostimulant selected from Fulvic acid or Amino acid.

2. The synergistic insecticidal composition as claimed in claim 1, wherein the Amino acid is selected from group consisting of Glycine, Proline, Hydroxyproline, Glutamic acid, Alanine, Arginine, or Phenylalanine.

3. The synergistic insecticidal composition as claimed in claim 1, wherein the composition further comprises inactive excipients selected from the group consisting of wetting agent, dispersing agent, emulsifier, spreader, antifoaming agent, rheology modifier, thickener, anti freezing agent, biocide, preservative, suspending aid, suspending agents, anti-caking agent, sticker, penetrant, deposition aid, or suspensind agent.

4. The synergistic insecticidal composition as claimed in claims 1 wherein the formulation is selected from Capsule suspension (CS), Dispersible concentrate (DC), Powder for dry seed treatment (DS), Emulsifiable concentrate (EC), Emulsion, water in oil (EO), Emulsion for seed treatment (ES), Emulsion, oil in water (EW), Flowable suspension/concentrate for seed treatment (FS), Granule/ soil applied (GR), Controlled (Slow or Fast) release granules (CR)Solution for seed treatment (LS), Micro-emulsion (ME), Oil dispersion (OD), Oil miscible flowable concentrate (oil miscible suspension (OF), Oil miscible liquid (OL), Suspension concentrate (= flowable concentrate) (SC), Suspo-emulsion (SE), Water soluble granule (SG), Soluble concentrate (SL), Water soluble powder (SP), Water dispersible granule (WG or WDG), Wettable powder (WP), Water dispersible powder for slurry treatment (WS), A mixed formulation of CS en SC (ZC), A mixed formulation of CS en SE (ZE), A mixed formulation of CS en EW (ZW).

5. The synergistic insecticidal composition as claimed in claims 4 wherein the formulation is Suspension Concentrate (SC).

6. A process for the preparation of synergistic insecticidal composition as claimed in claim 5 comprising the steps of:

i. Preparing Gum solution;
ii. Wetting agent, antifreeze agent, dispersing agent and suspending agent are homogenised to obtain a mixture;
iii. Adding technical and adjuvants in th mixture obtained in step (ii) followed by homogenizing to obtain uniform slurry;
iv. Adding halfpart of antifoam to the slurry obtained in step (iii);
v. Grinding the material obtained in step (iv);
vi. Adding remaining half part of antifoam in the formulation obtained in step (v);
vii. Adding Gum solution to the formulation obtained in step (v) to obtain the Suspension Concentrate.