DESC:FIELD OF THE INVENTION:
The present invention relates to synergistic insecticidal composition comprising A) Pymetrozine B) at least one insecticide selected from Flupyrimin and 5 Triflumezopyrim C) at least one more insecticide selected from Acephate, Chlorpyrifos, Profenofos, Fipronil, Bifenthrin, Lambda Cyhalothrin, Fenpropathrin, Acetamiprid, Clothianidin, Dinotefuran, Imidacloprid, Nitenpyram, Thiacloprid, Thiamethoxam, Sulfoxaflor, Flupyradifurone, Spinetoram, Spinosad, Abamectin, Emamectin Benzoate, Pyriproxyfen, Pyrifluquinazon, Afidopyropen, Diafenthiuron, 10 Cartap Hydrochloride, Thiocyclam Hydrogen Oxalate, Buprofezin, Methoxyfenozide, Tolfenpyrad, Indoxacarb, Chlorantraniliprole, Cyantraniliprole, Flubendiamide, Flonicamid and Azadirechtin with one or more inactive excipients. The present invention also relates to process for preparing the said composition and its use in crops. 15 BACKGROUND OF THE INVENTION
Pymetrozine was first disclosed in US4931439 and US4996325.Pymetrozine is chemically known as (E)-4,5-dihydro-6-methyl-4-(3-pyridylmethyleneamino)- 20 1,2,4-triazin-3(2H)-one and having chemical structure as below;
The mode of action of pymetrozine in insects has not been precisely determined 25 biochemically, but it may involve effects on neuroregulation or nerve-muscle interaction. Physiologically, it appears to act by preventing these insects from inserting their stylus in to the plant tissue.
Page 3 of 46
Pymetrozine is selective against Homoptera, causing them to stop feeding. Pymetrozine is used in control of aphids and whitefly in vegetables, potatoes, ornamentals, cotton, deciduous and citrus fruit, tobacco, hops; both juvenile and adult stages are susceptible and also control plant hoppers in rice. Pymetrozine application rates vary from 150 g/ha on potatoes to 200-300 g/ha on ornamentals, 5 tobacco and cotton; 10-30 g/hl on vegetables, fruit and hops. Pymetrozine is available in market with DP; GR; WP; WG formulation.
Flupyrimin was first disclosed in EP0268915A2. Flupyrimin, chemically known as [N-[(E)-1-(6-chloro-3-pyridylmethyl) pyridin-2(1H)-ylidene]- 2,2,2-10 trifluoroacetamide and having chemical structure as below;
Triflumezopyrim is an extremely effective hopper insecticide with low impact on non-target organisms including pollinators. This unique class of mesoionic 15 chemistry targets the nicotinic acetylcholine receptor, inducing a physiological action which is distinct from that of neonicotinoids. Triflumezopyrim is the first commercialized insecticide from this class and provides outstanding control of hoppers, including the brown planthopper, Nilaparvata lugens, which has developed strong resistance to neonicotinoids such as imidacloprid. 20
Triflumezopyrim acts by binding to and inhibiting the orthosteric site of the nicotinic acetylcholine receptor, deviating from action of neonicotinoids and other receptor agonists which, in contrast, stimulate the receptor, leading to over-
Page 4 of 46
excitation of the insect nervous system. Application timing is early in the growth of the rice, as soon as the population of hoppers reaches the economic threshold level.
CN 102388906 discloses a high-efficiency and low-toxicity compound insecticide which consists of clothianidin and pymetrozine and is particularly used for 25 5 application research on controlling rice plant hopper.
CN 101569312 discloses composition for preventing and treating rice plant hopper, relating to biodiesel cream and suspending agent containing pymetrozine and thiamethoxam. 10
CN102246766A describes an insecticidal composition containing flonicamid and pymetrozine. The insecticidal composition formed by the binary mixing of the flonicamid and the pymetrozine which serve as active ingredients, wherein a weight ratio of the two active ingredients is (1-80):(85-1), and preferably is (5-40):(75-10); 15 the total mass percentage content of the active ingredients in the insecticidal composition is between 1 and 90 percent, and preferably is between 8 and 70 percent, and the rest is auxiliary ingredients which are permitted to be used and acceptable in pesticides.
20 CN104920382A discloses pesticide, in particular to a low-volume spray containing pymetrozine and tolfenpyrad. The spray comprises, by mass, 10%-50% of pymetrozine, 1%-20% of tolfenpyrad, 5%-15% of tea saponin and the balance of water. In the preparation process, the water and the tea saponin are added into a mixing kettle to be evenly mixed, then the pymetrozine and the tolfenpyrad are 25 added to be sufficiently dispersed into the mixed liquor of the water and the tea saponin, grinding is performed through a sand mill, sampling is performed, and after the sample is detected to be qualified, filling and packaging are performed.
CN103621541A discloses a synergistic insecticidal composition 30 containing clothianidin and tolfenpyrad and applications thereof. The synergistic
Page 5 of 46
insecticidal composition employs clothianidin and tolfenpyrad as main effective components, wherein, the weight ratio of clothianidin to tolfenpyrad is 0.1-60:0.1-50.
CN101720769A relates to novel composition and a preparation method and 5 application thereof, wherein the insecticidal composition is a mixture comprising a compound (A), i.e. pymetrozine and a compound (B), i.e. chlorantraniliprole.
However still there is a need for an insecticidal composition which overcomes some of the existing problems and can be prepared easily without much complex 10 manufacturing process.
Inventors of the present invention have surprisingly found that the synergistic insecticidal composition comprising A) Pymetrozine B) at least one insecticide selected from Flupyrimin and Triflumezopyrim C) at least one more insecticide 15 selected from Acephate, Chlorpyrifos, Profenofos, Fipronil, Bifenthrin, Lambda Cyhalothrin, Fenpropathrin, Acetamiprid, Clothianidin, Dinotefuran, Imidacloprid, Nitenpyram, Thiacloprid, Thiamethoxam, Sulfoxaflor, Flupyradifurone, Spinetoram, Spinosad, Abamectin, Emamectin Benzoate, Pyriproxyfen, Pyrifluquinazon, Afidopyropen, Diafenthiuron, Cartap Hydrochloride, Thiocyclam 20 Hydrogen Oxalate, Buprofezin, Methoxyfenozide, Tolfenpyrad, Indoxacarb, Chlorantraniliprole, Cyantraniliprole, Flubendiamide, Flonicamid and Azadirechtin with one or more inactive excipients described herein in can provide solution to the above mentioned problems. 25 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 phytopathogenic harmful insects, at application rates which are as low as possible, compositions which, at a reduced 30 total amount of active compounds applied, have improved activity against the
Page 6 of 46
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 composition comprising A) Pymetrozine B) at least one insecticide 5 selected from Flupyrimin and Triflumezopyrim C) at least one more insecticide selected from Acephate, Chlorpyrifos, Profenofos, Fipronil, Bifenthrin, Lambda Cyhalothrin, Fenpropathrin, Acetamiprid, Clothianidin, Dinotefuran, Imidacloprid, Nitenpyram, Thiacloprid, Thiamethoxam, Sulfoxaflor, Flupyradifurone, Spinetoram, Spinosad, Abamectin, Emamectin Benzoate, Pyriproxyfen, 10 Pyrifluquinazon, Afidopyropen, Diafenthiuron, Cartap Hydrochloride, Thiocyclam Hydrogen Oxalate, Buprofezin, Methoxyfenozide, Tolfenpyrad, Indoxacarb, Chlorantraniliprole, Cyantraniliprole, Flubendiamide, Flonicamid and Azadirechtin with one or more inactive excipients.
15 Accordingly, in a main aspect of the present invention provides an synergistic insecticidal composition comprising A) Pymetrozine B) at least one insecticide selected from Flupyrimin and Triflumezopyrim C) at least one more insecticide selected from Acephate, Chlorpyrifos, Profenofos, Fipronil, Bifenthrin, Lambda Cyhalothrin, Fenpropathrin, Acetamiprid, Clothianidin, Dinotefuran, Imidacloprid, 20 Nitenpyram, Thiacloprid, Thiamethoxam, Sulfoxaflor, Flupyradifurone, Spinetoram, Spinosad, Abamectin, Emamectin Benzoate, Pyriproxyfen, Pyrifluquinazon, Afidopyropen, Diafenthiuron, Cartap Hydrochloride, Thiocyclam Hydrogen Oxalate, Buprofezin, Methoxyfenozide, Tolfenpyrad, Indoxacarb, Chlorantraniliprole, Cyantraniliprole, Flubendiamide, Flonicamid and Azadirechtin 25 with one or more inactive excipients.
Accordingly, in a second aspect, the present invention provides a method of preparing the synergistic insecticidal composition comprising A) Pymetrozine B) at least one insecticide selected from Flupyrimin and Triflumezopyrim C) at least one 30 more insecticide selected from Acephate, Chlorpyrifos, Profenofos, Fipronil, Bifenthrin, Lambda Cyhalothrin, Fenpropathrin, Acetamiprid, Clothianidin,
Page 7 of 46
Dinotefuran, Imidacloprid, Nitenpyram, Thiacloprid, Thiamethoxam, Sulfoxaflor, Flupyradifurone, Spinetoram, Spinosad, Abamectin, Emamectin Benzoate, Pyriproxyfen, Pyrifluquinazon, Afidopyropen, Diafenthiuron, Cartap Hydrochloride, Thiocyclam Hydrogen Oxalate, Buprofezin, Methoxyfenozide, Tolfenpyrad, Indoxacarb, Chlorantraniliprole, Cyantraniliprole, Flubendiamide, 5 Flonicamid and Azadirechtin with one or more inactive excipients.
Accordingly, in a third 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 insect-pest damage by applying to the plant 10 propagation material an insecticidal composition defined in the first aspect.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides solution to all the problems mentioned above by 15 providing the insecticidal composition.
The present invention provides synergistic insecticidal composition comprising A) Pymetrozine B) at least one insecticide selected from Flupyrimin and Triflumezopyrim C) at least one more insecticide selected from Acephate, 20 Chlorpyrifos, Profenofos, Fipronil, Bifenthrin, Lambda Cyhalothrin, Fenpropathrin, Acetamiprid, Clothianidin, Dinotefuran, Imidacloprid, Nitenpyram, Thiacloprid, Thiamethoxam, Sulfoxaflor, Flupyradifurone, Spinetoram, Spinosad, Abamectin, Emamectin Benzoate, Pyriproxyfen, Pyrifluquinazon, Afidopyropen, Diafenthiuron, Cartap Hydrochloride, Thiocyclam Hydrogen Oxalate, Buprofezin, 25 Methoxyfenozide, Tolfenpyrad, Indoxacarb, Chlorantraniliprole, Cyantraniliprole, Flubendiamide, Flonicamid and Azadirechtin with one or more inactive excipients.
"Effective amounts” as mentioned herein means that amount which, when applied to crops, is sufficient to kill/control target insect-pest. 30
Page 8 of 46
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 Suspension Concentrate (SC), Suspo emulsion 5 (SE), Capsule Suspension (CS), Oil Dispersion (OD), mixed formulation of CS and SC (ZC), a mixed formulation of CS and SE (ZE), a mixed formulation of CS and EW (ZW), Water Soluble Granules (SG), Water dispersible granule (WDG or WG), Water soluble bag formulation, Wettable Powder (WP), Soluble Powder (SP).. 10 As per one embodiment, synergistic insecticidal composition comprising A) Pymetrozine B) at least one insecticide selected from Flupyrimin and Triflumezopyrim C) at least one more insecticide selected from Acephate, Chlorpyrifos, Profenofos, Fipronil, Bifenthrin, Lambda Cyhalothrin, Fenpropathrin, Acetamiprid, Clothianidin, Dinotefuran, Imidacloprid, Nitenpyram, Thiacloprid, 15 Thiamethoxam, Sulfoxaflor, Flupyradifurone, Spinetoram, Spinosad, Abamectin, Emamectin Benzoate, Pyriproxyfen, Pyrifluquinazon, Afidopyropen, Diafenthiuron, Cartap Hydrochloride, Thiocyclam Hydrogen Oxalate, Buprofezin, Methoxyfenozide, Tolfenpyrad, Indoxacarb, Chlorantraniliprole, Cyantraniliprole, Flubendiamide, Flonicamid and Azadirechtin with one or more inactive excipients 20 wherein active ingredients are present in concentration as described below:
Compound A
Compound B
Compound C
Active ingredients
Pymetrozine
Flupyrimin Triflumezopyrim
Acephate, Chlorpyrifos, Profenofos, Fipronil, Bifenthrin, Lambda Cyhalothrin, Fenpropathrin, Acetamiprid, Clothianidin, Dinotefuran, Imidacloprid, Nitenpyram, Thiacloprid, Thiamethoxam, Sulfoxaflor, Flupyradifurone, Spinetoram, Spinosad, Abamectin, Emamectin Benzoate, Pyriproxyfen,
Page 9 of 46
Pyrifluquinazon, Afidopyropen, Diafenthiuron, Cartap Hydrochloride, Thiocyclam Hydrogen Oxalate, Buprofezin, Methoxyfenozide, Tolfenpyrad, Indoxacarb, Chlorantraniliprole, Cyantraniliprole, Flubendiamide, Flonicamid and Azadirechtin
Concentration
0.1 to40%
0.1 to 30%
0.1 to 30%
In another embodiment of the present invention the synergistic insecticidal composition comprising A) Pymetrozine B) at least one insecticide selected from Flupyrimin and Triflumezopyrim C) at least one more insecticide selected from 5 Acephate, Chlorpyrifos, Profenofos, Fipronil, Bifenthrin, Lambda Cyhalothrin, Fenpropathrin, Acetamiprid, Clothianidin, Dinotefuran, Imidacloprid, Nitenpyram, Thiacloprid, Thiamethoxam, Sulfoxaflor, Flupyradifurone, Spinetoram, Spinosad, Abamectin, Emamectin Benzoate, Pyriproxyfen, Pyrifluquinazon, Afidopyropen, Diafenthiuron, Cartap Hydrochloride, Thiocyclam Hydrogen Oxalate, Buprofezin, 10 Methoxyfenozide, Tolfenpyrad, Indoxacarb, Chlorantraniliprole, Cyantraniliprole, Flubendiamide, Flonicamid and Azadirechtin with one or more inactive excipients is effective for control of Insect-pests in the crops and plants selected genetically modified varieties or hybrid varieties or conventional varieties of Paddy (Oryza sativa), Cotton (Gossypium spp.), Jute (Corchorus oliotorus), Wheat (Triticum 15 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 20 (Sesamum indicum), Castor (Ricinus communis), Green gram (Vigna radiate), Black gram (Vigna mungo), Chickpea (Cicer aritinum), Cowpea (Vigna unguiculata), Redgram (Cajanus cajan), Frenchbean (Phaseolus vulgaris), Indian
Page 10 of 46
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 5 potato (Ipomoea batatas), Chilly (Capsicum annum), Garlic (Allium sativum), Cucumber (Cucumis sativus) and Melons (Cucumis melo), 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 10 (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 15 (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). 20
In one embodiment of the present invention, the pesticidal composition of present invention controls pests and insects belongs to the order Hemiptera, for example, rice leafhopper (Nephotettix nigropictus), rice brown plant hopper (Nilaparvata lugen), rice white backed plant hopper, Apple Mealy bug (Phenococcus aceris), 25 bean aphid (Aphis fabae), black citrus aphid (Toxoptera aurantii), citrus black scale (Saissetia oleae), cabbage aphid (Brevicoryne brassicae, Lipaphis erysimi), citrus red scale (Aonidiella aurantii), citrus mealybug (Planococcus citri), corn leaf aphid (Rhopalosiphum maidis), cotton aphid (Aphis gossypii), cotton leaf hoppers (Amrasca biguttula), cotton mealy bug (Planococcus spp. And Pseudococcus spp.), 30 cotton stainer (Dysdercus suturellus), cotton whitefly (Bemisia tabaci), cowpea aphid (Aphis crassivora), grain aphid (Sitobion avenae), golden glow aphid
Page 11 of 46
(Uroleucon spp.), grape mealybug (Pseudococcus maritimus), green peach aphid (Myzus persicae), greenhouse whitefly (Trialeurodes vaporariorum)spp., papaya mealy bug (Pracoccus marginatus), pea aphid (Acyrthosiphon pisum), sugarcane mealybug (Saccharicoccus sacchari), potato aphid (Myzus persicae), potato leaf hopper (Empoasca fabae), cotton whitefly (Bemisia tabaci), tarnished plant bug 5 (Lygus lineolaris), wooly apple aphid (Eriosoma lanigerum), yellow scale (Aonidiella citrine),order Lepidoptera, army worm (Mythimna unipuncta), asiatic rice borer (Chilo suppressalis), bean pod borer (Maruca vitrata), beet armyworm (Spodoptera exigua), black cutworm (Agrotis ipsilon), bollworm (Helicoverpa spp.),cabbage looper (Trichoplusia ni), codling moth (Cydia pomonella), croton 10 caterpillar (Achea janata), diamond backmoth (Plutella xylostella), cabbage worm (Pieris rapae), pink bollworm (Pectinophora gossypiella), sugarcane borer (Diatraea saccharalis), tobacco budworm (Heliothis virescens), tomato fruitworm (Helicoverpa zea), velvet bean caterpillar (Anticarsia gemmatalis), yellow stem borer (SCirpophaga incertulas), spotted bollworm (Earias vittella), rice leaffolder 15 (Cnaphalocrocis medinalis), pink stem borer (Sesamia spp.), tobacco leafeating caterpillar (Spodoptera litura), ; from the order Coleoptera, for example, apple twig borer (Amphicerus spp.), corn root worm (Diabrotica virgifera), cucumber beetle (diabrotica balteata), boll weevil (Anthonomus grandis), grape flea beetle (Altica chalybea), grape root worm (Fidia viticola), grape trunk borer (Clytoleptus 20 albofasciatus), radish flea beetle (Phyllotreta armoraciae), maize weevil (Sitophilus zeamais), northern corn rootworm (Diabrotica barberi), rice water weevil (Lissorhoptrus oryzophilus; from the order Orthoptera, for example, Gryllotalpa spp., Locusta spp., and Schistocerca is spp.; from the order Thysanoptera, for example, Frankliniella spp., Thrips palmi, Thrips tabaci and Scirtothrips dorsalis; 25 from the order Heteroptera, for example, Dysdercus spp., Leptocorisa spp., from the order Hymenoptera, for example, Solenopsis spp. ; from the order Diptera, for example, Antherigona soccata, Dacus spp., Liriomyza spp., Melanagromyza spp., from the order Acarina, for example, Aceria mangiferae, Brevipalpus spp., Eriophyes spp., Oligonychus mangiferus, Oligonychus punicae, Panonychus citri, 30 Panonychus ulmi, Polyphagotarsonemus latus, Tarsonemus spp., Tetranychus urticae, Tetranychus cinnabarinus,
Page 12 of 46
The insecticidal composition according to the 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 composition of present invention. 5
Method of Applications :
The composition of present invention can be applied by any of the below mentioned method;
Foliar application / spraying 10
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. 15 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 20 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 25 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 30
Page 13 of 46
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. 5 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 10 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 15 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 20 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. 25 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
Page 14 of 46
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 5 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 10 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 15 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 20 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. 25 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). 30
Page 15 of 46
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. 5 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 10 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 15 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 20 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 25 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 30
Page 16 of 46
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 5 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-10 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 15 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 20 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 25 ‘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 30 phosphate esters; aliphatic alcohol ethoxylates; alky ethoxylates; EO-PO block copolymers; and graft copolymers or mixtures thereof.
Page 17 of 46
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.
5 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 10 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 15 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 20 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 25 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 30 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
Page 18 of 46
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). 5 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 10 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 15 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. 20 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 25 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. 30
Page 19 of 46
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 5 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, 10 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 15 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 20 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 25 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.
30 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
Page 20 of 46
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 5 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 10 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. 15
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 etc., Dispersing agent cum Emulsifier: Polyalkoxy alkyl ether, 20 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: 25 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-30 3-one etc., Suspending aid: Aluminum Magnesium Silicate etc., Suspending and
Page 21 of 46
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 5 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 10 Wetting agent: Trisiloxane ethoxylate etc., Antifoam: Silicone antifoam emulsion etc., Suspending aid and anticaking agent: Silicone dioxide etc., Rheology Modifier,Thickner: Polysaccharide etc., Antifreezing Agent: Glycol (Monoethylene glycol, Diethylene glycol, Polypropylene glycol, Polyethylene glycol) etc., Biocide/Preservative: 1,2-benzisothiazolin-3-one, Sodium benzoate, 2-bromo-2-15 nitropropane-1,3-diol, Formaldehyde etc.,
Inactive excipients used in OD (Oil Dispersion) formulation: Solvent: N,N-Dimethyldecanamide, Non Ionic emulsifier: Unsaturated Fatty alcohol, Ethoxylated etc., Anionic emulsifier: Calcium Alkyl Benzen Sulphonate etc., Dispersing agent 20 and emulsifier: Ethoxylated TristyrylPhenol, Emulsifier and anti-flocculant: 2-Pyrrolidinone, 1-ethenylhexadecyl-,homopolymer etc., Rheology Modifier,Thickner: Polyamide etc., Green solvent and carrier: Fatty acid methyl ester etc., Spreading and wetting agent: Trisiloxane ethoxylate etc, Dispersing agent: Polyacrylate co-polymer, Polyarylalkylphenol polyethylene glycol 25 phosphoric acid ester, Polyether phosphate, Nonionic modified polyether etc.,
Inactive excipients used in EC(Emulsifiable concentrate) formulation : Solvent: Mixture of heavy aromatic hydrocarbons / C IX, Xylene, Biodiesel, n-Butanol (NBA), toluene, diesel, methanol, ethanol, n-butanol, isopropyl alcohol, turpentine, 30 mineral spirits, dimethylformamide, dimethyl sulfoxide, water and other solvents one or a mixture of more at an arbitrary ratio mixtures thereof, Solvent - C-9, N-
Page 22 of 46
Methyl-2-pyrrolidone etc., Emulsifiers, Wetting agents, Dispersants, Stabilizers: Polyaryl Phenol Ethoxylate etc., Emulsifier: Calcium Dodecyl Benzene Sulphonate with fatty acids, Blend of Polyaryl phenol ethoxylate and calcium dodecyl benzene sulfonate etc., Polyoxyethylene ethers, Polyoxyethylene alkylphenol ether sulfosuccinates, Styryl phenol ethoxylates, Nonyl phenol polyoxyethylene ethers, 5 polyoxyethylene castor oil, polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers any one or more at an arbitrary ratio mixtures thereof. Spreader, Sticker, Penetrant, Surface tension reducer: Alkyl polyethylene glycol ether etc., Sticker, Surface tension reducer, Binder: Polyvinylpyrrolidone etc.
10
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 15 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-20 methanol etc, defoaming agents: silicone antifoam emulsion etc, binders: corn starch, Polyvinylpyrrolidone etc, fillers: lactose, china clay/kaolin, titanium dioxide, talcum powder, diatomaceous earth, wetting, dispersing agent, stabilizer, sanitizers and defoaming agent: fatty amine ethoxylate etc., stabilizer, emulsifier and dispersing agent: polyacrylate co-polymer, polyacrylate polymer sodium salt 25 etc.
Inactive excipients used in WP (Wettable Powder) formulation: Anti caking agent: Urea formaldehyde resin / Urea-methanol etc., Binder: Polyvinylpyrrolidone etc., Binder and Filler: Corn starch etc., Defoamer: Silicone antifoam emulsion etc., 30 Dispersing agent: Sodium salt of naphthalene sulfonate condensate, Modified polyacrylate copolymer, Sodium polycarboxylate, Sodium Ligno sulfonate, Alkyl
Page 23 of 46
naphthalene sulfonate condensate, sodium salt, Polyacrylate co-polymer etc., Filler: Lactose, China clay/Kaolin, Titanium dioxide, Talcum powder, Diatomaceous earth etc., Suspending agent, Anti-caking Agent, Filler: Silicon dioxide, Wetting agent: blend of naphthalene sulfonate condensate, Sodium dodecylbenzene sulfonate, Sodium lauryl sulfate, Blend of alkyl naphthalene sulfonate and anionic wetting 5 agent, Sodium n-butyl naphthalene sulfonate, Sodium isopropyl naphthalene sulfonate, Blend of sodium alkyl aryl sulfonates, Wetting and Dispersing agent: Blend of naphthalene sulfonate condensate & phenol sulfonate condensate etc.
EXAMPLES 10 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. Example 1: Wettable Granule (WDG/WG) formulation of Pymetrozine 15 25%+Flupyrimin 10%+Thiamethoxam 10%
Chemical Composition
Percent (% w/w)
Pymetrozine a.i.
25.00
Flupyrimin a.i.
10.00
Thiamethoxam a.i.
10.00
Alkyl sulfonate
6.00
sodium salt of sulphonate napthalene formaldehyde condensate
3.00
Corn starch
20.00
Lactose
10.00
Silicon Antifoam
0.50
Silicon Dioxide
3.00
China clay
Q.S
Total
100.00
Manufacturing process (A ): Water Dispersible Granules (WG) by extrusion method 20
Step 1
Charge the required quantity of filler, wetting agent, dispersing agent, and suspending agent, & technical in premixing blender for homogenization for 30 minutes.
Page 24 of 46
Step 2
Pre-blended material is then grinded through Jet mill/ air classifier mills. Finely grinded material is blended in post blender till it becomes homogeneous. (For approx. 1.5 hr.)
Step 3
Finely grinded powder is mixed with required quantity of water to form extrudable dough.
Step 4
Dough is passed through extruder to get granules of required size.
Step 5
Wet granules are passed through Fluidized bed drier and further graded using vibrating screens.
Step 6
Final product is sent for QC approval.
Step 7
After approval material is packed in required pack sizes.
Manufacturing process (B): Water Dispersible Granules (WG) by spray dried method
Step 1
Charge required quantity of DM water need to be taken in designated vessel for production.
Step 2
Add required quantity of Wetting agent, dispersing agent, antifoam & suspending agents and homogenize the contents for 45 – 60 minutes using high shear homogenizer.
Step 3
Add required quantity technical and homogenized to get uniform slurry ready for grinding.
Step 4
Now material is subjected to grinding in Bead mill till desired particle size is achieved.
Step 5
After grinding process completes the material is sprayed at required temperature.
Step 6
After completion of spray drying process material is collected and sent for QC department approval.
Step 7
After approval material is packed in required pack sizes.
5
Storage stability of Wettable Granule (WDG/WG) of Pymetrozine 25%+Flupyrimin 10%+Thiamethoxam 10%
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
Pymetrozine content percent by mass
23.75 to 26.25
25.38
25.11
25.35
Flupyrimin contnet percent by mass
9.5 to 10.5
10.31
10.14
10.29
Thiamethoxam content percent by
9.5 to 10.5
10.29
10.18
10.28
Page 25 of 46
mass
Pymetrozine suspensibility percent min.
70
97.15
95.02
97.52
Flupyrimin suspensibility percent min.
70
95.36
91.15
94.56
Thiamethoxam suspensibility percent min.
70
95.75
93.11
94.25
pH range (1% aq. Suspension)
5.5 to 7.5
7.03
7.01
7.03
wettability sec. max.
60
8
9
9
wet sieve (45 micron) percent by mass min.
98.5
99.5
99.2
99.3
bulk density (g/ml)
0.45 to 0.75
0.47
0.46
0.47
moisture content percent by mass max.
max. 2%
1.1
0.8
1
Room temperature storage stability up to 12 months
Parameters
specification (in house)
Study Duration
1 month
6 month
12 months
Description
Off white colour granules
Complies
Complies
Complies
Pymetrozine content percent by mass
23.75 to 26.25
25.31
25.29
25.25
Flupyrimin contnet percent by mass
9.5 to 10.5
10.30
10.29
10.28
Thiamethoxam content percent by mass
9.5 to 10.5
10.29
10.28
10.26
Pymetrozine suspensibility percent min.
70
96.98
96.85
96.14
Flupyrimin suspensibility percent min.
70
95.12
94.46
94.16
Thiamethoxam suspensibility percent min.
70
95.24
95.02
94.58
pH range (1% aq. Suspension)
5.5 to 7.5
7.03
7.03
7.02
wettability sec. max.
60
8
8
9
wet sieve (45
98.5
99.30
99.30
99.20
Page 26 of 46
micron) percent by mass min.
bulk density (g/ml)
0.45 to 0.75
0.47
0.46
0.46
moisture content percent by mass max.
max. 2%
1.10
1.00
0.90
Example 2: Wettable Granules (WDG/WG) formulation of Pymetrozine 25%+Flupyrimin 10%+Chlorantraniliprole 6% 5
Chemical Composition
Percent (% w/w)
Pymetrozine a.i.
25.00
Flupyrimin a.i.
10.00
Thiamethoxam a.i.
6.00
Alkyl sulfonate
6.00
sodium salt of sulphonate napthalene formaldehyde condensate
3.00
Alkylated naphthalene sulfonate, sodium salt
2.00
Corn starch
20.00
Lactose
13.00
Silicon Antifoam
0.50
Silicon Dioxide
3.00
China clay
Q.S
Total
100.00
Manufacturing process as pre procedure in Example 1
Storage stability of Wettable Granule (WDG/WG) of Pymetrozine 10 25%+Flupyrimin 10%+Chlorantraniliprole 6%
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
Pymetrozine content percent by mass
23.75 to 26.25
25.47
25.11
25.41
Flupyrimin contnet percent by mass
9.5 to 10.5
10.21
10.15
10.2
Chlorantraniliprole content percent by
5.7 to 6.6
6.31
6.18
6.30
Page 27 of 46
mass
Pymetrozine suspensibility percent min.
70
96.94
93.15
96.15
Flupyrimin suspensibility percent min.
70
95.15
91.25
94.15
Chlorantraniliprole suspensibility percent min.
70
96.14
92.98
96.02
pH range (1% aq. Suspension)
5.5 to 7.5
7.03
7.01
7.03
wettability sec. max.
60
9
9
10
wet sieve (45 micron) percent by mass min.
98.5
99.5
99.2
99.3
bulk density (g/ml)
0.45 to 0.75
0.46
0.46
0.46
moisture content percent by mass max.
max. 2%
1.2
0.9
1
Room temperature storage stability up to 12 months
Parameters
specification (in house)
Study Duration
1 month
6 month
12 months
Description
Off white colour granules
Complies
Complies
Complies
Pymetrozine content percent by mass
23.75 to 26.25
25.46
25.45
25.43
Flupyrimin contnet percent by mass
9.5 to 10.5
10.21
10.19
10.18
Chlorantraniliprole content percent by mass
5.7 to 6.6
6.30
6.29
6.27
Pymetrozine suspensibility percent min.
70
96.59
96.55
96.51
Flupyrimin suspensibility percent min.
70
94.69
94.58
94.15
Chlorantraniliprole suspensibility percent min.
70
95.19
95.05
94.50
pH range (1% aq. Suspension)
5.5 to 7.5
7.03
7.03
7.01
wettability sec. max.
60
9
9
10
wet sieve (45 micron)
98.5
99.5
99.2
99.3
Page 28 of 46
percent by mass min.
bulk density (g/ml)
0.45 to 0.75
0.46
0.46
0.46
moisture content percent by mass max.
max. 2%
1.2
1.2
1.1
Example 3: Wettable Granule (WDG/WG) formulation of Pymetrozine 25%+Triflumezopyrim 4%+Chlorantraniliprole 6%
5
Chemical Composition
Percent (% w/w)
Pymetrozine a.i.
25.00
Triflumezopyrim a.i.
4.00
Chlorantraniliprole a.i.
6.00
Alkylated naphthalene sulfonate, sodium salt
5.00
Polyacrylate polymer sodium salt
4.00
alkyl sulfonate
5.00
Corn starch
22.00
Lactose
15.00
Silicon Antifoam
0.50
Silicon Dioxide
3.00
China clay
Q.S
Total
100.00
Manufacturing process as pre procedure in Example 1
Storage stability of Wettable Granule (WDG/WG) of Pymetrozine 25%+Triflumezopyrim 4%+Chlorantraniliprole 6%
10
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
Pymetrozine content percent by mass
23.75 to 26.25
25.62
25.16
25.6
Triflumezopyrim contnet percent by mass
3.80 to 4.40
4.25
4.19
4.18
Chlorantraniliprole content percent by mass
5.70 to 6.60
6.17
6.11
6.17
Pymetrozine suspensibility percent min.
70
97.15
95.16
97.05
Page 29 of 46
Triflumezopyrim suspensibility percent min.
70
96.15
94.54
96.01
Chlorantraniliprole suspensibility percent min.
70
97.15
93.15
97.03
pH range (1% aq. Suspension)
5.5 to 7.5
6.99
7.01
6.99
wettability sec. max.
60
9
10
10
wet sieve (45 micron) percent by mass min.
98.5
99.5
99.2
99.3
bulk density (g/ml)
0.45 to 0.75
0.46
0.46
0.46
moisture content percent by mass max.
max. 2%
1.4
1.2
1.1
Room temperature storage stability up to 12 months
Parameters
specification (in house)
Study Duration
1 month
6 month
12 months
Description
Off white colour granules
Complies
Complies
Complies
Pymetrozine content percent by mass
23.75 to 26.25
25.61
25.60
25.58
Triflumezopyrim contnet percent by mass
3.80 to 4.40
4.24
4.19
4.19
Chlorantraniliprole content percent by mass
5.70 to 6.60
6.17
6.16
6.15
Pymetrozine suspensibility percent min.
70
97.05
96.95
96.14
Triflumezopyrim suspensibility percent min.
70
96.02
95.62
95.51
Chlorantraniliprole suspensibility percent min.
70
96.65
96.61
96.15
pH range (1% aq. Suspension)
5.5 to 7.5
6.99
6.99
7.01
wettability sec. max.
60
9
10
10
wet sieve (45 micron) percent by mass min.
98.5
99.5
99.2
99.3
bulk density (g/ml)
0.45 to 0.75
0.46
0.46
0.46
moisture content
max. 2%
1.4
1.2
1.1
Page 30 of 46
percent by mass max.
Example 4: Suspension Concentrate (SC) formulation of Pymetrozine 15.63% + Triflumezopyrim 2.5% + Thiamethoxam 6.25%
5
Chemical Composition
Percent (% w/w)
Pymetrozine a.i.
15.63
Triflumezoptrim a.i.
2.50
Thiamethoxam a.i.
6.25
Ethoxylated Fatty Alcohol
2.00
Acrylic graft copolymer
3.00
Alkylated naphtalene sulfonate, sodium salt
0.50
Silicone antifoam
0.50
1,2-benzisothiazolin-3-one
0.20
Mono Ethylene Glycol
5.00
Xanthan powder
0.20
D.M Water
Q.S
Total
100.00
Step 1
Gum Solution should be made 12-18 hour prior to use. Take required quantity of water, biocide, and defoamer and homogenize, 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 homogenize the contents for 45 – 60 minutes using high shear homogenizer.
Step 4
Then add technical and other remaining adjuvants excluding ‘thickener’ are added to it and homogenized 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.
Storage stability of Suspension Concentrate (SC) formulation of Pymetrozine 15.63% + Triflumezopyrim 2.5% + Thiamethoxam 6.25%
10
Laboratory storage stability for 14 days
Parameters
Specification
Initial
Stability (for 14 days)
Page 31 of 46
(In house)
At 54±2 0C
At 0±2 0C
Description
Off white colour flowable liquid
Complies
Complies
Complies
Pymetrozine content percent by mass
14.85 to 16.41
15.69
15.67
15.68
Triflumezopyrim contnet percent by mass
2.38 to 2.75
2.58
2.55
2.58
Thiamethoxam content percent by mass
5.94 to 6.88
6.33
6.30
6.33
Pymetrozine suspensibility percent mini.
80
98.55
95.65
96.25
Triflumezopyrim suspensibility percent mini.
80
98.14
94.56
97.91
Thiamethoxam suspensibility percent mini.
80
97.13
94.25
96.10
pH range (1% aq. Suspension)
5.5 to7.5
7.05
7.04
7.05
Pourability
95 % min
98.70
97.70
97.60
Specific gravity
1.05 – 1.15
1.09
1.09
1.09
Viscosity at spindle no.62, 20 rpm
350 -800 cps
510
520
530
Particle size (micron)
D50 <3, D90 <10
2.2, 7.9
2.6, 8.5
2.7, 8.5
Persistent foam ml (after 1 minute) max.
60
nil
nil
nil
Room temperature storage data
Parameters
Specification (In house)
Study Duration
1 month
6 month
12 months
Description
Off white colour flowable liquid
Complies
Complies
Complies
Pymetrozine content percent by mass
14.85 to 16.41
15.65
15.68
15.67
Triflumezopyrim contnet percent by mass
2.38 to 2.75
2.58
2.57
2.58
Thiamethoxam content percent by mass
5.94 to 6.88
6.33
6.32
6.31
Pymetrozine suspensibility percent mini.
80
97.85
97.61
97.19
Triflumezopyrim suspensibility percent
80
97.62
97.14
96.33
Page 32 of 46
mini.
Thiamethoxam suspensibility percent mini.
80
96.15
96.56
95.65
pH range (1% aq. Suspension)
5.5 to7.5
7.05
7.04
7.04
Pourability
95 % min
98.70
98.60
98.30
Specific gravity
1.05 – 1.15
1.09
1.09
1.09
Viscosity at spindle no.62, 20 rpm
350 -800 cps
510
510
515
Particle size (micron)
D50 <3, D90 <10
2.2, 8
2.2, 8.1
2.3, 8.2
Persistent foam ml (after 1 minute) max.
60
nil
nil
nil
Example 5: Suspension Concentrate (SC) formulation of Pymetrozine 12.5% + Flupyrimin 5% + Thiamethoxam 5%
5
Chemical Composition
Percent (% w/w)
Pymetrozine a.i.
12.50
Flupyrimin a.i.
5.00
Thiamethoxam a.i.
5.00
Ethoxylated Fatty Alcohol
2.00
Acrylic graft copolymer
3.00
Alkylated naphtalene sulfonate, sodium salt
0.50
Silicone antifoam
0.50
1,2-benzisothiazolin-3-one
0.20
Mono Ethylene Glycol
5.00
Xanthan powder
0.15
D.M Water
Q.S
Total
100.00
Manufacturing process as pre procedure in Example 5
Storage stability of Suspension Concentrate (SC) formulation of Pymetrozine 12.5%+Flupyrimin 5%+Thiamethoxam 5%
10
Laboratory storage stability for 14 days
Parameters
Specification (In house)
Initial
Stability (for 14 days)
At 54±2 0C
At 0±2 0C
Description
Red colour flowable liquid
Complies
Complies
Complies
Page 33 of 46
Pymetrozine content percent by mass
11.86 to 13.13
12.62
12.53
12.61
Flupyrimin content percent by mass
4.75 to 5.50
5.24
5.13
5.23
Thiamethoxam content percent by mass
4.75 to 5.50
5.22
5.05
5.22
Pymetrozine suspensibility percent mini.
80
98.35
95.15
98.12
Flupyrimin suspensibility percent mini.
80
98.15
96.55
97.85
Thiamethoxam suspensibility percent mini.
80
97.85
95.19
97.50
pH range (1% aq. Suspension)
5.5 to7.5
7.05
7.08
7.05
Pourability
95 % min
98.70
97.70
97.60
Specific gravity
1.05 – 1.15
1.09
1.09
1.09
Viscosity at spindle no.62, 20 rpm
350 -800 cps
600
610
635
Particle size (micron)
D50 <3, D90 <10
2.2, 7.9
2.6, 8.5
2.7, 8.5
Persistent foam ml (after 1 minute) max.
60
nil
5
nil
Room temperature storage data
Parameters
Specification (In house)
Study Duration
1 month
6 month
12 months
Description
Off white colour flowable liquid
Complies
Complies
Complies
Pymetrozine content percent by mass
11.86 to 13.13
12.61
12.60
12.59
Flupyrimin content percent by mass
4.75 to 5.50
5.23
5.22
5.21
Thiamethoxam content percent by mass
4.75 to 5.50
5.21
5.20
5.19
Pymetrozine suspensibility percent mini.
80
98.38
98.75
98.54
Flupyrimin suspensibility percent mini.
80
97.75
97.68
97.15
Thiamethoxam suspensibility percent mini.
80
98.45
98.63
98..58
Page 34 of 46
pH range (1% aq. Suspension)
5.5 to7.5
7.05
7.06
7.06
Pourability
95 % min
98.70
98.60
98.30
Specific gravity
1.05 – 1.15
1.09
1.09
1.09
Viscosity at spindle no.62, 20 rpm
350 -800 cps
600
600
605
Particle size (micron)
D50 <3, D90 <10
2.2, 8
2.2, 8.1
2.3, 8.2
Persistent foam ml (after 1 minute) max.
60
nil
nil
3
Most Preferred formulations
AI-1
AI-2
AI3
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
6
AI-1
AI-2(i)
Clothianidin
25
10
10
45
WDG
500
125.0
50.0
50.0
7
AI-1
AI-2(i)
Clothianidin
12.5
5
5
22.5
SC
1000
125.0
50.0
50.0
8
AI-1
AI-2(i)
Thiamethoxam
25
10
10
45
WDG
500
125.0
50.0
50.0
9
AI-1
AI-2(i)
Thiamethoxam
12.5
5
5
22.5
SC
1000
125.0
50.0
50.0
10
AI-1
AI-2(i)
Dinotefuran
25
10
10
45
WP
500
125.0
50.0
50.0
11
AI-1
AI-2(i)
Tolfenpyrad
12.5
5
7.5
25
SC
1000
125.0
50.0
75.0
12
AI-1
AI-2(i)
Chlorantraniliprole
25
10
6
41
WDG
500
125.0
50.0
30.0
13
AI-1
AI-2(ii)
Clothianidin
15.63
2.5
6.25
24.38
SC
800
125.0
20.0
50.0
14
AI-1
AI-2(ii)
Dinotefuran
25
4
10
39
WP
500
125.0
20.0
50.0
15
AI-1
AI-2(ii)
Thiamethoxam
15.63
2.5
6.25
24.38
SC
800
125.0
20.0
50.0
16
AI-1
AI-2(ii)
Tolfenpyrad
12.5
2
7.5
22
SC
1000
125.0
20.0
75.0
17
AI-1
AI-2(ii)
Chlorantraniliprole
25
4
6
35
WDG
500
125.0
20.0
30.0
Biological examples 5
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
Page 35 of 46
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 5 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 % insect control data used to calculate the synergism, as per the below formula. 10
The synergistic pesticide action of the inventive mixtures calculated as follows:
Field experiments of inventive synergistic mixtures of pymetrozine+flupyrimin+thiamethoxam, pymetrozine+flupyrimin+tolfenpyrad, 15 pymetrozine+triflumezopyrim+thiamethoxam and pymetrozine+triflumezopyrim+tolfenpyrad on paddy/rice crop to evaluate the bio-efficacy against brown plant hopper (BPH) Nilaparvata lugens.
20
EXPERIMENT 1: Control of brown plant hopper (BPH), Nilaparvata lugen in paddy/rice crop.
Crop & Variety : Paddy, Basmati PR 1121
Location : Khanna, Punjab
Treatments : Twelve 25
Replication : Four
Plot size : 30 m2 (6 m x 5 m)
E = X + Y + Z -- { XY + YZ + XZ } + ( X Y Z )
100 10000
Where E = Expected % control by mixture of three products A, B and C in a defined dose
X = Observed % control by product A
Y = Observed % control by product B
Z = Observed % control by product C
Ratio = Observed Control %
Expected Control %
Ratio of O/E > 1, means synergism observed.
Page 36 of 46
Crop Stage at spraying: Panicle emergence stage (77 days after transplanting)
Method of Application: Foliar spray with back pack sprayer fitted with hollow cone nozzle
Agronomic Practices : Fertilizer, irrigation, inter culturing and weeding done as per
the crop requirement. 5
Observation Methods:
Record the number of brown plant hopper (nymph+adult) per hill. such ten hills per plot at 1, 5,
10 and 15 days after application (DAA).
Calculate percent insect control and then calculate Colby ratio to study synergism. 10
Table 1: Treatment composition
Treatment compositions
Formulation (ml/500 lit water)
gram active ingredient /500 lit water
Sample ABC-Pymetrozine 12.5%+Flupyrimin 5%+Thiamethoxam 5% SC
1000 ml
125+50+50
Sample ABD-Pymetrozine 12.5%+Flupyrimin 5%+Tolfenpyrad 7.5% SC
1000 ml
125+50+75
Sample AB-Pymetrozine 12.5%+Flupyrimin 5% SC
1000 ml
125+50
Sample AC-Pymetrozine 12.5%+Thiamethoxam 5% SC
1000 ml
125+50
Sample AD-Pymetrozine 12.5%+Tolfenpyrad 7.5% SC
1000 ml
125+75
Sample BC-Flupyrimin 5%+Thiamethoxam 5% SC
1000 ml
50+50
Sample BD-Flupyrimin 5%+Tolfenpyrad 7.5% SC
1000 ml
50+75
Sample A-Pymetrozine 50% WG
250 ml
125
Sample B-Flupyrimin 10% SC
500 ml
50
Sample C-Thiamethoxam 30% SC
167 ml
50
Sample D-Tolfenpyrad 15% EC
500 ml
75
UTC (Untreated Check)
0
0
ml- mili liter, sc-suspension concentrate, wg/wdg-water dispersible granule, ec-emulsifiable concentrate
Table 2: Synergistic activity against brown plant hopper (BPH), Nilaparvata lugen 15
Treatment compositions
% BPH Control Observed
% BPH Control Expected
Colby Ratio o/e
Page 37 of 46
3 DAA
7 DAA
3 DAA
7 DAA
3 DAA
7 DAA
Sample ABC
98.6
95.6
91.36
87.66
1.08
1.09
Sample ABD
97.6
94.8
91.76
88.91
1.06
1.07
Sample AB
82.8
77.4
83.45
79.15
0.99
0.98
Sample AC
78.8
72.4
79.33
74.07
0.99
0.98
Sample AD
79.6
75.6
80.28
76.70
0.99
0.99
Sample BC
77.2
69.8
78.18
71.82
0.99
0.97
Sample BD
78.4
72.4
79.18
74.68
0.99
0.97
Sample A
60.4
56.2
Sample B
58.2
52.4
Sample C
47.8
40.8
Sample D
50.2
46.8
UTC
0.0
0.0
DAA- Days after application
Field experiments shows synergistic activities read mix formulation of pymetrozine+flupyrimin+thiamethoxam, pymetrozine+flupyrimin+tolfenpyrad on brown plant hopper compared to their two active ingredient mixtures as well as solo application. 5
EXPERIMENT 2: Control of brown plant hopper (BPH), Nilaparvata lugen in paddy/rice crop.
Crop : Paddy 10
Location : Kurud, Raipur, Chhattishgarh
Treatments : Twelve
Replication : Four
Plot size : 30 m2 (6 m x 5 m)
Crop Stage at spraying: Before panicle emergence stage (65 days after 15 transplanting)
Method of Application: Foliar spray with back pack sprayer fitted with hollow cone nozzle
Agronomic Practices : Fertilizer, irrigation, inter culturing and weeding done as per
the crop requirement. 20
Observation Methods:
Record the number of brown plant hopper (nymph+adult) per hill. such ten hills per plot at 1, 5,
10 and 15 days after application (DAA).
Calculate percent insect control and then calculate Colby ratio to study synergism. 25
Table 3: Treatment composition
Treatment compositions
Formulation
gram active
Page 38 of 46
(ml/500 lit water)
ingredient /500 lit water
Sample AEC-Pymetrozine 15.63%+Triflumezopyrim 2.5%+Thiamethoxam 6.25% SC
800 ml
125+20+50
Sample AED-Pymetrozine 12.5%+Triflumezopyrim 2%+Tolfenpyrad 7.5% SC
1000 ml
125+20+75
Sample AE-Pymetrozine 12.5%+Triflumezopyrim 2% SC
1000 ml
125+20
Sample AC-Pymetrozine 15.63%+Thiamethoxam 6.25% SC
800 ml
125+50
Sample AD-Pymetrozine 12.5%+Tolfenpyrad 7.5% SC
1000 ml
125+75
Sample EC-Triflumezopyrim 2.5%+Thiamethoxam 6.25% SC
800 ml
20+50
Sample ED-Triflumezopyrim 2%+Tolfenpyrad 7.5% SC
1000 ml
20+75
Sample A-Pymetrozine 50% WG
250 ml
125
Sample E-Triflumezopyrim 20% SC
100 ml
20
Sample C-Thiamethoxam 30% SC
167 ml
50
Sample D-Tolfenpyrad 15% EC
500 ml
75
UTC (Untreated Check)
0
0
ml- mili liter, sc-suspension concentrate, wg/wdg-water dispersible granule, ec-emulsifiable concentrate
Table 4: Synergistic activity against brown plant hopper (BPH), Nilaparvata lugen
Treatment compositions
% BPH Control Observed
% BPH Control Expected
Colby Ratio o/e
3 DAA
7 DAA
3 DAA
7 DAA
3 DAA
7 DAA
Sample AEC
97.8
93.6
87.33
84.32
1.12
1.11
Sample AED
98.2
92.4
87.33
84.49
1.12
1.09
Sample AE
74.8
70.2
75.36
72.20
0.99
0.97
Sample AC
75.6
69.8
76.46
72.59
0.99
0.96
Sample AD
74.8
71.4
76.46
72.88
0.98
0.98
Sample EC
71.2
65.2
72.35
67.74
0.98
0.96
Sample ED
70.6
66.4
72.35
68.08
0.98
0.98
Sample A
54.2
51.4
Sample E
46.2
42.8
Sample C
48.6
43.6
Sample D
48.6
44.2
UTC
0.0
0.0
Page 39 of 46
Field experiments shows synergistic activities read mix formulation of pymetrozine +triflumezopyrim+thiamethoxam and pymetrozine+triflumezopyrim+tolfenpyrad on brown plant hopper compared to their two active ingredient mixtures as well as solo application.
5
Table 5: Residual control of brown plant hopper (BPH), Nilaparvata lugen infesting paddy crop
This experiment was conducted in Kurud, Raipur, Chhatishgarh area and experimental details was same as Experiment 2, where number of treatments were 18 (eighteen). The field observations were recorded to judge the residual control of 10 brown plant hopper.
Treatment compositions
% BPH control Observed
1 DAA
5 DAA
10 DAA
15 DAA
Sample ABC
98.2
96.2
91.4
86.2
Sample ABD
98.8
97.0
92.4
88.6
Sample AEC
97.6
94.6
90.2
85.4
Sample AED
98.6
95.2
91.2
85.8
Sample AB
88.6
84.2
75.4
56.2
Sample AC
86.4
82.5
70.2
54.2
Sample AD
87.2
81.4
68.8
52.4
Sample BC
86.2
80.2
64.6
46.8
Sample BD
85.8
77.4
68.2
50.2
Sample AE
84.6
76.2
65.6
38.6
Sample EC
86.2
79.8
62.6
40.6
Sample ED
83.6
78.4
64.8
45.2
Sample A
74.6
62.4
42.0
18.6
Sample B
72.3
58.2
38.2
20.4
Sample C
70.8
57.8
28.6
0.0
Sample D
73.4
59.2
27.6
0.0
Sample E
72.6
56.8
24.6
5.6
Untreated Control
0.0
0.0
0.0
0.0
Field experiments shows that synergistic ready mix formulation of pymetrozine 15 +flupyrimin+thiamethoxam, pymetrozine+flupyrimin+tolfenpyrad, pymetrozine
Page 40 of 46
+triflumezopyrim +thiamethoxam and pymetrozine+triflumezopyrim+tolfenpyrad provide residual (longer duration) control of brown plant hopper (> 85% control upto 15 days) on paddy/rice crop compared to their two active ingredient mixtures as well as their solo application. ,CLAIMS:CLAIMS We claim; [CLAIM 1]. An synergistic insecticidal composition comprising: A) Pymetrozine; B) at least one insecticide selected from Flupyrimin and Triflumezopyrim; C) at least one more insecticide selected from Acephate, Chlorpyrifos, Profenofos, Fipronil, Bifenthrin, Lambda Cyhalothrin, Fenpropathrin, Acetamiprid, Clothianidin, Dinotefuran, Imidacloprid, Nitenpyram, Thiacloprid, Thiamethoxam, Sulfoxaflor, Flupyradifurone, Spinetoram, Spinosad, Abamectin, Emamectin Benzoate, Pyriproxyfen, Pyrifluquinazon, Afidopyropen, Diafenthiuron, Cartap Hydrochloride, Thiocyclam Hydrogen Oxalate, Buprofezin, Methoxyfenozide, Tolfenpyrad, Indoxacarb, Chlorantraniliprole, Cyantraniliprole, Flubendiamide, Flonicamid and Azadirechtin; and D) one or more other inactive excipients. [CLAIM 2]. The synergistic composition as claimed in claim 1 wherein the component (A) Pymetrozine is in ratio of 0.1 to40%, component (B) at least one insecticide selected from Flupyrimin and Triflumezopyrim is in ratio of 0.1 to 30% and component (C) at least one more insecticide selected from Acephate, Chlorpyrifos, Profenofos, Fipronil, Bifenthrin, Lambda Cyhalothrin, Fenpropathrin, Acetamiprid, Clothianidin, Dinotefuran, Imidacloprid, Nitenpyram, Thiacloprid, Thiamethoxam, Sulfoxaflor, Flupyradifurone, Spinetoram, Spinosad, Abamectin, Emamectin Benzoate, Pyriproxyfen, Pyrifluquinazon, Afidopyropen, Diafenthiuron, Cartap Hydrochloride, Thiocyclam Hydrogen Oxalate, Buprofezin, Methoxyfenozide, Tolfenpyrad, Indoxacarb,
Page 42 of 46
Chlorantraniliprole, Cyantraniliprole, Flubendiamide, Flonicamid and Azadirechtin is in ratio of 0.1 to 30% [CLAIM 3]. The synergistic composition as claimed in claim 1 or 2, 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 and buffering agent. [CLAIM 4]. The synergistic composition as claimed in claim 1-4, wherein the formulations comprises of Suspension Concentrate (SC), Suspo emulsion (SE), Capsule Suspension (CS), Oil Dispersion (OD), mixed formulation of CS and SC (ZC), a mixed formulation of CS and SE (ZE), a mixed formulation of CS and EW (ZW), Water dispersible granule (WDG or WG), Water soluble bag formulation, Wettable Powder (WP), Soluble Powder (SP). [CLAIM 5]. The formulation comprising the synergistic composition as claimed in claim 1 or 4, wherein the Wettable Granule (WDG/WG) formulation comprises: a) component (A) Pymetrozine is in ratio of 0.1 to 40%, component (B) at least one insecticide is in ratio of 0.1 to 30% and component (C) at least one more insecticide is in ratio of 0.1 to 30%; b) Alkyl sulfonate c) sodium salt of sulphonate napthalene formaldehyde condensate d) Corn starch e) Lactose f) Silicon Antifoam g) Silicon Dioxide h) China clay.
Page 43 of 46
[CLAIM 6]. The formulation comprising the synergistic composition as claimed in claim 1 or 4, wherein the Suspension Concentrate (SC) formulation comprises: a) component (A) Pymetrozine is in ratio of 0.1 to 40%, component (B) at least one insecticide is in ratio of 0.1 to 30% and component (C) at least one more insecticide is in ratio of 0.1 to 30%; b) Ethoxylated Fatty Alcohol c) Acrylic graft copolymer d) Alkylated naphtalene sulfonate, sodium salt e) Silicone antifoam f) 1,2-benzisothiazolin-3-one g) Mono Ethylene Glycol h) Xanthan powder i) D.M Water [CLAIM 7]. 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 genetically modified varieties or hybrid varieties or conventional varieties of Paddy (Oryza sativa), Cotton (Gossypium spp.), Wheat (Triticum aestavum), Maize (Zea mays), Sugarcane (Saccharum officinarum), Soybean (Glycin max), Peanut (Arachis hypogaea), Sunflower (Helianthus annuus), Mustard (Brassica juncea), Green gram (Vigna radiate), Black gram (Vigna mungo), Chickpea (Cicer aritinum), Cowpea (Vigna unguiculata), 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), Cucumber (Cucumis sativus) and Melons (Cucumis melo),
Page 44 of 46
Apple (Melus domestica), Banana (Musa spp.), Citrus groups (Citrus spp.), Grape (Vitis vinifera), Mango (Mangifera indica), Papaya (Carica papaya), Pomegranate (Punica granatum) , Tea (Camellia sinensis), Coffea (Coffea Arabica), Cumin (Cuminum cyminum). [CLAIM 8]. The synergistic composition as claimed in any of the preceding claims, wherein the said composition control pests and insects from the order Hemiptera, for example, rice leafhopper (Nephotettix nigropictus), rice brown plant hopper (Nilaparvata lugen), rice white backed plant hopper, Apple Mealy bug (Phenococcus aceris), bean aphid (Aphis fabae), black citrus aphid (Toxoptera aurantii), citrus black scale (Saissetia oleae), cabbage aphid (Brevicoryne brassicae, Lipaphis erysimi), citrus red scale (Aonidiella aurantii), citrus mealybug (Planococcus citri), corn leaf aphid (Rhopalosiphum maidis), cotton aphid (Aphis gossypii), cotton leaf hoppers (Amrasca biguttula), cotton mealy bug (Planococcus spp. And Pseudococcus spp.), cotton stainer (Dysdercus suturellus), cotton whitefly (Bemisia tabaci), cowpea aphid (Aphis crassivora), grain aphid (Sitobion avenae), golden glow aphid (Uroleucon spp.), grape mealybug (Pseudococcus maritimus), green peach aphid (Myzus persicae), greenhouse whitefly (Trialeurodes vaporariorum)spp., papaya mealy bug (Pracoccus marginatus), pea aphid (Acyrthosiphon pisum), sugarcane mealybug (Saccharicoccus sacchari), potato aphid (Myzus persicae), potato leaf hopper (Empoasca fabae), cotton Jassid (Amrasca biguttula biguttula), cotton whitefly (Bemisia tabaci), tarnished plant bug (Lygus lineolaris), wooly apple aphid (Eriosoma lanigerum), yellow scale (Aonidiella citrine),order Lepidoptera, army worm (Mythimna unipuncta), asiatic rice borer (Chilo suppressalis), bean pod borer (Maruca vitrata), beet armyworm (Spodoptera exigua), black cutworm (Agrotis ipsilon), bollworm (Helicoverpa spp.),cabbage looper (Trichoplusia ni), codling moth (Cydia pomonella), croton caterpillar (Achea janata), diamond
Page 45 of 46
backmoth (Plutella xylostella), cabbage worm (Pieris rapae), pink bollworm (Pectinophora gossypiella), sugarcane borer (Diatraea saccharalis), tobacco budworm (Heliothis virescens), tomato fruitworm (Helicoverpa zea), velvet bean caterpillar (Anticarsia gemmatalis), yellow stem borer (SCirpophaga incertulas), spotted bollworm (Earias vittella), rice leaffolder (Cnaphalocrocis medinalis), pink stem borer (Sesamia spp.), tobacco leafeating caterpillar (Spodoptera litura), ; from the order Coleoptera, for example, apple twig borer (Amphicerus spp.), corn root worm (Diabrotica virgifera), cucumber beetle (diabrotica balteata), boll weevil (Anthonomus grandis), grape flea beetle (Altica chalybea), grape root worm (Fidia viticola), grape trunk borer (Clytoleptus albofasciatus), radish flea beetle (Phyllotreta armoraciae), maize weevil (Sitophilus zeamais), northern corn rootworm (Diabrotica barberi), rice water weevil (Lissorhoptrus oryzophilus); from the order Orthoptera, for example, Gryllotalpa spp., Locusta spp., and Schistocerca is spp.; from the order Thysanoptera, for example, Frankliniella spp., Thrips palmi, Thrips tabaci and Scirtothrips dorsalis; from the order Heteroptera, for example, Dysdercus spp., Leptocorisa spp., from the order Hymenoptera, for example, Solenopsis spp. ; from the order Diptera, for example, Antherigona soccata, Dacus spp., Liriomyza spp., Melanagromyza spp., from the order Acarina, for example, Aceria mangiferae, Brevipalpus spp., Eriophyes spp., Oligonychus mangiferus, Oligonychus punicae, Panonychus citri, Panonychus ulmi, Polyphagotarsonemus latus, Tarsonemus spp., Tetranychus urticae, Tetranychus cinnabarinus