DESC:FIELD OF THE INVENTION:

The present invention relates to novel liquid formulations comprising synergistic bioactive amounts of Tolfenpyrad and Bifenthrin. The present invention also relates to process for preparing the said liquid formulations comprising of synergistic bioactive amounts of Tolfenpyrad and Bifenthrin along with one or more inactive excipients.

BACKGROUND OF THE INVENTION

Tolfenpyrad was first disclosed in US5039693.Tolfenpyrad is chemically known as 4-chloro-3-ethyl-1-methyl-N-[4-(p-tolyloxy)benzyl]pyrazole-5-carboxamide and having chemical structure as below;

Tolfenpyrad is a pyrazole insecticide, and was discovered by Mitsubishi Chemical Corporation in 1991. The compound acts mainly through the inhibition of the mitochondrial electron transport system.

Tolfenpyrad acts by poisoning by ingestion, contact activity, anti-feeding activity against leps. Targeted crops of Tolfenpyrad include vegetable, cucurbits, cole crops, fruits and nuts, selected row crops and ornamentals. Tolfenpyrad is effective against disease including hemiptera, coleoptera, dipteral, lepidoptera, thysanoptera, orthoptera and acarina.

Bifenthrin was first disclosed US 4238505. Bifenthrin is chemically known as [1a,3a(Z)]-(±)-3-(2-Chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylic acid (2-methyl[1,1¢-biphenyl]-3-yl)methyl ester and having chemical structure as below

Bifenthrin is a pyrethroid insecticide used primarily against the red imported fire ant by influencing its nervous system. On a large scale, bifenthrin is often used against red imported fire ants. It is also effective against aphids, worms, ants, gnats, moths, beetles, grasshoppers, mites, midges, spiders, ticks, yellow jackets, maggots, thrips, caterpillars, flies, and fleas. It is mostly used in orchards, nurseries, and homes. In the agricultural sector, it is used in great amounts on certain crops, such as corn.

The main concern with the use of pesticide is the development of resistance by the pests for that particular pesticide and at the end one has to apply more concentrated formulation of the pesticide. The high amount of pesticide may results in the toxicity to human beings as well as has bad effect on environment.

Previously people have tried many alternatives and option to overcome this problem and as a result developed poly mixture of pesticide, use of non-toxic ingredients and developing novel formulations which provides effective amount of the pesticide and at the required part only.

However the use of poly mixture containing large number of pesticides poses a problem in many was like preparing formulation of multiple pesticides with different chemical properties and behavior and physical properties. It also creates challenge for formulator in term of compatibility and stability of all the pesticide along with used excipients in the formulation.

CN 103238604 A claims composition of pyriproxyfen and tolfenpyrad and the balance being an auxiliary agent; the weight ratio of the two active components pyriproxyfen and tolfenpyrad is 1:80-80:1; and the insecticidal composition can be made into wettable pulvis, water dispersible granules, a suspending agent, a suspoemulsion, an emulsion in water and a micron emulsion.
CN 104351192 A claims suspoemulsion for cotton and in particular relates to a suspoemulsion for preventing and controlling cotton bollworms. The effective ingredients of the suspoemulsion comprise tolfenpyrad and allicin, and the accessory ingredients of the suspoemulsion comprise calcium alkylbenzene sulfonate, sodium dodecyl benzene sulfonate, acetonitrile, polyoxyethylene nonyl phenyl ether phosphate, silicone, guar gum and propanediol.
However use of a composition of Tolfenpyrad in combination with one more insecticide, specifically with bifenthrin which overcomes some of the existing problems and can be prepared easily without much complex manufacturing process.

Inventors of the present invention have surprisingly found that the novel liquid formulations of Tolfenpyrad and Bifenthrin as described herein in can provide solution to the above mentioned problems.
Creating stable emulsions that contain at least one solid component, so-called suspo-emulsions, presents significant challenges to the formulation chemist. These challenges increase the greater the number and complexity of the components. Suspo-emulsion formulations are especially sensitive to the shear forces during manufacture of the formulation, and also during dilution and mixing of the formulation with water by the agricultural operator. These forces accelerate hetero-flocculation, caused by agglomeration of the solid particles with droplets of the emulsion phase. Hetero-flocculation causes poor storage stability and may result in blocked nozzle filters during spraying of the diluted formulation by the agricultural operator. These problems are exacerbated when formulations contain large amounts of oily components which are often required to improve translocation of the active ingredient into the plant.
The challenge for the formulation chemist is to choose the right wetting agent, quick coating agent and emulsifiers to produce a stable system. Typically this is achieved by coating the solid particles with a polymer dispersant forming a steric layer around each particle; the oil component is then emulsified into the mixture with the aid of an emulsifier. The emulsion can be thermodynamically or kinetically stabilised. Kinetically stabilised systems will eventually coalesce back to a single oil phase, typically this takes about 2 to 3 years, i.e. the duration of the shelf life of the product. The thermodynamically stable systems spontaneously form microemulsion/solubilised systems when mixed together in the correct proportions.
Thus, attempts at providing stable suspo-emulsion formulations have typically involved the use of specific wetting agent and dispersing agent to keep the droplets and particles physically apart. However these attempts have not found general applicability, because although they can be applied to specific, simple systems, they are not applicable to more complex suspo-emulsions. It is therefore the objective of the invention to provide a suspo-emulsion formulation that overcomes the above-mentioned problems.

SUMMARY OF THE INVENTION

According to one aspect of the invention there is provided a liquid formulation comprises:
a) Tolfenpyrad in the range from 5:1;
b) Bifenthrin, in the range from 1:5;
c) wetting agent or emulsifier as octyl phenol ethoxylate;
d) Dispersing agent as acrylic copolymers;
e) suitable adjuvants, carriers and/or inactive excipients

According to another aspect the present invention relates to a novel suspo emulsion formulation comprising Tolfenpyrad, Bifenthrin and one or more inactive excipient wherein the ratio of Tolfenpyrad to Bifenthrin is in the range from 5:1 to 1:5.

According to further aspect of the present invention also relates to process for preparing novel formulations which comprises synergistic bioactive amounts of Tolfenpyrad, Bifenthrin and one or more inactive excipients.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides novel liquid formulations which comprises of bioactive amounts of Tolfenpyrad, Bifenthrin and one or more excipients.

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

Tolfenpyrad and Bifenthrin which are bio active ingredient for the present novel formulation and are present in ratio of 5:1 to 1:5.

As per preferred embodiment, suspoemulsion formulation of the present invention is to be used in management of Insect-pests in GMO (Genetically Modified Organism) and Non GMO varieties of Cotton (Gossypium spp.), Paddy (Oryza sativa), Wheat (Triticum aestavum), Maize (Zea mays), Sugarcane (Saccharum officinarum) , Soybean (Glycin max), Peanut (Arachis hypogaea), Sunflower (Helianthus annuus) , Mustard (Brassica juncea), Rape seed (Brassica napus), Green gram (Vigna radiate), Black gram (Vigna mungo), Chickpea (Cicer aritinum), Redgram (Cajanus cajan), Brinjal (Solanum melongena), Cabbage (Brassica oleracea var. capitata), Cauliflower (Brassica oleracea var. botrytis), Okra (Abelmoschus esculentus) , Onion (Allium cepa L.), Tomato (Solanum lycopersicun) , Potato (Solanum tuberosum) , Chilly (Capsicum annum), Garlic (Allium sativum), Cucumber (Cucumis sativus), Muskmelons (Cucumis melo), Watermelon (Citrullus lanatus), Bottle gourd (Lagenaria siceraria), Bitter gourd (Momordica charantia), Apple (Melus domestica), Banana (Musa spp.), Citrus groups (Citrus spp.), Grape (Vitis vinifera), Mango (Mangifera indica), Pomegranate (Punica granatum), Tea (Camellia sinensis), Coffea (Coffea Arabica), Cumin (Cuminum cyminum), Rose (Rosa spp.).

The novel liquid formulations of the present invention can be used to control the insects-pests belongs to the order lepidopterans (Lepidoptera), for example Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheima-tobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, , Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bou-liana, Feltia subterranea, Galleria mellonella, Grapholitha funebrana, Grapholitha mo-lesta, Heliothis armigera, Heliothis virescens, Heliothis zea, Hellula undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keiferia lycopersicella, Lamb-dina fiscellaria, Laphygma exigua, Leucoptera coffeella, Leucoptera scitella, Lithocol-letis blancardella, Lobesia botrana, Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra brassicae, Orgyia pseu-dotsugata, Ostrinia nubilalis, Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris bras-sicae, Plathypena scabra, Plutella xylostella, Pseudoplusia includens, Rhyacionia frus-trana, Scrobipalpula absoluta, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni and Zeiraphera canadensis, beetles (Coleoptera), for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscu-rus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Aphthona euphoridae, Athous haemorrhoidalis, Atomaria linearis, Blasto-phagus piniperda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata, Cetonia aurata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Ctenicera ssp., Diabrotica longicornis, Diabrotica semipunctata, Diabrotica 12-punctata Diabrotica speciosa, Diabrotica virgifera, Epila-chna varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, Ips typographus, Lema bilineata, Lema melanopus, Leptinotarsa decemlineata, Limonius califomicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, Oulema oryzae, Ortiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon cochleariae, Phyllobius pyri, Phyllotreta chrysocephala, Phyllophaga sp., Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus and Sito-philus gran aria, flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, An-astrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles mini-mus, Anopheles quadrimaculatus, Calliphora vicina, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Contarinia sorghicola Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Dacus cucurbi-tae, Dacus oleae, Dasineura brassicae, Delia antique, Delia coarctata, Delia platura, Delia radicum, Dermatobia hominis, Fannia canicularis, Geomyza Tripunctata, Gaster-ophilus intestinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hylemyia platura, Hypoderma lineata, Leptoconops torrens, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mansonia titillanus, Mayetiola destructor, Musca domestica, Muscina stabulans, Oestrus ovis, Opomyza florum, Oscinella frit, Pegomya hysocyami, Phorbia antiqua, Phorbia brassicae, Phor-bia coarctata, Phlebotomus argentipes, Psorophora columbiae, Psila rosae, Psoro-phora discolor, Prosimulium mixtum, Rhagoletis cerasi, Rhagoletis pomonella, Sar-cophaga haemorrhoidalis, Sarcophaga sp., Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, and Tabanus similis, Tipula ol-eracea, and Tipula paludosa. thrips (Thysanoptera), e.g. Dichromothrips corbetti, Dichromothrips ssp , Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Scirtothrips dorsalis, Thrips oryzae, Thrips palmi and Thrips tabaci, termites (Isoptera), e.g. Calotermes flavicollis, Leucotermes flavipes, Heterotermes aureus, Reticulitermes flavipes, Reticulitermes virginicus, Reticulitermes lucifugus, Termes natalensis, and Coptotermes formosanus, cockroaches (Blattaria - Blattodea), e.g. Blattella germanica, Blattella asahinae, Penplaneta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blatta orientalis, true bugs (Hemiptera), e.g. Acrosternum hilare, Amrasca biguttula biguttula, Amrasca devastans, Blissus leucopterus, Cyrtopeltis nota-tus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridu-la, Piesma quadrata, Solubea insularis , Thyanta perditor, Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis crassivora, Aphis grossulariae, Aphis schneideri, Aphis spiraecola, Aphis sambuci, Acyrtho-siphon pisum, Aulacorthum solani, Bemisia argentifolii, Bemisia tabaci, Brachycaudus cardui, Brachy-caudus helichrysi, Brachycaudus persicae, Brachycaudus prunicola, Brevicoryne brassicae, Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordmannianae, Dreyfusia piceae, Dysaphis radicola, Dysaulacorthum pseudosolani, Dysaphis plantaginea, Dysaphis pyri, Empoasca fabae, Hyalopterus pruni, Hyperomyzus lactucae, Lipaphis erysimi, Macrosiphum avenae, Macrosiphum euphorbiae, Ma-crosiphon rosae, Megoura viciae, Melanaphis pyrarius, Metopolophium dirhodum, My-zus persicae, Myzus ascalonicus, Myzus cerasi, Myzus varians, Nasonovia ribis-nigri, Nilaparvata lugens, Nephotettix spp., Nettigoniclla spectra, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla mail, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Rhopalosi-phum padi, Rhopalosiphum insertum, Sappaphis mala, Sappaphis mail, Schizaphis graminum, Schizoneura lanuginosa, Sitobion avenae, Trialeurodes vaporariorum, Toxoptera aurantiia d, Viteus vitifolii, Cimex lectularius, Cimex hemipterus, Reduvius senilis, Triatoma spp., and Arilus critatus, Trialeurodes vaporariorum, Amrasca biguttula, Empoasca spp., Myzus spp., Nephotettix spp., Nilaparvata spp., Planococcus spp., Pseudococcus spp., Psylla spp., Rhopalosiphum spp., Sitobion spp., Amritodus atkinsoni, Idioscopus spp. ants, bees, wasps, sawflies (Hymenoptera), e.g. Athalia rosae, Atta cephalotes, Atta capiguara, Atta cephalotes, Atta laevigata, Atta robusta, Atta sexdens, Atta texana, Crematogaster spp., Hoplocampa minuta, Hoplocampa testudinea, Monomorium pha-raonis, Solenopsis geminata, Solenopsis invicta, Solenopsis richteri, Solenopsis xyloni, Pogonomyrmex barbatus, Pogonomyrmex californicus, Pheidole megacephala, Dasy-mutilla occidentalis, Bombus spp. Vespula squamosa, Paravespula vulgaris, Paraves-pula pennsylvanica, Paravespula germanica, Dolichovespula maculata, Vespa crabro, Polistes rubiginosa, Camponotus floridanus, and Linepithema humile, crickets, grasshoppers, locusts (Orthoptera), e.g. Acheta domestica, Gryllotalpa gryllo-talpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femurrubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Schistocerca americana, Schistocerca gregaria, Dociostaurus maroccanus, Tachycines asynamorus, Oedaleus senegalensis, Zonozerus variegatus, Hieroglyphus daganensis, Kraussaria angulifera, Calliptamus italicus, Chortoicetes terminifera, and Locustana pardalina, Arachnoidea, such as arachnids (Acarina), e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum, Amblyomma variegatum, Ambryomma maculatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Dermacentor andersoni, Dermacentor variabilis, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ixodes scapularis, Ixodes holocyclus, Ixodes pacificus, Ornithodorus moubata, Ornithodorus hermsi, Ornithodo-rus turicata, Ornithonyssus bacoti, Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus sanguineus, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes scabiei, and 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.

As per preferred embodiment, suspo emulsion formulation of present invention is used to control insects-pets belongs to Chilo partellus, Chilo suppressalis, Cnaphalocrocis medinalis, Earias vittella, Exelastis atomosa, Helicoverpa armigera, Leucinodes orbonalis, Maruca testulalis, Mythimna separata, Pectinophora gossypiella, Phyllocnistis citrella, Pieris brassicae, Plutella xylostella, Scirpophaga incertulas, Spodoptera litura, Spodoptera exigua, Tuta absoluta, Diabrotica punctata, Dicladispa armigera, Epila-chna varivestis, Holotrichia consanguinea, Holotrichia serrata, Leptinotarsa decemlineata, Phyllotreta striolata, Popillia japonica, Dacus cucurbi-tae, Liriomyza trifolii, Frankliniella occidentalis, Scirtothrips dorsalis, Thrips tabaci, Coptotermes formosanus, Heterotermes aureus, Leucotermes flavipes, Microtermes obesi, Odontotermes obesus, Amrasca biguttula biguttula, Amrasca devastans, Amritodus atkinsoni, Aphis gossypii, Aphis crassivora, Bemisia argentifolii, Bemisia tabaci, Diaphornia citri, Lygus lineolaris, Myzus persicae, Nilaparvata lugens, Nephotettix virescens, Nephotettix nigropictus, Planococcus spp., Pseudococcus spp., Pyrilla perpusilla, Psylla mali, Rhopalosiphum maidis, Trialeurodes vaporariorum, Toxoptera aurantiia, Psylla spp., Gryllotalpa gryllo-talpa, Locusta migratoria, Schistocerca gregaria, Eriophyes sheldoni; Polyphagotarsonemus latus; Brevipalpus phoenicis; Tetranychus cinnabarinus, Tetranychus telarius, Tetranychus urticae, Panonychus ulmi, Panony-chus citri, and Oligonychus pratensis.

As per one embodiment of the present invention, a novel suspoemulsion formulation comprises Tolfenpyrad, Bifenthrin and one or more inactive excipient wherein the ratio of Tolfenpyrad to Bifenthrin is in the range from 5:1 to 1:5.

As per one preferred embodiment, a novel suspoemulsion formulation comprises Tolfenpyrad, Bifenthrin wherein the Tolfenpyrad is present in the range from 10 to 20%, more preferably 15%.

As per one preferred embodiment, a novel suspoemulsion formulation comprises Tolfenpyrad, Bifenthrin wherein the Bifenthrin is present in the range from 2 to 15%, more preferably 7.5%.

The novel liquid formulations of the present invention in addition to Tolfenpyrad and Bifenthrin further comprises inactive excipients including but not limited to dispersant, anti-freezing agent, anti-foam agent, wetting agent, suspension aid, anti-microbial agent, thickener, or sticking agents (also referred to as “stickers” or “binders”) and buffering agent.

A dispersant is a substance which adsorbs onto the surface of particles and helps to preserve the state of dispersion of the particles and prevents them from re-aggregating. Dispersants are added to agrochemical formulations to facilitate dispersion and suspension during manufacture, and to ensure the particles re-disperse into water in a spray tank. They are widely used in wettable powders, suspension concentrates, suspoemulsion and water-dispersible granules. Surfactants that are used as dispersants have the ability to adsorb strongly onto a particle surface and provide a charged or steric barrier to re-aggregation of particles. The most commonly used surfactants are anionic, non-ionic, or mixtures of the two types. For suspoemulsion, preferred dispersant or dispersing agent include but not limited to sodium lignosulphonates; sodium naphthalene sulphonate formaldehyde condensates; acrylic polymer; tristyrylphenolethoxylate phosphate esters; aliphatic alcohol ethoxylates; alky ethoxylates; EO-PO block copolymers; and graft copolymers or mixtures thereof. As per one embodiment, the dispersing agent is present in the range from 0.1 to 5% w/w.

As per preferred embodiment, the dispersant for present suspoemulsion formulation is acrylic polymer, preferably in the range from 0.1 to 5% w/w.

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

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

A wetting agent is a substance that when added to a liquid increases the spreading or penetration power of the liquid by reducing the interfacial tension between the liquid and the surface on which it is spreading. Wetting agents are used for two main functions in agrochemical formulations: during processing and manufacture to increase the rate of wetting of powders in water to make concentrates for soluble liquids or suspension concentrates; and during mixing of a product with water in a spray tank or other vessel to reduce the wetting time of wettable powders and to improve the penetration of water into water-dispersible granules. Examples of wetting agents used in wettable powder, suspension concentrate, and water-dispersible granule formulations include but not limited to sodium lauryl sulphate; octyl phenol ethoxylate; sodium dioctylsulphosuccinate; alkyl phenol ethoxylates; and aliphatic alcohol ethoxylates or mixtures thereof. As per preferred embodiment the wetting agent is present in the range from 2 to 20% w/w.

As per preferred embodiment, the wetting agent is octyl phenol ethoxylate, preferably in the range from 2 to 20 % w/w.

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

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

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

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

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

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

As per one preferred embodiment, the inactive excipient for suspoemulsion are as provided below in addition to above described;

Name Function
n-Octanol Solvent
Octyl Phenol Ethoxylate, Polyoxyethylene (8) nonyl phenol, Sodium dioctyl sulfosuccinate Wetting agent & Emulsifier
Acrylic graft copolymer Dispersing agent
Polyalkoxy alkyl ether, Ethylene oxide/propylene oxide block copolymer, Sodium salt of naphthalene sulfonate condensate Dispersing agent & Emulsifier
Polyarylphenyl ether phosphate Dispersing agent & Wetting agent
Ethoxylated Fatty Alcohol Co-dispersant/Wetting agent
Trisiloxane ethoxylate Spreader & Wetting agent
Silicone antifoam emulsion Antifoam
Silicone dioxide Suspending aid, Ant caking agent
Polysaccharide Rheology Modifier, Thickner
Glycol (Monoethylene glycol, Diethylene glycol, Polypropylene glycol, Polyethylene glycol) Antifreezing Agent
1,2-benzisothiazolin-3-one, Sodium benzoate, 2-bromo-2-nitropropane-1,3-diol, Formaldehyde Biocide/Preservative

As per one embodiment, wetting agent and dispersing agent plays an important role in the preparation of effective and stable suspoemulsion formulation of present invention.

As per one embodiment of the present invention is to provide process for preparing novel liquid composition which is in the form of suspoemulsion comprising step described below;

1. Preparation of Mill base
Charge water to the vessel, equipped with a High Shear mixer (or equivalent). Under stirring add stabilizing agent, antifoam agent and the preheated (70 °C) surfactant in that order to the water. Agitate until homogeneity of the mixture. Add the surfactant and continue to stir until the mixture is homogeneous. Then add in the following order: antifreeze, dispersing agent and Tolfenpyrad technical slowly avoiding dust and agitate until homogeneity. Grind the resulting mixture through Dyno Mill till required particle size is achieved (D90 <10 micron and D50<5 micron). The temperature should not exceed 25 °C during the milling process. Now add thickener and preservative to the mixture and mix until homogeneity.

2. Preparation of Premix (Oil phase)
Add together Solvents, surfactant and Bifenthrin (melted at 50-55 degree). Mix until homogeneity with a 3 blade stirrer. Let the mixture stay until the foam disappears and the mixture is a clear liquid.

3. Preparation of Final Product
To a suitable vessel or tank equipped with a high-shear mixer, charge the Mill base and start agitation. Then add the Premix and water. Mix until homogeneity. Add thickener and preservative. Agitate until homogeneity. Pass the product through a 60 mesh screen and to QC for quality check before packing to final suitable packing material.

EXAMPLE
Example 1: (Recipe 1) Tolfenpyrad 15%+Bifenthrin 7.5% SE (SuspoEmulsion)
Chemical Composition Percent (% w/w)
Tolfenpyrad a.i. 15.00
Bifenthrin a.i. 7.50
Octyl phenol ethoxylate 10.00
Polyarylphenyl ether sulphate ammonium salt 1.10
Polyalkoxylated butyl ether 2.50
Ethoxylated polyarylphenol 1.50
Glycol 5.00
Acrylic copolymer 0.50
Silicon emulsion 0.20
Aluminium magnesium silicate 0.50
Silicon dioxide 0.50
Benzisothiazoline 0.20
Polysaccharides 0.08
Water QS
TOTAL 44.58

Procedure:
Step 1 Take required quantity of water, biocide, and defoamer and homogenize, then slowly add gum powder to it and stir till complete dissolution. Preparing Gum Solution 12 to 18 hours prior to use.
Step 2 Oil Phase: Technical dissolved in solvent and emulsifier.
Step 3 Aqueous phase: Charge 90% of total quantity of water in a vessel and then add preservative and MEG and stir well.
Step 4 Add required quantity of Wetting agent, dispersing agent & suspending agents and homogenize the contents for 45 – 60 minutes using high shear homogenizer.
Step 5 Then add technical and other remaining adjuvants excluding ‘antifreeze & thickeners’ are added to it and homogenized to get uniform.
Step 6 Now add oil phase in aqueous phase and stir for 30 minutes using homogenizer.
Step 6 Before grinding of step no. 6, half quantity of antifoam was added and then material was subjected to three cycles of grinding in bead mill.
Step 7 Half quantity of the antifoam was added along with antifreeze after grinding process completes and before sampling for in process analysis.
Step 8 Finally add gum solution to this formulation and Send to QC for quality check.

Storage stability
Parameters Specification Initial Stability (for 14 days)
In House At 54±2 0C At 0±2 0C
Description Off White colour flowable liquid Complies Complies Complies
Tolfenpyrad content percent by mass 14.25 to 15.75 15.28 15.09 15.26
Bifenthrin content percent by mass 7.875 to 8.25 7.65 7.56 7.62
Tolfenpyrad suspensibility percent mini. 80 98.87 97.01 98.69
Bifenthrin suspensibility percent mini. 80 98.89 97.12 98.57
pH range (1% aq. Suspension) 5.5 to7.5 7.2 7.1 7.2
Pourability 95 % min 98.30 97.50 97.10
Specific gravity 1.05 – 1.15 1.05 1.05 1.05
Viscosity at spindle no.62, 20 rpm 350 -800 cps 430 455 460
Particle size (micron) D50 <3, D90 <10 2.3, 7.9 2.4, 8.5 2.7, 8.3
Persistant foam ml (after 1 minute) max. 60 5 5 5

Room temperature storage data
Parameters Specification Study Duration
In House 1 month 6 month 12 months 24 months
Tolfenpyrad content percent by mass 14.25 to 15.75 15.25 15.23 15.21 15.15
Bifenthrin content percent by mass 7.875 to 8.25 7.64 7.62 7.58 7.55
Tolfenpyrad suspensibility percent mini. 80 98.75 98.51 98.08 97.64
Bifenthrin suspensibility percent mini. 80 98.74 98.65 97.97 97.65
pH range (1% aq. Suspension) 5.5 to7.5 7.2 7.2 7.1 7.1
Pourability 95 % min 98.30 98.15 97.90 97.60
Specific gravity 1.05 – 1.15 1.05 1.05 1.05 1.05
Viscosity at spindle no.62, 20 rpm 350 -800 cps 430 435 439 451
Particle size (micron) D50 <3, D90 <10 2.3, 8 2.3, 8.1 2.4, 8.2 2.5, 8.4
Persistant foam ml (after 1 minute) max. 60 5 5 5 5

Example 2: (Recipe 2) Tolfenpyrad 15%+Bifenthrin 7.5% SE (SuspoEmulsion)
Chemical Composition Percent (% w/w)
Tolfenpyrad a.i. 15.00
Bifenthrin a.i. 7.50
Polyarylphenyl ether sulphate ammonium salt 1.50
Polyalkoxylated butyl ether 2.50
Ethoxylated polyarylphenol 2.00
Glycol 5.00
Silicon emulsion 0.20
Aluminium magnesium silicate 0.50
Silicon dioxide 0.50
Benzisothiazoline 0.20
Polysaccharides 0.08
Water QS
TOTAL 34.98

Procedure: As per Example 1
Storage stability
Parameters Specification Initial Stability (for 14 days)
In House At 54±2 0C At 0±2 0C
Description Off White colour flowable liquid Complies Complies Complies
Tolfenpyrad content percent by mass 14.25 to 15.75 15.17 15.01 15.15
Bifenthrin content percent by mass 7.875 to 8.25 7.67 7.49 7.63
Tolfenpyrad suspensibility percent mini. 80 96.88 93.05 96.81
Bifenthrin suspensibility percent mini. 80 95.98 78.05 83.77
pH range (1% aq. Suspension) 5.5 to7.5 7.1 6.1 7.1
Pourability 95 % min 98.10 96.20 95.50
Specific gravity 1.05 – 1.15 1.06 1.06 1.06
Viscosity at spindle no.62, 20 rpm 350 -800 cps 450 485 495
Particle size (micron) D50 <3, D90 <10 2.5, 8.1 2.6, 11.5 3.7, 9.8
Persistant foam ml (after 1 minute) max. 60 10 10 10

Room temperature storage data
Parameters Specification Study Duration
In House 1 month 6 month 12 months 24 months
Tolfenpyrad content percent by mass 14.25 to 15.75 15.15 15.11 15.05 15.01
Bifenthrin content percent by mass 7.875 to 8.25 7.65 7.59 7.54 7.51
Tolfenpyrad suspensibility percent mini. 80 96.41 90.12 85.88 81.76
Bifenthrin suspensibility percent mini. 80 95.11 91.65 89.76 69.15
pH range (1% aq. Suspension) 5.5 to7.5 7.1 6.9 6.5 6.5
Pourability 95 % min 98.00 97.50 97.10 80.50
Specific gravity 1.05 – 1.15 1.06 1.06 1.06 1.06
Viscosity at spindle no.62, 20 rpm 350 -800 cps 450 455 730 840
Particle size (micron) D50 <3, D90 <10 2.5, 8.2 2.5, 8.2 2.7, 8.5 3.9, 10.6
Persistant foam ml (after 1 minute) max. 60 10 10 10 7

Example 3: Bio efficacy trials
The synergistic pesticide action of the inventive mixtures can be demonstrated by the experiments below. A synergistic effect exists wherever the action of a combination (ready-mix) or tank mix 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 pesticide activity than the sum of the pesticide 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:
Colby’s Formula:

To study the synergistic effect of Tolfenpyrad and Bifenthrin, various sets of experiments were conducted in different crops like rice, cotton and cabbage.
Trial 1: The objective of the present study was to study the synergism between Tolfenpyrad and Bifenthrin.
Details of Experiment:
a) Experiment design : Randomized Block Design
b) Replication : Three
c) Treatments : Nine
d) Plot size : 10 sq.m. (micro plot)
e) Spacing : 2 seedlings per hill
f) Test Crop & Variety : Rice, Sona sugandh
g) Time of application : after BPH (brown plant hopper) infestation.
Average >50 insects (nymph+adult) per hill.
h) Spray method : Manually operated knap sack sprayer, using 500
liter per hectare Water volume

Evaluation Method : The observation was recorded by counting the no. of hoppers (adult and nymph) per hill, 10 hills per plot were observed to record the insect population on 7th days after spraying. The percent insect control was worked out by below formula:
Number of hoppers in treated plot
% Insect Control = 100 - ------------------------------------------------- X 100
Number of hoppers in untreated plot

Table 1: Rice BPH Control
Treatments % BPH control
Obs.Value Cal. Value Ratio
Tolfenpyrad 15% EC+ Bifenthrin 10% EC, 1.2 ml+1.2 ml/l 97.24 78.61 1.24
Tolfenpyrad 15% EC+ Bifenthrin 10% EC, 0.6 ml+1.2 ml/l 91.88 71.41 1.29
Tolfenpyrad 15% EC+ Bifenthrin 10% EC, 1.2 ml+0.6 ml/l 93.12 73.12 1.27
Tolfenpyrad 15% EC+ Bifenthrin 10% EC, 0.6 ml+0.6 ml/l 86.36 64.06 1.35
Tolfenpyrad 15% EC, 0.6 ml/l 42.28
Tolfenpyrad 15% EC, 1.2 ml/l 56.82
Bifenthrin 10% EC, 0.6 ml/l 37.74
Bifenthrin 10% EC, 1.2 ml/l 50.46
Untreated Check (UTC) 0.00
Where EC- Emulsifiable concentrate, BPH Brown Plant Hopper (Nilaparvata lugens)

The results of above experiment show that combination of Tolfenpyrad and Bifenthrin shows synergistic action, in terms of % BPH control.

Trial 2
Details of Experiment:
a) Experiment design : Randomized Block Design
b) Replication : Three
c) Treatments : Nine
d) Plot size : 25 sq.m.
e) Spacing : 90 cm x 45 cm
f) Test Crop & Variety : Cotton, VCH 5
g) Time of application : after Jassid & Thrips infestation.
h) Spray method : Manually operated knap sack sprayer, using 400
liter per hectare Water volume
Evaluation Method : The observation was recorded by counting the no. of insects per leaf. Record observations from 3 leaves per plant and 5 plants per plot. The percent insect control was worked out by below formula:
Number of live insect in treated plot
% Insect Control = 100 - ----------------------------------------------------- X 100
Number of live insects in untreated plot

Table 2: Synergistic action against Cotton Leaf hopper (Jassid),Amrasca biguttula biguttula and Thrips, Thrips tabaci
Treatments % Leaf Hopper control % Thrips control
Obs.Value Cal. Value Ratio Obs.Value Cal. Value Ratio
Tolfenpyrad 15% EC+ Bifenthrin 10% EC,
1ml+1 ml/l 98.26 81.02 1.21 99.27 74.49 1.33
Tolfenpyrad 15% EC+ Bifenthrin 10% EC,
0.5 ml+1 ml/l 93.73 71.01 1.32 92.82 67.99 1.37
Tolfenpyrad 15% EC+ Bifenthrin 10% EC,
1ml+0.5 ml/l 93.18 77.17 1.21 95.36 75.74 1.26
Tolfenpyrad 15% EC+ Bifenthrin 10% EC,
0.5 ml+0.5 ml/l 88.62 65.14 1.36 90.57 69.55 1.30
Tolfenpyrad 15% EC, 0.5 ml/l 45.67 47.83
Tolfenpyrad 15% EC, 1 ml/l 64.42 58.43
Bifenthrin 10% EC, 0.5 ml/l 35.83 41.64
Bifenthrin 10% EC, 1 ml/l 46.65 38.64
Untreated Check (UTC) 0.00 0.00

The combination of Tolfenpyrad and Bifenthrin also shows synergism and provides excellent control of cotton Jassid and thrips compared to their individual application.

Trial 3: To study the effect of recipe on residual control (Recipe comparison)
Details of Experiment:
a) Experiment design : Randomized Block Design
b) Replication : Three
c) Treatments : Eight (including untreated check)
d) Plot size : 25 sq.m.
e) Spacing : 2 seedlings per hill
f) Test Crop & Variety : Rice, Sona sugandh
g) Time of application : after BPH (brown plant hopper) infestation.
Average >50 insects (nymph+adult) per hill.
i) Spray method : Manually operated knap sack sprayer, using 500
liter per hectare Water volume
Evaluation Method : The observation was recorded by counting the no. of hoppers (adult and nymph) per hill, 10 hills per plot were observed to record the insect population on 1st, 5th, 10th, 15th and 20th days after application (DAA). The percent insect control was worked out by below formula given in Trial 1.
Table 3: Residual control of Rice BPH Nilaparvata lugens
Treatments details Formulation (g or ml/h) Rate (g.a.i/h) % BPH Control
1 DAA 5 DAA 10 DAA 15 DAA 20 DAA
T1 -Recipe 1-Tolfenpyrad 15%+ Bifenthrin 7.5% SE 750 112.5+56.25 97.27 98.18 95.75 92.64 90.78
T2 -Recipe 2-Tolfenpyrad 15%+ Bifenthrin 7.5% SE 750 112.5+56.25 95.37 90.83 85.64 77.63 65.36
T3 -Prior Art 1-Tolfenpyrad 15% EC + Bifenthrin 10% EC 750+562.5 112.5+56.25 89.86 80.17 69.75 58.62 40.28
T4 -Prior Art 2-Tolfenpyrad 15% EC + Bifenthrin 8.8% SC 750+639 112.5+56.25 90.78 82.58 71.48 60.73 43.62
T5 -Tolfenpyrad 15% EC 750 112.5 77.47 62.64 42.37 12.58 0
T6 -Bifenthrin 10% EC 562.5 56.25 60.62 48.28 26.47 0.00 0
T7 -Bifenthrin 8.8% SC 639 56.25 62.18 50.73 30.59 0.00 0
T8 -Untreated Check (Water spray) 0 0 0.00 0.00 0.00 0.00 0
Where EC- Emulsifiable concentrate, SC Suspension Concentrate, BPH Brown Plant Hopper.

The trial results shows that T1-Recipe 1 of Tolfenpyrad 15%+Bifenthrin 7.5% SE provides longer residual control of rice BPH compared to T2-Recipe 2 and other prior art treatments. T1-Recipe-1 provides approx. 10%, 15% and 25% higher control than T2-Recipe 2, which also indicates that T1-Recipe 1 formulation of Tolfenpyrad 15%+Bifenthrin 7.5% SE is more stable and highly efficacious compare to T2-Recipe 2 and other prior art treatments.

Trial 4: To evaluate residual efficacy of different formulation of Tolfenpyrad 15% + Bifenthrin 7.5% against diamond back moth on cabbage.
Details of Experiment: A Lab.-field bioassay to study the residual control
a) Experiment design : Complete Block Design
(3 middle rows to be considered as 3 replications)
b) Treatments : Eight (including untreated check)
c) Plot size : 20 m2.
d) Spacing : 30 cm X 30 cml
e) Test Crop & Variety : Cabbage, Sutton Express
f) Time of application : after BPH (brown plant hopper) infestation.
Average >50 insects (nymph+adult) per hill.
g) Spray method : CO2 Sprayer fitted with hollow cone nozzle (TXVS-4 green) Spray volume-500 liter per hectare
Evaluation Method: Immediately after spraying, wet (sprayed) leaves should be marked by clipping the tip with scissors. Treated leaves from each treatment should be collected at 5, 7, 10, 14, 17 and 21 days after treatment. Collected leaves should be cut in to pieces of 1 sq inch and placed in HIS trays with moist filter paper. 2nd instar diamond backmoth (Plutella xylostella) larvae from lab culture to be used for experiment. One tray for each rep, so total 48 larvae per 3 reps per treatment. Trays should be kept in incubator at 26 degree C temperature and 14: 10 hrs L:D. Evaluation at 72 hrs after release for % mortality (dead + moribund) and % feeding. Larval mortality was calculated as below:
Number of dead larvae in treated plot
% Larval mortality = ---------------------------------------------------- X 100
Number of dead larvae in untreated plot

Table 4: Residual control of Tolfenpyrad 15%+Bifenthrin 10% SE against diamond backmoth, Plutella xylostella
Treatments details Formulation (g or ml/h) Rate (g.a.i/h) % Larval control of Diamond back moth
5 Days 7 Days 10 Days 14 Days 21 Days
T1 -Recipe 1-Tolfenpyrad 15%+ Bifenthrin 7.5% SE 750 112.5+56.25 100.00 100.00 98.27 94.84 90.22
T2 -Recipe 2-Tolfenpyrad 15%+ Bifenthrin 7.5% SE 750 112.5+56.25 98.37 96.92 91.42 85.37 78.64
T3 -Prior Art 1-Tolfenpyrad 15%+ Bifenthrin 7.5% EC 750 112.5+56.25 95.63 92.48 84.53 74.82 60.57
T4 -Prior Art 2-Tolfenpyrad 15% EC + Bifenthrin 10% EC tank mix 750+562.5 112.5+56.25 88.28 80.82 71.48 58.62 48.73
T5 -Prior Art 3-Tolfenpyrad 15% EC + Bifenthrin 8.8% SC tank mix 750+639 112.5+56.25 90.72 82.47 73.62 61.28 52.53
T6 -Tolfenpyrad 15% EC 750 112.5 80.72 70.62 58.48 42.38 21.64
T7 -Bifenthrin 10% EC 562.5 56.25 64.63 42.39 13.63 0.00 0.00
T8 -Bifenthrin 8.8% SC 639 56.25 70.62 51.38 22.47 0.00 0.00
T9 -Untreated Check (Water spray) 0 0 0.00 0.00 0.00 0.00 0.00
Where SE Suspo Emuslion, EC Emulsifiable Concentrate, SC Suspension concentrate

The test result of a lab field bioassay shows that T1-Recipe 1 of Tolfenpyrad 15%+Bifenthrin 7.5% SE gave longer residual control compared to T2-Recipe 2 and all the prior art treatment. The longer residual control significantly reduces the number of spray applications in the field and thereby reduce the load of active ingredients in to the environment.
,CLAIMS:CLAIMS
We claim;
[CLAIM 1]. A novel liquid formulations comprises:
a) Tolfenpyrad in the range from 5:1;
b) Bifenthrin, in the range from 1:5;
c) wetting agent or emlsifer as octyl phenol ethoxylate;
d) dispersing agent as acrylic copolymers;
e) suitable adjuvants, carriers and/or inactive excipients.

[CLAIM 2]. A novel liquid formulations according to claim 1 is suspoemulsion.

[CLAIM 3]. A novel liquid formulations according to claim 1 or 2 wherein wetting agent is octyl phenol ethoxylate, preferably in the range from 2 to 20 % w/w.

[CLAIM 4]. A novel liquid formulations according to claim 1 or 2 wherein, acrylic copolymers are, poly(styrene-co maleic anhydride), cellulosic polymers such as ethyl cellulose, cellulose acetate, cellulose acetatebutyrate, acetylated mono, di, and triglycerides, poly(vinylpyrrolidone), vinyl acetate polymers and copolymers, poly(alkylene glycol), styrene butadiene copolymers, poly(orthoesters), alkyd resins, and mixtures of two or more of these.

[CLAIM 5]. A novel liquid formulation according to claims 1, wherein Tolfenpyrad is present in the range from 5 to 25%.

[CLAIM 6]. A novel liquid formulation according to claims 6, wherein Tolfenpyrad is present in 15%.

[CLAIM 7]. A novel liquid formulation according to claims 1, wherein Bifenthrin is present in the range from 2 to 15%.

[CLAIM 8]. A novel liquid formulation according to claims 8, wherein Bifenthrin is present in 7.5%.

[CLAIM 9]. A novel liquid formulations according to claim 1 or 2 , wherein inactive excipients can be selected from the group consisting of dispersant, anti-freezing agent, anti-foam agent, wetting agent, suspension aid, anti-microbial agent, thickener, or sticking agents and buffering agent.

[CLAIM 10]. A novel liquid formulations according to claim 1 or 2, wherein the said formulation is to be used in management of insect or pastes in GMO (Genetically Modified Organism) and Non GMO varieties of Cotton (Gossypium spp.), Paddy (Oryza sativa), Wheat (Triticum aestavum), Maize (Zea mays), Sugarcane (Saccharum officinarum) , Soybean (Glycin max), Peanut (Arachis hypogaea), Sunflower (Helianthus annuus) , Mustard (Brassica juncea), Rape seed (Brassica napus), Green gram (Vigna radiate), Black gram (Vigna mungo), Chickpea (Cicer aritinum), Redgram (Cajanus cajan), Brinjal (Solanum melongena), Cabbage (Brassica oleracea var. capitata), Cauliflower (Brassica oleracea var. botrytis), Okra (Abelmoschus esculentus) , Onion (Allium cepa L.), Tomato (Solanum lycopersicun) , Potato (Solanum tuberosum) , Chilly (Capsicum annum), Garlic (Allium sativum), Cucumber (Cucumis sativus), Muskmelons (Cucumis melo), Watermelon (Citrullus lanatus), Bottle gourd (Lagenaria siceraria), Bitter gourd (Momordica charantia), Apple (Melus domestica), Banana (Musa spp.), Citrus groups (Citrus spp.), Grape (Vitis vinifera), Mango (Mangifera indica), Pomegranate (Punica granatum), Tea (Camellia sinensis), Coffea (Coffea Arabica), Cumin (Cuminum cyminum), Rose (Rosa spp.).

[CLAIM 11]. A novel liquid formulations according to claim 1, wherein the formulation is used to control insects-pets belongs to Chilo partellus, Chilo suppressalis, Cnaphalocrocis medinalis, Earias vittella, Exelastis atomosa, Helicoverpa armigera, Leucinodes orbonalis, Maruca testulalis, Mythimna separata, Pectinophora gossypiella, Phyllocnistis citrella, Pieris brassicae, Plutella xylostella, Scirpophaga incertulas, Spodoptera litura, Spodoptera exigua, Tuta absoluta, Diabrotica punctata, Dicladispa armigera, Epila-chna varivestis, Holotrichia consanguinea, Holotrichia serrata, Leptinotarsa decemlineata, Phyllotreta striolata, Popillia japonica, Dacus cucurbi-tae, Liriomyza trifolii, Frankliniella occidentalis, Scirtothrips dorsalis, Thrips tabaci, Coptotermes formosanus, Heterotermes aureus, Leucotermes flavipes, Microtermes obesi, Odontotermes obesus, Amrasca biguttula biguttula, Amrasca devastans, Amritodus atkinsoni, Aphis gossypii, Aphis crassivora, Bemisia argentifolii, Bemisia tabaci, Diaphornia citri, Lygus lineolaris, Myzus persicae, Nilaparvata lugens, Nephotettix virescens, Nephotettix nigropictus, Planococcus spp., Pseudococcus spp., Pyrilla perpusilla, Psylla mali, Rhopalosiphum maidis, Trialeurodes vaporariorum, Toxoptera aurantiia, Psylla spp., Gryllotalpa gryllo-talpa, Locusta migratoria, Schistocerca gregaria, Eriophyes sheldoni; Polyphagotarsonemus latus; Brevipalpus phoenicis; Tetranychus cinnabarinus, Tetranychus telarius, Tetranychus urticae, Panonychus ulmi, Panony-chus citri, and Oligonychus pratensis.

[CLAIM 12]. A novel liquid formulations according to claim 1 or 2 is suspoemulsion comprises:
a) Bifenthrin
b) Tolfenpyrad
c) Octyl phenol ethoxylate
d) Polyarylphenyl ether sulphate ammonium salt
e) Polyalkoxylated butyl ether
f) Ethoxylated polyarylphenol
g) Glycol
h) Acrylic copolymer
i) Silicon emulsion
j) Aluminium magnesium silicate
k) Silicon dioxide
l) Benzisothiazoline
m) Polysaccharides
n) Water