DESC:FIELD OF THE INVENTION:

The present invention relates to a novel formulation of bioactive amounts of Pyriproxyfen and Fenpyroximate having insecticidal property. The present invention also relates to process for preparing the said formulation comprising bioactive amounts of Pyriproxyfen and Fenpyroximate and one or more inactive excipients.

BACKGROUND OF THE INVENTION

Pesticides are chemicals that may be used to kill fungus, bacteria, insects, plant diseases, snails, slugs, or weeds among others. These chemicals can work by ingestion or by touch and death may occur immediately or over a long period of time.

Insecticides are a type of pesticide that is used to specifically target and kill insects. Some insecticides include snail bait, ant killer, and wasp killer.

An insecticide is a substance used to kill insects. They include ovicides and larvicides used against insect eggs and larvae, respectively. Insecticides are used in agriculture, medicine, industry and by consumers.

Insecticides can be classified by many ways. One of many classifications is as below:

Systemic insecticides are those in which the active ingredient is taken up, primarily by plant roots, and transported (translocated) to locations throughout the plant, such as growing points, where it can affect plant-feeding pests. Systemic insecticides move within the vascular tissues, either through the xylem (water-conducting tissue) or the phloem (food-conducting tissue) depending on the characteristics of the material.

Contact insecticides are toxic to insects when brought into direct contact. Efficacy is often related to the quality of pesticide application, with small droplets (such as aerosols) often improving performance.

Natural insecticides, such as nicotine, pyrethrum and neem extracts are made by plants as defenses against insects. Nicotine-based insecticides are widely used in the US and Canada, but are barred in the European Union.

Plant-incorporated protectants (PIPs) are systemic insecticides produced by transgenic plants. For instance, a gene that codes for a specific Bacillus thuringiensis biocidal protein was introduced into corn and other species. The plant manufactures the protein which kills the insect when consumed.

Inorganic insecticides are contact insecticides that manufactured with metals and include arsenates, copper and fluorine compounds, which are now seldom used, and sulfur, which is commonly used.

Organic insecticides are contact insecticides that comprise the largest numbers of pesticides available for use today.

The mode of action describes how the pesticide kills or inactivates a pest. It provides another way of classifying insecticides. Mode of action is important in understanding whether an insecticide will be toxic to unrelated species, such as fish, birds and mammals.

Insecticidal classes which covers majority of the insecticides are as below:

Organophosphates and carbamates
Organophosphates target the insect's nervous system. Organophosphates interfere with the enzymes acetylcholinesterase and other cholinesterases, disrupting nerve impulses and killing or disabling the insect. Organophosphate insecticides and chemical warfare nerve agents (such as sarin, tabun, soman, and VX) work in the same way. Organophosphates have a cumulative toxic effect to wildlife, so multiple exposures to the chemicals amplify the toxicity.

Carbamate insecticides have similar mechanisms to organophosphates, but have a much shorter duration of action and are somewhat less toxic.

Organochlorides
The best-known organochloride, DDT (Dichlorodiphenyltrichloroethane), was created by Swiss scientist Paul Müller. For this discovery, he was awarded the 1948 Nobel Prize for Physiology or Medicine. DDT was introduced in 1944. It functions by opening sodium channels in the insect's nerve cells. The contemporaneous rise of the chemical industry facilitated large-scale production of DDT and related chlorinated hydrocarbons.

Neonicotinoids
Neonicotinoids are synthetic analogues of the natural insecticide nicotine (with much lower acute mammalian toxicity and greater field persistence). These chemicals are acetylcholine receptor agonists. They are broad-spectrum systemic insecticides, with rapid action (minutes-hours). They are applied as sprays, drenches, seed and soil treatments. Treated insects exhibit leg tremors, rapid wing motion, stylet withdrawal (aphids), disoriented movement, paralysis and death. Imidacloprid may be the most common.

Pyrethroids
Pyrethroid pesticides mimic the insecticidal activity of the natural compound pyrethrum. These compounds are nonpersistent sodium channel modulators and are less toxic than organophosphates and carbamates. Compounds in this group are often applied against household pests.

Ryanoids
Ryanoids are synthetic analogues with the same mode of action as ryanodine, a naturally occurring insecticide extracted from Ryania speciosa (Flacourtiaceae). They bind to calcium channels in cardiac and skeletal muscle, blocking nerve transmission.

Plant-incorporated protectants
Transgenic crops that act as insecticides began in 1996 with BT corn that produces the Cry protein, derived from the bacterium Bacillus thuringiensis, which is toxic to moth larvae such as the European corn borer. The technique has been expanded to include the use of RNA interference RNAi that fatally silences crucial insect genes. RNAi likely evolved as a defense against viruses. Midgut cells in many larvae take up the molecules and help spread the signal. The technology can target only insects that have the silenced sequence, as was demonstrated when a particular RNAi affected only one of four fruit fly species. The technique is expected to replace many other insecticides, which are losing effectiveness due to the spread of pesticide resistance.

Pyriproxyfen was first disclosed in US 4,751,225. Chemically known as 4-Phenoxyphenyl 2-(2-pyridyloxy)propyl ether and chemical structure is as below;

Pyriproxyfen is a pyridine-based pesticide which is found to be effective against a variety of arthropoda. It was introduced to the US in 1996, to protect cotton crops against whitefly. It has also been found useful for protecting other crops. It is also used for prevention of fleas on household pets.

Pyriproxyfen is a juvenile hormone analog and a relatively stable aromatic compound. It functions as an insecticide by overloading the hormonal system of the target insect, ultimately affecting egg production, brood care and other social interactions, and inhibiting growth (Glancey, B.M., N. Reimer and W.A. Banks. 1990. Effects of IGR Fenoxycarb and Sumitomo S-31183 on the queens of two myrmicine ant species. In: Applied Myrmecology: A World Perspective. Eds. Robert K. Vander Meer, Klaus Jaffe, and Aragua Cedeno. Boulder:Westview Press, 604-613.)

Mechanism of action of Pyriproxyfen (Jonathan Sullivan, ENVIRONMENTAL FATE OF PYRIPROXYFEN, Environmental Monitoring & Pest Management Branch Department of Pesticide Regulation 2000)

Two major insect-hormones act to control metamorphosis: the molting hormone and the juvenile hormone (JH). High concentrations of JH and low concentrations of molting hormone cause molting larva to continue growing as larval instars (a stage of an insect or other arthropod between molts). Presence of the molting hormone coupled with the absence of JH in insect circulation results in larvae which change into adults. Insects often go through a number of instars however when the JH secretion stops metamorphosis follows (Staal, G.B. 1972. Biological activity and bioassay of juvenile hormone analogs. In: Insect Juvenile Hormones: Chemistry and Action. Ed. Menn, J.J., Beroza, M. Academic Press. New York). JH maintains the "youthful character" of the insect and prevents the insect from becoming an adult before it is fully grown. Abnormal amounts of JH often result in the eventual death of the larva.

The search to apply knowledge of JHs to the development of effective insecticides has since been limited to the area of JH analogs (JHAs) (Matolcsy, G. Nadasy, M., and V. Andriska. 1988. Pesticide Chemistry: Studies in Environmental Science, Elsevier. New York.). JHAs act in the same manner as JHs, but are much more chemically stable.

Pyriproxyfen is a JHA and a fenoxycarb derivative in which part of the aliphatic chain has been replaced by pyridyloxyethylene. Although these active JHA compounds bear little resemblance to JHs, their high stability allows them to compete for JH binding site receptors (Riddiford, L.M. 1994. Cellular and molecular actions of juvenile hormone: general considerations and premetamorphic actions. Advances in Insect Physiology, 24: 213-274).). Pyriproxyfen mimics the action of the juvenile hormones on a number of physiological processes, and is a potent inhibitor of embryogenesis, metamorphosis and adult formation (Ishaaya, I and A.R. Horowitz. 1992. Novel phenoxy hormone analog (pyriproxyfen) suppresses embryogenesis and adult emergence of sweet potato whitefly. J. Econ. Entomol. 85, 21132117.).
Fenpyroximate was first disclosed in EP234045.Fenpyroximate is chemically known as tert-butyl (E)-a-(1,3-dimethyl-5-phenoxypyrazol-4-yl methylene aminooxy)-p-toluate and having chemical structure as below;

Fenpyroximate is from phenoxypyrazole class of insecticide and is used against wide range of phytophagous mites. It has a novel chemical structure, and has been proven effective against most phytophagous (plant-eating) mites on various crops worldwide. Fenpyroximate has quick action or knock down activity on active stages with long lasting effect. It has molting inhibition on immature stages.

Fenpyroximate is primarily act as a contact miticide. It is effective on all stages of two-spotted spider mite and is most effective on larvae followed by nymphs, adults and eggs. Fenpyroximate is a mitochondrial electron transport inhibitor (METI) and when it comes in contact with target mites, it blocks cell respiration causing the pest to losemotor control and collapse. In addition to this contact activity, Fenpyroximate provides cumulative mortality at each successive life stage through inhibition of molting as is seen with insect growth regulators.

Fenpyroximate is active against a wide range of mite pests and is suitable for use on most agricultural and horticultural tree fruit, citrus fruit, nut and vine crops. Fenpyroximate is also used for mite control on vegetables, tea and ornamental crops.

The main concern with the use of insecticide is the development of resistance by the insects for that particular insecticide and at the end one has to apply more concentrated formulation of the insecticide. The high amount of insecticide 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 insecticide, use of non-toxic ingredients and developing novel formulations which provides effective amount of the insecticide and at the required part only.

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

US 6,296,864 discloses a pesticidal composition comprising (a) 1 to 50% by weight of a lipophilic compound as a pesticidally active ingredient (including Pyriproxyfen), (b) 0.1 to 10% by weight of at least one nonionic surfactant, (c) 0.3 to 4% by weight of at least one anionic surfactant selected from the group consisting of alkylarylsulfonic acid salts and alkylbiphenylsulfonic acid salts, (d) 15 to 40% by weight of a fatty acid ester.

JP10120502 discloses emulsifiable concentrates of Pyriproxyfen, comprising (a) the active agent, (b) one or more nonoinic surfactants selected from POE/POP-block polymer, POE/POP-alkylaryl ether, POE/POP-alkyl ether, POE/POP-polyaryl ether, fatty ester of POE/POP-block polymer, (c) one or more anionicsurfactants selected from alkyl aryl sulphonate and alkyl biphenyl sulphonate, (d) vegetable oil and (e) an aromatic hydrocarbon solvent.

US 8,709,513 describes a suspension concentrate compositions comprising by weight based on the total weight of the composition, (a) from about 0.1 to about 50% of one or more carboxamidearthropodicides that are solid at room temperature; ( b) from 0 to about 50% of one or more biologically active agents (including Pyriproxyfen) other than the carboxamidearthropodicides; (c) from about 20 to about 70% of water; (d) from about 10 to about 70% of one or more water-immiscible liquid compounds; and (e) from about 1 to about 55% of a surfactant component having a dispersing property.

CA2725744 discloses a composition for controlling insects or representatives of the order Acarina, which comprises (i) a compound of the formula (see formula A); (ii) one or more compounds selected from the group consisting of: (I) aldicarb; (II) azinphos-methyl; (III) benfuracarb; (IV) buprofezin; (V) carbofuran; (VI) chlorofluazuron; (VII) chloropyrifos; (VIII) diflubenzuron; (IX) endosulfan; (X) ethiofencarb; (XI) fenitrothion; (XII) fenobucarb; (XIII) formothion; (XIV) methiocarb; (XV) heptenophos; (XVI) isoprocarb; (XVII) methamidophos; (XVIII) methomyl; (XIX) mevinphos; (XX) parathion; (XXI) parathion-methyl; (XXII) phosalone; (XXIII) pirimicarb; (XXIV) teflubenzuron; (XXV) terbufos; (XXVI) triazamate; (XXVII) abamectin; (XXVIII) tebufenozide; (XXX) silafluofen; (XXXI) fenpyroximate; (XXXII) pyridaben; (XXXIII) fenazaquin; (XXXIV) pyriproxyfen; and (XXXV) pyrimidifen; and (iii) at least one auxiliary. The composition may be used for controlling pests selected from insects and representatives of the order Acarina and for protecting plant propagation material.

JP2006213664 describes a plant disease pest control composition which comprises a microbial ingredient and an insecticidal ingredient and can exhibit high activity, even when the content of the microbial ingredient is lowered. The plant disease pest control composition contains penthiopyrad as an ingredient I and one or more compounds selected from the group consisting of Imidacloprid, Thiamethoxam, Acetamiprid, Nitenpyram, Clothianidin, Dinotefuran, Lufenuron, Chlorfluazuron, Teflubenzuron, Triflumuron, Bistrifluron, Buprofezin, Cyromazine, Pyriproxyfen, Triazamate, Fenbutatin oxide, Hexythiazox, Acequinocyl, Fenpyroximate, Bifenazate, Bromopropylate, Endosulfan, Indoxacarb, Chlorfenapyr, Tolfenpyrad, Pyridalyl, Abamectin, Spinosad, Emamectin benzoate and the same, as an ingredient II.

CN 101380020 relates to a pesticide composite, which consists of a component A and a component B, wherein the component A is fenpyroximate, and the component B is selected from one of bifenthrin and clofentezine. A formulation screening test result shows that the respective combination of either fenpyroximate and bifenthrin or fenpyroximate and clofentezine, according to a certain proportion, can generate obvious synergism on orange red spiders. The pesticide composite can be prepared into an emulsifiable concentrate, an aqueous emulsion, a microemulsion, a suspending agent, a water dispersible granule and a wettable powder. The composite has the advantages of overcoming and deferring the drug resistance of the pests, enlarging a control spectrum, killing acaridan quickly, reducing medication cost and lightening toxicity, thus being particularly suitable for controlling resistant red and white spiders. The effect of the composite is obviously higher than the single-dose use of pesticides.

CN 102204549 relates to a pesticide insecticidal composition, and the effective components are spirotetramat and fenpyroximate. The weight ratio of spirotetramat and fenpyroximate is 1-80:80-1 and the contents of spirotetramat and fenpyroximate in the composite preparation are 1-80%. The composite pesticide composition adopts a method which is widely-known by technicians of the field, and can be prepared into dosage forms such as emulsifiable concentrate, suspension, wettable powder, water dispersible granules, water emulsion, and the like. The insecticidal composition of the invention is applicable to the control of insects with piercing-sucking mouthparts for vegetables and fruit, and is especially applicable to the control of aphid, whitefly, mealybug, scale insects, plant hoppers, thrips, tea leafhoppers, and mite insects of fruit and vegetables.

However still there is a need for a formulation of specific insecticides 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 formulation of Pyriproxyfen and Fenpyroximate as described herein in can provide solution to above problems.

SUMMARY OF THE INVENTION

The present invention is all about a insecticidal formulation which comprises of bioactive amounts of Pyriproxyfen and Fenpyroximate.

Further the present invention also relates to process for preparing the novel formulation comprising bioactive amounts of Pyriproxyfen and Fenpyroximate with one or more inactive excipients.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides novel formulation comprising bioactive amounts of Pyriproxyfen and Fenpyroximate with one or more inactive excipients.

The term “pesticide” or “pesticidal” is similar to “insecticide” or “insecticidal” and used interchangeably in this whole specification.

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

The pesticidal or insecticidal formulation can be classified as below:

a) Dry - Sprayable

a.1) WP – Wettable powders:
A solid pesticide formulation – micronized to powder form and typically applied as suspended particles after dispersion in water.

a.2) WG or WDG – Water dispersible granule:
A pesticidal formulation consisting of granules to be applied after disintegration and dispersion in water. Water dispersible granules can be formed by a) agglomeration, b) spray drying, or c) extrusion techniques.

b) Liquid Sprayable

b.1) SL – Soluble Concentrate:
A soluble concentrate is in powder form intended for dilution with water or directly in solution from. In both the case, the end result will be clear solution of the insecticide in the water without any visible un-dissolved particles.

b.2) SC – Suspension Concentrate
A stable suspension of solid pesticide(s) in a fluid usually intended for dilution with water before use. For a good formulation or ideal SC formulation, it should be stable and do not sediment over time.

b.3) EC – Emulsifiable Concentrate
A solution of a pesticide with emulsifying agents in a water insoluble organic solvent which will form an emulsion when added to water. In most of the case it is oil in water type emulsion to make it easy for application. EC formulation should be storage stable without any visible cracking of emulsion.

b.4) ME – Microemulsion
A solution of a pesticide with emulsifying agents in a water insoluble organic solvent which will form a solution/emulsion when added to water. The difference between EC and ME is the particle size of the actives in the final form.

b.5) OD – Oil Dispersion
Oil dispersions (OD) are one type of liquid formulation which is stable suspensions of active ingredients in a water-immiscible fluid which may contain other dissolved active ingredients and is intended for dilution with water before use.

b.6) CS – Capsule Suspension
Suspension of micro-encapsulated active ingredient in an aqueous continuous phase, intended for dilution with water before use.

b.7) SE- Suspension emulsion
A suspension emulsion or suspo emulsion (SE) consists of an organic phase with a dissolved active ingredient and an aqueous suspension phase, in which the active ingredient is dispersed in water.

c) Dry – Spreadable Granule
Dry spreadable granules are dry granules which can be applied with a dry spreader to a target area and later when such granules get exposed to water via, for example, rain or irrigation, will not only readily disintegrate, but actively spread on solid substrates so as to achieve disintegration area diameter to original granule diameter ratios.

Dry spreadable granules should possess good hardness and an ability to maintain integrity upon normal, commercial handling in a dry spreading operation and yet be capable of quickly disintegrating or scattering upon what may be a minimal exposure to water, such as, for example, a light rain.

d) GR – Soil applied Granule on inert or fertilizer carrier
This formulation is in the form of granules which can be applied on inert carrier or the carrier which is fertilizer.

e) Mixed formulation

e.1) ZC Formulation (Mix of CS and SC)
“ZC formulation” is the international denominations adopted by the FAO (Food and Agricultural Organization of the United Nations) to designate "stable aqueous suspension of microcapsules and solid fine particles"

ZC is a mixed formulation of CS and SC and is a stable aqueous suspension of microcapsules and solid fine particles, each of which contains one or more active ingredients. The formulation is intended for dilution into water prior to spray application. Formulating the active ingredients together eliminates the need for tank mixing, which can lead to incompatibility, and facilitates control of a wider range of pests with fewer applications. Like other aqueous liquid formulations, ZC formulations are easy to handle and measure, dust free, non-flammable and offer good miscibility with water.

One or more of the active ingredients is encapsulated for various purposes, such as to increase the residual biological activity, or to reduce the acute toxicity, or to obtain a physical or chemically stable water-based formulation. The purpose determines whether the “free” active ingredient and the “release rate” are relevant properties of a specific product.

Formulation of the present invention can be in any of the form described above.

Pyriproxyfen and Fenpyroximate which are active ingredients of the present invention are present in ratio of 50:1 to 1:20, preferably 15:1 to 1:10, most preferably 5: 1 to 1: 1.

Bioactive Pyriproxyfen and Fenpyroximate are present in the formulation with minimum 95% purity. Pyriproxyfen and Fenpyroximate as mentioned in whole the specification to be considered as technicals with minimum 95% of purity.

The of crops which can be protected by the present formulation are Cotton (Gossypium spp.), Maize (Zea mays), Soybean (Glycin max), Peanut (Arachis hypogaea), Sunflower (Helianthus annuus) , Brinjal (Solanum melongena), Okra (Abelmoschus esculentus) , Onion (Allium cepa L.), Tomato (Solanum lycopersicun) , Potato (Solanum tuberosum) , Chilly (Capsicum annum), Garlic (Allium sativum), Cucumber (Cucumis sativus) and Melons (Cucumis melo), Apple (Melus domestica), Banana (Musa spp.), Citrus groups (Citrus spp.), Grape (Vitis vinifera), Guava (Psidium guajava), Litchi (Litchi chinensis), Mango (Mangifera indica), Papaya (Carica papaya), Pomegranate (Punica granatum) , Sapota (Manilkara zapota), Tea (Camellia sinensis), Coffea (Coffea Arabica), Coconut (Coco nucifera), Rose (Rosa spp.).

The formulation of the present invention can be used to control the insects-pests belongs to the order Homoptera, for example, Aonidiella spp., Aphididae, Aphis spp., Bemisia tabaci, Trialeurodes vaporariorum, Amrasca biguttula, Empoasca spp., Myzus spp., Nephotettix spp., Nilaparvata spp., Planococcus spp., Pseudococcus spp., Psylla spp., Rhopalosiphum spp., Sitobion spp., from order Lepidoptera, Cydia spp., Earias spp., Heliothis spp., Hellula spp., Pectinophora gossypiella,; from the order Coleoptera, for example, Anthonomus spp., Diabrotica spp., Epilachna 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 Diptera, for example, Antherigona soccata, Dacus spp., Liriomyza spp., Melanagromyza spp.; from the order Acarina, for example, Brevipalpus spp., Eriophyes spp., Olygonychus spp., Panonychus spp., Polyphagotarsonemus latus, Tarsonemus spp. and Tetranychus spp.

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

A dispersant is a substance which adsorbs onto the surface of particles and helps to preserve the state of dispersion of the particles and prevents them from re-aggregating. Dispersants are added to agrochemical formulations to facilitate dispersion and suspension during manufacture, and to ensure the particles re-disperse into water in a spray tank. They are widely used in wettable powders, suspension concentrates and water-dispersible granules. Surfactants that are used as dispersants have the ability to adsorb strongly onto a particle surface and provide a charged or steric barrier to re-aggregation of particles. The most commonly used surfactants are anionic, non-ionic, or mixtures of the two types. For wettable powder formulations, the most common dispersants are sodium lignosulphonates. For suspension concentrates, very good adsorption and stabilization are obtained using polyelectrolytes, such as sodium naphthalene sulphonate formaldehyde condensates. Tristyrylphenol ethoxylate phosphate esters are also used. Non-ionics such as alkylarylethylene oxide condensates and EO-PO block copolymers are sometimes combined with anionics as dispersants for suspension concentrates. In recent years, new types of very high molecular weight polymeric surfactants have been developed as dispersants. These have very long hydrophobic ‘backbones’ and a large number of ethylene oxide chains forming the ‘teeth’ of a ‘comb’ surfactant. These high molecular weight polymers can give very good long-term stability to suspension concentrates because the hydrophobic backbones have many anchoring points onto the particle surfaces. Examples of dispersants used herein include but not limited to sodium lignosulphonates; sodium naphthalene sulphonate formaldehyde condensates; tristyrylphenol ethoxylate phosphate esters; aliphatic alcohol ethoxylates; alky ethoxylates; EO-PO block copolymers; and graft copolymers or mixtures thereof.

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

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

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

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

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

Thickeners or gelling agents are used mainly in the formulation of suspension concentrates, emulsions and 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 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, polsaccharides such as starch and cellulose derivatives, vinyl alcohol, vinyl acetate and vinyl pyrrolidone 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 method 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 ester - aliphatic polyester blends, modified corn starch, polycaprolactone, poly(n-amylmethacrylate), wood rosin, polyan-hydrides, polyvinylalcohol, polyhydroxybutyrate-valerate, 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.

WDG formulations offer a number of advantages in packaging, ease of handling and safety. The WDG are preferably of uniform size and which are free flowing, low dusting and readily disperse in water to form a homogenous solution of very small particles which may pass through conventional spray nozzles. Ideally WDG formulations when dispersed in water under gentle agitation for five minutes have residues of less than 0.01% on a 150 µm sieve screen and less than 0.5% on a 53 µm screen. The granules can usually be measured accurately by volume which is convenient for the end user.

The SC formulation can be prepared by below described method;
STEP-I: Adding anti-microbial agent and gum in water under continuous stirring followed by slow addition. Continuing stirring until homogeneous dispersion is formed.
STEP-II: Mixing anti-freezing agent, dispersant, wetting agent, anti-microbial agent and anti-foaming agent in water for 30 minute until homogeneous solution is formed. Finally Pyriproxyfen and Fenpyroximate are added slowly under continuous stirring for about 30 minutes till homogeneous dispersion is obtained. Milling the slurry through bead mill until required particle size is achieved.
Step-III: Adding rest of water, anti-foaming agent and gum solution under continuous stirring to get desired viscosity of the suspension. Continue stirring for about 4 hrs to obtain homogeneous formulation.

ZC formulation can be prepared by a) preparing SC formulation of one ingredient. B) Preparing CS formulation of another ingredient and finally mixing SC and CS formulation with stirring to obtain the final ZC formulation.

The process for preparing the present novel formulation can be modified accordingly by any person skilled in the art based on the knowledge of the manufacturing the formulation. However all such variations and modifications are still covered by the scope of present invention.

The following examples are intended to illustrate the present invention and to teach one of ordinary skill in the art how to make and use the invention. They are not intended to limit the invention in any way.

EXAMPLES

Example 1: Suspension Concentrate (SC)

COMPOSITIONS Pyriproxyfen 30% + Fenpyroximate 0.6% Pyriproxyfen 20% + Fenpyroximate 4% Pyriproxyfen 15% + Fenpyroximate 4% Pyriproxyfen 15% + Fenpyroximate 5% Pyriproxyfen 10% + Fenpyroximate 4% Pyriproxyfen 10% + Fenpyroximate 5% Pyriproxyfen 1% + Fenpyroximate 20%
Pyriproxyfen
(Min 95% purity) 32.10 21.50 16.30 16.30 11.00 11.00 1.60
Fenpyroximate
(Min 95% purity) 0.85 4.70 4.70 5.80 4.70 5.80 21.50
Tristyrylphenol polyethoxyester phosphate 3.00 3.00 3.00 3.00 3.00 3.00 3.00
Lignosulfonic acid, ethoxylated, sodium salts 0.80 0.80 0.80 0.80 0.80 0.80 0.80
Copolymer butanol EO/PO 2.50 2.50 2.50 2.50 3.50 2.50 2.50
DL-propanediol-(1,2) 5.00 5.00 5.00 5.00 5.00 5.00 5.00
Polydimethylsiloxane 0.20 0.20 0.20 0.20 0.20 0.20 0.20
1,2-benzisothiazol-3-one 0.01 0.01 0.01 0.01 0.01 0.01 0.01
Xanthan Gum 0.20 0.20 0.20 0.20 0.20 0.20 0.20
Water 55.3 62.09 67.29 66.19 71.6 71.49 65.19
TOTAL 100.00 100.00 100.00 100.00 100.00 100.00 100.00

Procedure

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 Flowable concentrate/ Suspension concentrate/ Flowable slurry production.
Step 3 Add required quantity of Wetting agent, dispersing agent & suspending agents, colourant/dye and homogenize the contents for 45 – 60 minutes using high shear homogenizer.
Step 4 Then add technical and other remaining adjuvants excluding ‘antifreeze & thickeners’ 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 three cycles of grinding in Dyno mill.
Step 6 Half quantity of the antifoam was added along with antifreeze after grinding process completes and before sampling for in process analysis.
Step 7 After completion of grinding cycles sample is sent to QC for A.I. & particle size analysis
Step 8 After approval from QC required quantity of gum solution should be added and homogenize the sample using high shear for 60 minutes, again send sample for viscosity check to QC and final approval.

Example 2: Oil Dispersion (OD)

COMPOSITIONS Pyriproxyfen 7.5% + Fenpyroximate 2% OD Pyriproxyfen 7.5% + Fenpyroximate 2.5% OD Pyriproxyfen 5% + Fenpyroximate 2% OD Pyriproxyfen 5% + Fenpyroximate 2.5% OD
Pyriproxyfen
(Min 95% purity) 8.20 8.20 5.80 5.80
Fenpyroximate
(Min 95% purity) 2.60 2.90 2.60 2.90
2-pyrrolidinone, 1-ethenylhexadecyl-, homopolymer 2.50 2.50 2.50 2.50
Tristyrenephenole with 16 moles EO 3.00 3.00 3.00 3.00
Dodecyl benzene sulphonic acid sodium salt 2.00 2.00 2.00 2.00
Fatty alcohol ethoxylate 5.00 5.00 5.00 5.00
Silicondioxide 1.00 1.00 1.00 1.00
Cyclohexanone 10.00 10.00 10.00 10.00
rape seed oil methyl ester 65.70 65.40 68.10 67.80
TOTAL 100.00 100.00 100.00 100.00

Procedure

Step 1 Charge required quantity of vegetable oil in vessel and add polyvinyl pyrrollidone, mix well for 30 minutes using high shear homogenizer and pass through horizontal bead mill.
Step 2 Add required quantity of Wetting agent, dispersing agent & suspending agents and homogenize the contents for 45 – 60 minutes using high shear homogenizer.
Step 3 Then add technical materials and homogenize for further 30 minutes.
Step 4 Now pass this homogenized material through horizontal bead mill to get required particle size.
Step 5 After completion of grinding cycles sample is sent to QC for A.I. & particle size analysis
Step 6 After approval from QC, material is transferred to storage tank till packing.

Example 3: Zeon Concentration (ZC)

COMPOSITIONS Pyriproxyfen 15% + Fenpyroximate 4% ZC Pyriproxyfen 15% + Fenpyroximate 5% ZC Pyriproxyfen 10% + Fenpyroximate 4% ZC Pyriproxyfen 10% + Fenpyroximate 5% ZC
Pyriproxyfen
(Min 95% purity) 16.30 16.30 11.00 11.00
Fenpyroximate
(Min 95% purity) 4.70 5.80 4.70 5.80
Tristyrylphenol polyethoxyester phosphate 3.00 3.00 3.00 3.00
Lignosulfonic acid, ethoxylated, sodium salts 0.80 0.80 0.80 0.80
Copolymer butanol EO/PO 2.50 2.50 2.50 2.50
DL-propanediol-(1,2) 5.00 5.00 5.00 5.00
Polydimethylsiloxane 0.20 0.20 0.20 0.20
1,2-benzisothiazol-3-one 0.01 0.01 0.01 0.01
Xanthan Gum 0.20 0.20 0.20 0.20
Polyurea capsule wall 2.50 2.50 2.50 2.50
Mixture of heavy aromatic hydrocarbons 20.00 20.00 20.00 20.00
Dodecyl-benzene sulfonic acid Ca-salt linear 2.00 2.00 2.00 2.00
Ammonia 0.20 0.20 0.20 0.20
Sulphuric acid 0.60 0.60 0.60 0.60
Water 42.0 40.89 47.29 46.19
TOTAL 100.00 100.00 100.00 100.00

Procedure
Step 1 Pyriproxiyen premix formulation: Charge water to a stainless steel vessel. Under agitation, add the dodecylbenzenesulfonic acid sodium salt into the vessel. Under agitation, heat the vessel to 60°C. As soon as a clear solution is formed, add the molten copolymer butanol PO/EO and continue the agitation. Once the solution is clear, add 1, 2-benzisothiazol-3-one and cool to room temperature.
Step 2 Charge a stainless steel reactor, equipped with a high shear disperser and a bulk-mixing agitator, with water. While mixing, add the lignosulfonate sodium salt. Then, add the ‘Emulsifier Premix’ and agitate to ensure complete blending. Cool the mixture to room temperature
Step 3 While mixing, charge a stainless steel reactor with a mixture of heavy aromatic hydrocarbons. Then, slowly add melted Pyriproxyfen technical to the reactor. Afterwards, charge isocyanic acid methyl-m-phenylene ester to the reactor. Continue mixing. Cool the reactor contents to room temperature.
Step 4 Using a high shear disperser, charge the ‘Organic Solution’ into the ‘Aqueous Phase Solution’ and continue to shear for 30 min. Then, heat the reactor to around 50 °C. During heating, reduce the agitation.
Step 5 After the wall polymerization reaction, increase the agitator to high speed. Add the antifoam to the mixture. Under slight vacuum, allow the mixture to de-gas for approximately 30 minutes to remove CO2 from the solution. Add ammonium hydroxide, the linear polysaccharide and propylene glycol. Then, add 1, 2-benzisothiazol-3-one and mix for some minutes. Add sulfuric acid for pH adjustment. Check the formulation to specifications
Fenproximate Premix formulation:
Step 6 2% Gel Preparation: Charge the required quantity of water to a vessel, equipped with a high shear stirrer and start the agitation. Add the required amount of 1,2-benzisothiazol-3-one preservative. Mix until homogenous. Add the required amount of heteropolysaccharide thickener and mix vigorously until it is fully wetted.
Step 7 Charge the required quantity of water to a vessel, equipped with bulk agitator and a high shear device and start agitation. Add the required amount of propylene glycol and mix until uniform. Add the polydimethylsiloxane antifoam and ensure that it is well dispersed. Add the tristyrylphenol polyethoxyester phosphate dispersing agent and mix until uniform. Ensure that the dispersing agent is fully dispersed.
Step 8 Add the sodium ligninsulfonate dispersing agent and mix until it is fully dispersed. Continue agitating the vessel contents until both dispersing agents are dissolved. Add Fenproximate technical and mix until the active ingredient is fully dispersed. Mill this mixture through a Colloid mill and subsequently through a Dynomill to meet the specified particle size.
Step 9 Add propylene glycol, the polydimethylsiloxane antifoam, the thickener and the Fenpyroximate millbase to a vessel, equipped with bulk agitator. Mix until uniform. Add the required amount of 2% aqueous pre-gel and continue agitation until the formulation is homogeneous and has the target viscosity. Mix well. Adjust the pH by adding the potassium hydroxide solution or sulfuric acid to around 5. Adjust the volume of water. Mix well.
Step 10 Charge the remaining quantity of water to a vessel, equipped with bulk agitator and start agitation. Add the Fenproximate Premix and Pyriproximate Premix and mix until uniform. Add the required amount of 2% pre-gel and continue agitation until the formulation is homogeneous and a target viscosity of around 600 mPa.s is reached. Mix well. Adjust the pH by adding potassium hydroxide solution or sulfuric acid until a target pH of around 5-7 is reached. Mix well.
Step 11 Final product is sent for QC approval.
Step 12 After approval material is packed in requied pack sizes.

Example 4: Emulsifiable Concentrate (EC)

COMPOSITIONS Pyriproxyfen 15% + Fenpyroximate 4% EC Pyriproxyfen 15% + Fenpyroximate 5% EC Pyriproxyfen 10% + Fenpyroximate 4% EC Pyriproxyfen 10% + Fenpyroximate 5% EC
Pyriproxyfen
(Min 95% purity) 16.30 16.30 11.00 11.00
Fenpyroximate
(Min 95% purity) 4.70 5.80 4.70 5.80
Dodecyl-benzene sulfonic acid Ca-salt linear 6.00 6.00 6.00 6.00
Condensation product of castor oil and ethyleneoxide 6.00 6.00 6.00 6.00
Cyclohexanone 10.00 10.00 10.00 10.00
Mixture of aromatic hydrocarbons 57.00 55.90 62.30 61.20
TOTAL 100.00 100.00 100.00 100.00

Procedure
Step 1 Charge half quantity of solvent and then mix the technical into this solvent until completely soluble
Step 2 Now add surfactants dose as per screening ration
Step 3 Now add remaining solvent to this mixture
Step 4 Final product is sent for QC approval.
Step 5 After approval material is packed in required pack sizes.

Example 5: Water Dispersible Granules (WG)

COMPOSITIONS Pyriproxyfen 30%+Fenpyroximate 0.6% WG Pyriproxyfen 15%+Fenpyroximate 4% WG Pyriproxyfen 15%+Fenpyroximate 5% WG Pyriproxyfen 10%+Fenpyroximate 4% WG Pyriproxyfen 10%+Fenpyroximate 5% WG Pyriproxyfen 1%+Fenpyroximate 20% WG
Pyriproxyfen
(Min 95% purity) 32.10 16.30 16.30 11.00 11.00 1.60
Fenpyroximate
(Min 95% purity) 0.85 4.70 5.80 4.70 5.80 21.60
Sodium Lauryl Sulfate 3.00 3.00 3.00 3.00 3.00 3.00
Sodium alkylnaphthalenesulfonate, formaldehyde condensate 7.00 7.00 7.00 7.00 7.00 7.00
Polyvinyl pyrollidone 0.50 0.50 0.50 0.50 0.50 0.50
PPT silica 15.00 15.00 15.00 20.00 20.00 25.00
Starch 5.00 10.00 10.00 10.00 10.00 10.00
China clay 36.6 43.5 42.4 43.8 42.7 31.3
TOTAL 100.00 100.00 100.00 100.00 100.00 100.00

Procedure
Step 1 Charge the required quantity of filler, wetting agent, dispersing agent, and suspending agent, & technical in premixing blender for homogenization for 30 minutes.
Step 2 Pre-blended material is than 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 Homogeneous material is analyzed. After getting approval from QC dept. material is unloaded into 25 kg. HDPE bag with LDPE liner inside.
Step 4 Finely grinded powder is mixer with required quantity of water to form extrudable dough.
Step 5 Dough is passed through extruder to get granules of required size.
Step 6 Wet granules are passed through Fluidized bed drier and further graded using vibrating screens.
Step 7 Final product is sent for QC approval.
Step 8 After approval material is packed in required pack sizes.

Example 6: Stability studies

6.1) Storage stability Study Data of Pyriproxyfen 15% + Fenpyroximate 4% SC (Suspension Concentrate)

Specification Initial Heat stability study at 54 + 2 0C for 14 days Cold storage stability at 0 + 2 0C for 14 days
Parameters In House
Description Off-white to Yellowish to flowable liquid Complies Complies Complies
Pyriproxyfen Content 14.25-15.75 15.5 15.2 15.5
Pyriproxyfen Suspensibility Mini 80% 95 94 95
Fenpyroximate Content 3.8-4.4 4.25 4.1 4.25
Fenpyroximate Suspensibility Mini 80% 96 95 96
pH (1%) 4.5-7.0 6 5.9 6
Particle size D50 <3, D90 <10 D50 <2.1, D90 <8 D50 <2.9, D90 <9 D50 <2.9, D90 <9
Pourability Mini 95% 97 97 96
Specific gravity 1.02 – 1.15 1.1 1.1 1.1
Viscosity 200-700 350 390 380

Room temperature storage data
Specification Study Duration

Parameters In house 1st day 6 month 12 months 36 months
Description Off-white to Yellowish to flowable liquid Complies Complies Complies Complies
Pyriproxyfen Content 14.25-15.75 15.5 15.5 15.45 15
Pyriproxyfen Suspensibility Mini 80% 95 95 95 93
Fenpyroximate Content 3.8-4.4 4.25 4.25 4.25 3.95
Fenpyroximate Suspensibility Mini 80% 96 96 96 94
pH 4.5-7.0 6 6 6 5.6
Particle size D50 <3, D90 <10 D50 <2.1, D90 <8 D50 <2.1, D90 <8 D50 <2.1, D90 <8 D50 <2.9, D90 <9
Pourability Mini 95% 97 97 97 97
Specific gravity 1.02 – 1.15 1.1 1.1 1.1 1.1
Viscosity 200-700 350 350 350 390

6.2) Storage stability Study Data of Pyriproxyfen 7.5% + Fenpyroximate 2% OD (Oil Dispersion)

Specification Initial Heat stability study at 54 + 2 0C for 14 days Cold storage stability at 0 + 2 0C for 14 days
Parameters In House
Description Off-white to Yellowish to flowable liquid Complies Complies Complies
Pyriproxyfen Content 7.125-8.25 8.2 8.1 8.2
Pyriproxyfen Suspensibility Mini 80% 95 95 95
Fenpyroximate Content 1.9-2.2 2.2 2.1 2.1
Fenpyroximate Suspensibility Mini 80% 96 94 96
pH 4.5-7.0 6 6 5.8
Particle size D50 <3, D90 <10 D50 <2.1, D90 <8 D50 <2.1, D90 <8 D50 <2.1, D90 <8
Pourability Mini 95% 97 97 97
Specific gravity 1.02 – 1.15 1.1 1.1 1.1
Viscosity 300-900 500 550 600

Room temperature storage data

Specification Study Duration

Parameters In house 1st day 6 month 12 months 36 months
Description Off-white to Yellowish to flowable liquid Complies Complies Complies Complies
Pyriproxyfen Content 7.125-8.25 8.2 8.2 8.2 8
Pyriproxyfen Suspensibility Mini 80% 95 95 95 94
Fenpyroximate Content 1.9-2.2 2.2 2.2 2.2 2
Fenpyroximate Suspensibility Mini 80% 96 96 96 95
pH 4.5-7.0 6 6 5.9 5.7
Particle size D50 <3, D90 <10 D50 <2.1, D90 <8 D50 <2.1, D90 <8 D50 <2.1, D90 <8 D50 <2.1, D90 <8
Pourability Mini 95% 97 97 97 97
Specific gravity 1.02 – 1.15 1.1 1.1 1.1 1.1
Viscosity 300-900 500 500 500 550

6.3) Storage stability Study Data of Pyriproxyfen 15% + Fenpyroximate 4% ZC (Zeon Concentration)

Specification Initial Heat stability study at 54 + 2 0C for 14 days Cold storage stability at 0 + 2 0C for 14 days
Parameters In House
Description Off-white to Yellowish to flowable liquid Complies Complies Complies
Pyriproxyfen Content 14.25-15.75 15.5 15.2 15.5
Pyriproxyfen Suspensibility Mini 80% 95 94 95
Fenpyroximate Content 3.8-4.4 4.25 4.1 4.25
Fenpyroximate Suspensibility Mini 80% 96 95 96
pH 4.5-7.0 6 5.9 6
Particle size D50 <3, D90 <10 D50 <2.1, D90 <8 D50 <2.9, D90 <9 D50 <2.9, D90 <9
Pourability Mini 95% 97 97 96
Specific gravity 1.02 – 1.15 1.1 1.1 1.1
Viscosity 200-700 350 390 380

Room temperature storage data

Specification Study Duration
Parameters In house 1st day 6 month 12 months 36 months
Description Off-white to Yellowish to flowable liquid Complies Complies Complies Complies
Pyriproxyfen Content 14.25-15.75 15.5 15.5 15.45 15
Pyriproxyfen Suspensibility Mini 80% 95 95 95 93
Fenpyroximate Content 3.8-4.4 4.25 4.25 4.25 3.95
Fenpyroximate Suspensibility Mini 80% 96 96 96 94
pH 4.5-7.0 6 6 6 5.6
Particle size D50 <3, D90 <10 D50 <2.1, D90 <8 D50 <2.1, D90 <8 D50 <2.1, D90 <8 D50 <2.9, D90 <9
Pourability Mini 95% 97 97 97 97
Specific gravity 1.02 – 1.15 1.1 1.1 1.1 1.1
Viscosity 200-700 350 350 350 390

6.4) Storage stability Study Data of Pyriproxyfen 15% + Fenpyroximate 4% EC(Emulsifiable Concentration)

Specification Initial Heat stability study at 54 + 2 0C for 14 days Cold storage stability at 0 + 2 0C for 14 days
Parameters In House
Description Off-white to Yellowish liquid Complies Complies Complies
Pyriproxyfen Content 14.25-15.75 15.5 15.3 15.5
Fenpyroximate Content 3.8-4.4 4.2 4.05 4.2
pH 4.5-7.0 6.5 6.2 6.5
Specific gravity 0.99 – 1.02 0.99 0.99 0.99

Room temperature storage data

Specification Study Duration
Parameters In house 1st day 6 month 12 months 36 months
Description Off-white to Yellowish liquid Complies Complies Complies Complies
Pyriproxyfen Content 14.25-15.75 15.5 15.5 15.45 15.1
Fenpyroximate Content 3.8-4.4 4.2 4.2 4.2 4
pH 4.5-7.0 6.5 6.5 6.5 6
Specific gravity 0.99 – 1.02 0.99 0.99 0.99 0.99

6.5) Storage stability Study of Pyriproxyfen 15% + Fenpyroximate 4% WDG (Water Dispersible Granules)

Specification Initial Heat stability study at 54+2 0C for 14 days Cold storage stability at 0+2 0C for 14 days
Parameters In House
Description White to off-white granules Complies Complies Complies
Pyriproxyfen Content 14.25-15.75 15.5 15.4 15.5
Pyriproxyfen Suspensibility Mini 60% 94% 91% 93%
Fenpyroximate Content 3.8-4.4 4.3 4.2 4.3
Fenpyroximate Suspensibility Mini 60% 94% 91% 93%
pH 4.5-7.0 6.5 6.3 6.5
Wet-sieve (45 micron sieve) Mini 99.5% 99.6 99.6 99.6
Bulk density 0.35 -0.45 0.4 0.4 0.4
Wettability 60 Sec Max 20 26 20

Room temperature storage data

Specification Study Duration
Parameters In house 1st day 6 month 12 months 36 months
Description White to off-white granules Complies Complies Complies Complies
Pyriproxyfen Content 14.25-15.75 15.5 15.5 15.5 15.2
Pyriproxyfen Suspensibility Mini 60% 94% 94% 94% 89%
Fenpyroximate Content 3.8-4.4 4.3 4.3 4.3 4.1
Fenpyroximate Suspensibility Mini 60% 94% 94% 94% 91%
pH 4.5-7.0 6.5 6.5 6.5 6
Wet-sieve (45 micron sieve) Mini 99.5% 99.6 99.6 99.6 99.6
Bulk density 0.35 -0.45 0.4 0.4 0.4 0.4
Wettability 60 Sec Max 20 20 20 30

Example 7: Field efficacy trials

The field study was carried out to evaluate the interaction / synergistic effect of Pyriproxyfen and Fenpyroximate. The testing samples with various novel formulations with different ratio of Pyriproxyfen and Fenpyroximate were developed in-house.
The key objective of these experiments were:
1. To find out the optimum ratio for maximum insecticidal action / synergistic action and thereby reducing pesticidal load in environment
2. To evaluate the efficacy of novel formulations with different ratio of Pyriproxyfen and Fenpyroximate
3. To evaluate the efficacy by checking viral diseases in chilli crop
4. To study the impact of novel formulations with different ration on beneficial / predatory insects in crop eco-system
5. To find out the impact on crop yield.
Table 1: Sample compositions comprising of Pyriproxyfen and Fenpyroximate, their formulations and use rate
S.No Sample Code Type of Formulation A.I.(%) in formulation Formulation per Hectare (g or ml) Active Ingredient/Hectare Ratio of Pyriproxyfen : Fenpyroximate
Pyriproxyfen Fenpyroximate Pyriproxyfen Fenpyroximate

1 PF1 SC 30.0% 0.6% 500 150 3 50 : 1
2 PF2 SC 20.0% 4.0% 500 100 20 5 : 1
3 PF3 SC 20.0% 5.0% 500 100 25 4 : 1
4 PF4 SC 20.0% 6.0% 500 100 30 3.33 : 1
5 PF5 SC 15.0% 4.0% 500 75 20 3.75 : 1
6 PF6 SC 15.0% 5.0% 500 75 25 3 : 1
7 PF7 SC 15.0% 6.0% 500 75 30 2.5 : 1
8 PF8 SC 10.0% 4.0% 500 50 20 2.5 : 1
9 PF9 SC 10.0% 5.0% 500 50 25 2 : 1
10 PF10 SC 10.0% 6.0% 500 50 30 1.67 : 1
11 PF11 SC 1.0% 20.0% 500 5 100 1 : 20
12 PF12 OD 7.5% 2.0% 1000 75 20 3.75 : 1
13 PF13 OD 7.5% 2.5% 1000 75 25 3 : 1
14 PF14 OD 5.0% 2.0% 1000 50 20 2.5 : 1
15 PF15 OD 5.0% 2.5% 1000 50 25 2 : 1
16 PF16 ZC 15.0% 4.0% 500 75 20 3.75 : 1
17 PF17 ZC 15.0% 5.0% 500 75 25 3 : 1
18 PF18 ZC 10.0% 4.0% 500 50 20 2.5 : 1
19 PF19 ZC 10.0% 5.0% 500 50 25 2 : 1
20 PF20 EC 15.0% 4.0% 500 75 20 3.75 : 1
21 PF21 EC 15.0% 5.0% 500 75 25 3 : 1
22 PF22 EC 10.0% 4.0% 500 50 20 2.5 : 1
23 PF23 EC 10.0% 5.0% 500 50 25 2 : 1
24 PF24 WDG 30.0% 0.6% 500 150 3 50 : 1
25 PF25 WDG 15.0% 4.0% 500 75 20 3.75 : 1
26 PF26 WDG 15.0% 5.0% 500 75 25 3 : 1
27 PF27 WDG 10.0% 4.0% 500 50 20 2.5 : 1
28 PF28 WDG 10.0% 5.0% 500 50 25 2 : 1
29 PF29 WDG 1.0% 20.0% 500 5 100 1 : 20
30 Prior Art 1 EC 10% _ 1000 100 _
31 Prior Art 2 EC _ 5% 600 _ 30 _
32 Prior Art 3 EC+EC 10% 5% 1000ml+600ml 100 30 _
33 Prior Art 4 EC+EC 10% 5% 750ml+400ml 75 20 _
34 Prior Art 5 EC+EC 10% 5% 500ml+400ml 50 20 _
35 Prior Art 6 EC+EC 10% 5% 750ml+500ml 75 25 _
36 Prior Art 7 EC+EC 10% 5% 500ml+500ml 50 25 _
37 Untreated Check _ _ _
Note :
A. I. -Active Ingredient, g- Gram, mi –milli liter, SC- Suspension Concentrate, OD –Oil Dispersion, ZC –Zeon Concentration, EC- Emulsifiable Concentrate, WDG -Water Dispersible Granules, PF1 to PF29- Laboratory developed Samples (Pyriproxyfen+Fenpyroximate).

Chilly (Capsicum annum L.) is spice crop, cultivated across the India. Many sucking insects damage the crop from seedling stage to harvesting. The key pests are Mites, Polyphagotarsonemus latus, Thrips, Thrips tabaci (Linnman), Whitefly Bemisia tabaci (Gennadius) and Aphid (Aphis gossypii). They cause severe damage to the crop and fruit yield. They are also responsible for many serious viral diseases in chilly crops like whitefly carries TLCV (Tobacco Leaf Curl Virus) and Thrips acts as a vector for Tospo (Tomato Spotted Wilt Virus). Hence the chemical control is necessary to keep the population of sucking pests under check.
The experiment was conducted in chilly crop at Anand District of Gujarat state. The Complete Randomized Block used with 5 m X 5 m net plot size and 37 sets of treatments including one untreated check and seven sets of prior art samples. The chilly crop was raised with all standard agronomic practices. Spraying was done with back pack sprayer with 500 liter of water spray volume. The experiment initiated as soon as infestation of Whitefly (Bemisia tabaci) and Yellow mite (Polyphagotarsonemus latus) observed on young leaves. The observations was recorded by counting the no. of motile stages of mites per twig (3 twigs per plant), no. of whitefly per leaf (5 leaves per plant) and five plants were assessed per plot. The mite damage to the crop also evaluated by visual observation (% leaf curling, 0 to 100%). The viral disease incidence of Tobacco Leaf Curl Virus (TLCV) was assessed by counting no. of healthy and infected plants from entire plot. The observations were recorded at before spraying and 5 and 10 days after spraying. The field observations were presented in below table. The observations on beneficial insects i.e. Predatory mites, and Chrysopa spp. were also recorded along with harmful insects to assess the harmful impact of all formulations on beneficial insects. The efficacy of various treatments was also judged at the time of harvest by considering green fruit yield.
Table 2- Control of Yellow mite and Whitefly in Chilly crop treated with Pyriproxyfen and Fenpyroximate formulations

Sample Code Type of Formulation Active Ingredient/Hectare Number of Motile stage of Mites Number of Insects per 3 leaves
Pyriproxyfen Fenpyroximate Yellow Mite, Polyphagotarsonemus latus Whitefly, Bemisia tabaci
BS 5 DAT 10 DAT BS 5 DAT 10 DAT
PF1 SC 150 3 16 12 20 17 9 15
PF2 SC 100 20 13 2 4 15 3 6
PF3 SC 100 25 18 3 3 19 2 4
PF4 SC 100 30 20 0 2 21 1 3
PF5 SC 75 20 11 3 6 17 5 8
PF6 SC 75 25 15 2 5 23 4 6
PF7 SC 75 30 13 1 3 18 3 5
PF8 SC 50 20 12 4 7 26 7 10
PF9 SC 50 25 17 3 7 21 6 8
PF10 SC 50 30 19 4 8 15 5 7
PF11 SC 5 100 15 6 13 18 11 18
PF12 OD 75 20 19 2 5 22 6 10
PF13 OD 75 25 12 1 3 21 5 8
PF14 OD 50 20 21 3 6 19 8 12
PF15 OD 50 25 15 2 4 21 6 9
PF16 ZC 75 20 16 2 3 25 6 9
PF17 ZC 75 25 20 0 2 20 4 7
PF18 ZC 50 20 14 2 7 19 9 12
PF19 ZC 50 25 18 3 5 23 7 10
PF20 EC 75 20 12 2 7 24 7 9
PF21 EC 75 25 20 2 5 21 5 7
PF22 EC 50 20 16 3 6 18 8 11
PF23 EC 50 25 21 2 4 23 6 8
PF24 WDG 150 3 16 12 22 25 7 12
PF25 WDG 75 20 13 3 5 21 6 9
PF26 WDG 75 25 22 1 3 20 5 7
PF27 WDG 50 20 14 3 7 19 8 12
PF28 WDG 50 25 17 2 4 25 7 9
PF29 WDG 5 100 20 8 15 22 9 15
Prior Art 1 EC 100 _ 15 14 28 18 12 16
Prior Art 2 EC _ 30 18 10 22 25 16 23
Prior Art 3 EC+EC 100 30 21 8 17 28 9 16
Prior Art 4 EC+EC 75 20 14 12 23 24 15 28
Prior Art 5 EC+EC 50 20 18 14 26 21 15 32
Prior Art 6 EC+EC 75 25 15 9 27 29 10 18
Prior Art 7 EC+EC 50 25 17 10 30 25 14 24
Untreated Check _ _ 16 21 38 23 32 49

Note: BS –Before Spray, DAT –Days after Treatment

The field experiment data on insect population show very good efficacy control of Pyriproxyfen and Fenpyroximate compared with all prior art treated and untreated control. All the formulations of Pyriproxyfen and Fenpyroximate effectively reduce the mites and whitefly population after spray. The formulation ratio of Pyriproxyfen and Fenpyroximate ranges from 5 : 1 to 1.67 : 1 provides excellent efficacy with longer residual control which will helpful in reducing the number of spray application per crop cycle and thereby reducing the pesticidal load in the environment. The observations also show high level of synergism between Pyriproxyfen and Fenpyroximate.

Table 3- Effect of Pyriproxyfen and Fenpyroximate on leaf curling by mites and viral disease incidence

Sample Code Type of Formulation Active Ingredient/Hectare % Leaf curling due to Mites % Viral Diseases Incidence (Tobacco Leaf Curl Virus)
Pyriproxyfen Fenpyroximate

PF1 SC 150 3 10% 2.2%
PF2 SC 100 20 5% 0.5%
PF3 SC 100 25 0 0.5%
PF4 SC 100 30 0 0.2%
PF5 SC 75 20 0 0.8%
PF6 SC 75 25 0 0.6%
PF7 SC 75 30 0 0.5%
PF8 SC 50 20 5% 1.8%
PF9 SC 50 25 5% 1.4%
PF10 SC 50 30 5% 1%
PF11 SC 5 100 10% 3.2%
PF12 OD 75 20 0 0.8%
PF13 OD 75 25 0 1%
PF14 OD 50 20 5% 1.5%
PF15 OD 50 25 5% 1.2%
PF16 ZC 75 20 0 1.4%
PF17 ZC 75 25 0 0.9%
PF18 ZC 50 20 5% 1.8%
PF19 ZC 50 25 5% 1.5%
PF20 EC 75 20 0 1.4%
PF21 EC 75 25 0 1.1%
PF22 EC 50 20 5% 2.5%
PF23 EC 50 25 5% 2.1%
PF24 WDG 150 3 10% 2.4%
PF25 WDG 75 20 0 1.8%
PF26 WDG 75 25 0 1.5%
PF27 WDG 50 20 5% 2.1%
PF28 WDG 50 25 5% 1.9%
PF29 WDG 5 100 10% 3.6%
Prior Art 1 EC 100 _ 20% 4.1%
Prior Art 2 EC _ 30 15% 4.8%
Prior Art 3 EC+EC 100 30 15% 10.1%
Prior Art 4 EC+EC 75 20 25% 12.6%
Prior Art 5 EC+EC 50 20 30% 14.5%
Prior Art 6 EC+EC 75 25 20% 10.6%
Prior Art 7 EC+EC 50 25 20% 11.4%
Untreated Check _ _ 40% 24.2%

The visual observations on leaf curling due to Mites indicate almost no damage to minimal leaf curling observed in all the Pyriproxyfen and Fenpyroximate formulations compared to all the all prior art treatments. The deadliest viral diseases like Tobacco Leaf Curl Virus incidence were also observed lowest in Pyriproxyfen and Fenpyroximate formulations as compared to all the prior art treatments. The lower viral disease incidence and minimal mites damage in all the treatments of Pyriproxyfen and Fenpyroximate also reflects in green chilly fruit yield.
Sample Code Type of Formulation Active Ingredient/Hectare Green Fruit yield per plot (kg)
Pyriproxyfen Fenpyroximate

PF1 SC 150 3 5.1
PF2 SC 100 20 6.4
PF3 SC 100 25 6.2
PF4 SC 100 30 6.6
PF5 SC 75 20 6.5
PF6 SC 75 25 6.3
PF7 SC 75 30 6.4
PF8 SC 50 20 5.7
PF9 SC 50 25 6.0
PF10 SC 50 30 6.2
PF11 SC 5 100 4.9
PF12 OD 75 20 6.2
PF13 OD 75 25 6.5
PF14 OD 50 20 5.6
PF15 OD 50 25 5.8
PF16 ZC 75 20 6.1
PF17 ZC 75 25 6.3
PF18 ZC 50 20 5.7
PF19 ZC 50 25 5.9
PF20 EC 75 20 5.9
PF21 EC 75 25 6.0
PF22 EC 50 20 5.5
PF23 EC 50 25 5.6
PF24 WDG 150 3 5.0
PF25 WDG 75 20 6.1
PF26 WDG 75 25 6.2
PF27 WDG 50 20 5.4
PF28 WDG 50 25 5.5
PF29 WDG 5 100 4.7
Prior Art 1 EC 100 _ 4.2
Prior Art 2 EC _ 30 3.9
Prior Art 3 EC+EC 100 30 4.5
Prior Art 4 EC+EC 75 20 3.9
Prior Art 5 EC+EC 50 20 3.8
Prior Art 6 EC+EC 75 25 4.3
Prior Art 7 EC+EC 50 25 4.2
Untreated Check _ _ 2.8

Green fruit yield observation shows higher green fruit (marketable) yield has been obtained from Pyriproxyfen and Fenpyroximate formulations as compared to all the prior art treatments.

Table 4- Effect of insecticidal treatments on population of beneficial insects in crop eco-system

Sample Code Type of Formulation Active Ingredient/Hectare Beneficial Insects Population before and after sprays
Pyriproxyfen Fenpyroximate Predatory Mites Chrysopera spp.
1 DBT 3 DAT 7 DAT 1 DBT 3 DAT 7 DAT
PF1 SC 150 3 4 6 7 4 5 8
PF2 SC 100 20 3 4 11 3 6 9
PF3 SC 100 25 5 6 10 2 5 8
PF4 SC 100 30 4 5 7 3 6 7
PF5 SC 75 20 2 7 8 4 5 11
PF6 SC 75 25 4 5 6 3 7 12
PF7 SC 75 30 3 6 10 2 5 8
PF8 SC 50 20 2 5 8 3 4 10
PF9 SC 50 25 3 6 7 4 5 9
PF10 SC 50 30 5 7 9 3 6 8
PF11 SC 5 100 3 5 10 2 5 12
PF12 OD 75 20 4 6 9 3 7 8
PF13 OD 75 25 2 4 6 3 5 9
PF14 OD 50 20 3 5 11 2 6 8
PF15 OD 50 25 4 6 10 4 5 10
PF16 ZC 75 20 2 5 10 3 6 9
PF17 ZC 75 25 4 7 9 2 7 10
PF18 ZC 50 20 3 5 8 4 6 8
PF19 ZC 50 25 2 6 9 3 5 11
PF20 EC 75 20 3 5 7 2 4 5
PF21 EC 75 25 4 6 6 3 4 4
PF22 EC 50 20 5 4 6 4 3 3
PF23 EC 50 25 2 5 6 3 3 4
PF24 WDG 150 3 3 6 7 2 5 8
PF25 WDG 75 20 4 5 8 3 6 10
PF26 WDG 75 25 3 4 9 4 4 9
PF27 WDG 50 20 4 6 10 3 6 11
PF28 WDG 50 25 5 5 6 2 5 10
PF29 WDG 5 100 2 4 8 3 6 8
Prior Art 1 EC 100 _ 3 4 4 4 5 4
Prior Art 2 EC _ 30 4 3 3 3 4 5
Prior Art 3 EC+EC 100 30 3 4 4 2 3 5
Prior Art 4 EC+EC 75 20 5 4 2 4 3 4
Prior Art 5 EC+EC 50 20 3 2 3 3 4 3
Prior Art 6 EC+EC 75 25 2 3 4 3 3 4
Prior Art 7 EC+EC 50 25 3 3 3 4 3 4
Untreated Check _ _ 4 7 11 3 8 10

The observations on beneficial insects at 10 days after treatments indicate comparatively higher population of both the beneficial insects i.e. Predatory mites and Chysopa spp. has been observed in formulations of Pyriproxyfen and Fenpyroximate compared to all the prior art treatments. This indicates the safety of SC, OD, ZC and WDG formulations of Pyriproxyfen and Fenpyroximate as compared to all prior treatments.

Further the formulation of the present invention also provides good control over more than one pests that tend to be present on the plant at the same time.
,CLAIMS:WE CLAIM,

1. A novel formulation comprising of Pyriproxyfen and Fenpyroximate and one or more inactive excipients.
2. The novel formulation as claimed in claim 1 wherein the ratio of Pyriproxyfen and Fenpyroximate is 50:1 to 1:20.
3. The novel formulation 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, quick coating agent or sticking agents and buffering agent.
4. The novel formulation as claimed in claim 1 or 2 wherein the formulation can be selected from Suspension Concentrate (SC), Oil Dispersion (OD), Zeon Concentration (ZC), Emulsifiable Concentrate (EC) and Water dispersible granules (WDG).
5. The novel formulation as claimed in any of the preceding claims, wherein the said formulation is used for control of pests in Cotton (Gossypium spp.), Maize (Zea mays), Soybean (Glycin max), Peanut (Arachis hypogaea), Sunflower (Helianthus annuus) , Brinjal (Solanum melongena), Okra (Abelmoschus esculentus), Onion (Allium cepa L.), Tomato (Solanum lycopersicun) , Potato (Solanum tuberosum) , Chilly (Capsicum annum), Garlic (Allium sativum), Cucumber (Cucumis sativus) and Melons (Cucumis melo), Apple (Melus domestica), Banana (Musa spp.), Citrus groups (Citrus spp.), Grape (Vitis vinifera), Guava (Psidium guajava), Litchi (Litchi chinensis), Mango (Mangifera indica), Papaya (Carica papaya), Pomegranate (Punica granatum) , Sapota (Manilkara zapota), Tea (Camellia sinensis), Coffea (Coffea Arabica), Coconut (Coco nucifera), Rose (Rosa spp.).

6. The novel formulation as claimed in claim 5, wherein the said formulation is used to control insects-pests belongs to order Homoptera, for example, Aonidiella spp., Aphididae, Aphis spp., Bemisia tabaci, Trialeurodes vaporariorum, Amrasca biguttula, Empoasca spp., Myzus spp., Nephotettix spp., Nilaparvata spp., Planococcus spp., Pseudococcus spp., Psylla spp., Rhopalosiphum spp., Sitobion spp., from order Lepidoptera, Cydia spp., Earias spp., Heliothis spp., Hellula spp., Pectinophora gossypiella,; from the order Coleoptera, for example, Anthonomus spp., Diabrotica spp., Epilachna 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 Diptera, for example, Antherigona soccata, Dacus spp., Liriomyza spp., Melanagromyza spp.; from the order Acarina, for example, Brevipalpus spp., Eriophyes spp., Olygonychus spp., Panonychus spp., Polyphagotarsonemus latus, Tarsonemus spp. and Tetranychus spp.

7. A novel formulation of Pyriproxyfen and Fenpyroximate as claimed in any of the preceding claims and exemplified with working examples as disclosed.