FIELD OF THE INVENTION
The present invention is related to a synergistic miticidal composition comprising an effective amount of Pyriproxyfen, Diafenthiuron and at least one (C8-C16) alkyl amide as organic solvent, wherein the organic solvent is present in an amount ranging from about 1% to about 14% by weight, widening the spectrum of action on a plurality of mite’s family with an increased safety upon use.

BACKGROUND OF THE INVENTION
Pesticides are substances that are meant to control pests or weeds. The Food and Agriculture Organization (FAO) has defined pesticide as: any substance or mixture of substances intended for preventing, destroying, or controlling any pest, including vectors of human or animal disease, unwanted species of plants or animals, causing harm during or otherwise interfering with the production, processing, storage, transport, or marketing of food, agricultural commodities, wood and wood products or animal feedstuffs, or substances that may be administered to animals for the control of insects, arachnids, or other pests in or on their bodies. The term includes substances intended for use as a plant growth regulator, defoliant, desiccant, or agent for thinning fruit or preventing the premature fall of fruit. Also used as substances applied to crops either before or after harvest to protect the commodity from deterioration during storage and transport.
Insecticides are agents of chemical or biological origin that control insects. Control may result from killing the insect or otherwise preventing it from engaging in behaviors deemed destructive. Insecticides may be natural or manmade and are applied to target pests in a myriad of formulations and delivery systems. The science of biotechnology has, in recent years, even incorporated bacterial genes coding for insecticidal proteins into various crop plants that deal death to unsuspecting pests that feed on them. The primary benefits are the consequences of the pesticides' effects – the direct gains expected from their use.
Mites are very small arthropods having four pairs or eight legs. Usually they live in very specialized habitats like plants, animals, stored products, soil and water. Plant-dwelling mites are predators of plant pest mites, some may feed on plants but don't cause noticeable damage, and others can be beneficial by feeding on leaf fungus. Mites have been broadly classified depending on their characteristics. The Prostigmata is a suborder of mites belonging to the order Trombidiformes, which contains the "sucking" members of the "true mites" (Acariformes). Many species are notorious pests on plants. Well-known examples of prostigmatan plant parasites are species of the gall mites (Eriophyidae, e.g. the redberry mite Acalitus essigi), Tarsonemidae (e.g. the cyclamen mite, Steneotarsonemus pallidus), and the spider mites of the Tetranychidae (e.g. the two-spotted spider mite, Tetranychus urticae). Sub order Acaridida (Astigmata) comprises of parasitic mites that are pest in homes (house dust, furniture, food) and stored products. The phytoseiid family of order Mesostigmata comprises of parasitic pest of farm animals. Prostigmatid mites (Order: Trombidiformes) are associated with fruits trees, vegetable, ornamentals and wild vegetation. The major plant feeding mites belong to families of spider mite (Tetranychidae), false spider mite (Tenuipalpidae) and gall mite (Eriophyidae).Red spider mite and yellow mite are very much important from agriculture point of view which comes under Tetranychidae and Tarsonemidae family respectively.
Physiological characteristics of plant mites
Mites are microscopic pest which are small in size approximately 0.5 to 1 mm in length, they are associated with an apparent loss of true segmentation and reduction in internal and external features. Adult mites have 8 legs, immature stages have six legs and mites in the superfamily Eriophyoidea have only four legs. In the body of mites head, thorax and abdomen fused together make one segment (Cephalothorax). Simple eyes that are sensitive to light intensity; they do not see images but just hazy spots of lights. Many species spin silk webbing which help to protect the colony from predators. Mites in general have four stages in their life cycle: egg–larvae–nymph–adult. Larvae are very special; they have only three pairs of legs instead of four. The nymph looks like a small adult (with four legs) but cannot reproduce; their reproductive organs are not mature. Tetranychidae: These mites are largest group of plant feeding mites. They are spider mites having round to oval-shaped bodies and are as large as or smaller than a pin head (about 0.3 to 0.8 mm long). Their colour vary from green, red, brown, yellow, orange, black or combinations of any of these, depending on the species and the life stage. Most tetranychid species have a wide host range, other than the generally more host specific like Eriophyoidea. Some species, especially Tetranychus spp., can produce extensive webbing which impedes effective control of these pests. Example: Tetranychus urticae (Red Spider mite). Tarsonemidae: Adults of this kind of mites are large, oval, broad and yellowish in colour. Larva or nymphs are very tiny with white translucent colour and a translucent stripe on dorsal side while quiescent larva is elongated at both ends and sedentary (immovable). Example: Polyphagotarsonemus latus (Yellow mite)
Problems created by plant mites
Plant mites may injure the plant’s leaf or fruit surface by piercing the plant cells with their chelicerae and sucking out the contents. Plant-feeding mites can cause injury to plant in several ways, among which some are listed as below,
• Small Feeding Punctures
• Brown wilted leaves
• Curled yellow leaves (Downward curling)
• Foliage that is speckled
• As feeding continues, the leaves turn to yellowish or reddish and then drop
off.
• Formation of tiny web-like structures in plants
• Mottled or discolored needles on conifers like pine, spruce, and hemlock
(Needle loss can occur in severe infestations)
• Fruit may develop unsightly lesions, Bronzing of leaves in plants.
• Often, large amounts of webbing which cover leaves, twigs, and fruit.
• Damage is usually worse when compounded by water stress.

Besides this, phytophagous mites also inject toxic substances into hosts causing disruption in tissues and increase in localized growth. Sometimes plants may produce galls or other malformed plant parts in response to mite feeding. The mite may shelter within these malformed plant parts to feed and reproduce.

Conditions for attack of plant mites
Phytophagous mites like red spider mite and yellow mite problem is pronounced during hot and humid time of the year. They affect variety of vegetables and other crops like cotton, peas, soybean, groundnut, wheat. They are also predominant in Poly houses. Poly houses are built of a Pre-galvanized channel cum tubular structure wherein, crops are grown under a favorable controlled environment and other conditions viz. temperature, humidity, light intensity, ventilation, soil media, disease control, irrigation, fertigation and other agronomical practices throughout the season irrespective of the natural conditions outside. Spider mites are known to feed on several hundred species of plants. These mites are present throughout the year in tropic and sub-tropic regions.
Depending on the species and on the environmental conditions (21.1°C and 27°C temperatures and 5 to 75% relative humidity) the time required to complete the life cycle of plant mites varies enormously. High level of temperature decreased the time of development of all life stages of mites, as compared to lower level.
Necessity to have solution for protection of plant from mites
The mites suck the plant sap and also cause a lot of other damage to the growing plants. Ultimately, in spite of all the efforts vested in by the grower the result or output achieved is not up to the mark. Sometime heavy mite attack may also lead to complete crop failure. Secondly the mites belong to class Arachanida are different from the insects that infest the crop. Mostly the insecticides used by the farmer do not have any effect on the mites and they can only be controlled by the use of a potent acaricide. Thus, all the cost spent in the use of insecticides is not justified if ultimately the crop fails due to mite infestation. The proper solution against the mites will definitely help the farmers to protect the crop against this pest and help them achieve good yields.
One major factor of mites that they develop quick resistance to pesticide. Under optimal conditions (approximately 80 °F or 27 °C), the two-spotted spider mite can hatch in as little as 3 days, and become sexually mature in as little as 5 days. One female can lay up to 20 eggs per day and can live for 2 to 4 weeks, laying hundreds of eggs. This accelerated reproductive rate allows spider mite populations to adapt quickly to resist pesticides, so chemical control methods can become somewhat ineffectual when the same pesticide is used over a prolonged period.
So there is requirement of formulation of specific composition, which is used to eliminate plant mites problem and also, delay the development of resistance of plant mites. The present invention provide significant solution to the problem of plant mites. The solvent used in present invention provides spreadable and translaminar property to the formulation which give excellent synergistic mode of action in effectively control of the target pest. Pyriproxyfen, chemically known as 2-[1-Methyl-2-(4-phenoxyphenoxy) ethoxy] pyridine and having chemical structure represented as below,

Pyriproxyfen
Pyriproxyfen is a pyridine-based pesticide which is found to be effective against a variety of arthropods. It was introduced to the United States in 1996, to protect cotton crops against whitefly. It has also been found useful for protecting other crops. It is also used as a prevention for flea control on household pets, for killing indoor and outdoor ants and roaches. Methods of application include aerosols, bait, carpet powders, foggers, shampoos and pet collars. Pyriproxyfen is a juvenile hormone analog and an insect growth regulator. It prevents larvae from developing into adulthood and thus rendering them unable to reproduce.
In United States, pyriproxyfen is often marketed under the trade name Nylar. In Europe, pyriproxyfen is known under the brand names Cyclio (Virbac) and Exil Flea Free TwinSpot (Emax).
Diafenthiuron, chemically known as N-[2, 6-bis (1-methylethyl)-4-phenoxyphenyl]-N'-(1,1-dimethylethyl)thiourea or 1-tert-butyl-3-(2,6-diisopropyl-4-phenoxyphenyl)thiourea or 1-tert-butyl-3-[4-phenoxy-2,6-di(propan-2-yl)phenyl]thiourea and having chemical structure represented as below,

Diafenthiuron
Diafenthiuron is a chemical compound from the group of thioureas. It was introduced in 1990 by Ciba-Geigy as an insecticide and acaricide. Diafenthiuron individually controls two-spotted mite and cotton aphids and suppresses silver leaf whitefly in cotton. Diafenthiuron acts after conversion by either light or in vivo, to the corresponding carbodiimide, which is an inhibitor of mitochondrial respiration.
The main concern of this invention is the development of stable miticidal formulation, which is on one hand is effective in wider range to control different families of mites with respect to different plants and also on another hand it is highly safe to the environment.
Surprisingly, it has now been found that the composition of pyriproxyfen, diafenthiuron and at least one (C8-C16) alkyl amide as organic solvent, widening the spectrum of action on the pests and on the other hand has increased safety upon use. The substituted amide solvent provides spreadable property and enhance the translaminar property of active ingredients of formulation which give excellent synergistic mode of action in effectively control of target pest.
Some documents are available as prior art which suggest the use of Pyriproxyfen, Diafenthiuron and different solvents in various formulation.
G.B. Patent No. GB2533083A, discloses dipropylene/diethylene glycol dibenzoate in the composition with active ingredients. The weight ratio of the dipropylene/diethylene glycol dibenzoate to the active ingredient is preferably at least 1:1, in some preferred embodiments at least 1:2, in other preferred embodiments at least 1:3. In particular, the dipropylene/diethylene glycol dibenzoate is preferably present in an amount to provide a weight ratio of the active ingredient to the dipropylene/diethylene glycol dibenzoate from 1:1 to 1:100, preferably from 1:1 to 1:90, more preferably from 1:2 to 1:20, still more preferably from 1:3 to 1:15. Preferably the active ingredient disclosed is one or more of bifenthrin, clethodim, clomazone, pyriproxyfen, lufenron and/or abamectin. The drawback of this invention is that this invention comprises the combination of two solvent dipropylene/diethylene glycol dibenzoate in EC (Emulsifiable concentrate) formulation. Further, this document GB2533083A does not discloses the synergistic effect against mites. In the present invention combination of pyriproxyfen, diafenthiuron and alkyl amide as organic solvent providing synergistic effect against plant mites.
WO2009/134375A2, discloses low volatile organic compound (VOCs) pesticidal composition comprising from about 0.1% to about 30% by weight of pyriproxyfen (2-[1-methyl-2-(4-phenoxyphenoxy)ethoxy]pyridine); from about 1% to about 30% by weight of a surfactant; and from about 40% to about 90% by weight of methyl esters of derivatives of cis fatty acids, wherein the weight percentages are based on the total weight of the pesticidal composition. The low VOCs pesticidal composition of the present invention comprises a co-solvent. Preferably, ethyl hexyl lactate, N, N-dimethyloctanamide and N, N-dimethyldecanamide or a blend thereof. The main problem associated with this prior invention is that it does not discloses the synergistic effect of pyriproxyfen and diafenthiuron and any solution to existing problems of mites in plants. Further, prior invention comprises N, N-dimethyloctanamide and N, N-dimethyldecanamide as co-solvents. In comparison to this prior art the present invention is providing synergistic effect of pyriproxyfen and diafenthiuron in the presence of alkyl amide as solvent to overcome the existing problems of mites in plants.
CN104115843A, discloses an insect and mite killing composition containing pyriproxyfen and etoxazole, wherein the weight ratio of pyriproxyfen to etoxazole is (30 to 1)-(1 to 30). Etoxazole is a narrow spectrum systemic acaricide used to combat spider mites. It targets variety of mites in the egg, larvae and nymph stages however not at the adult stage. This prior invention is disclosing miticidal effect due to Etoxazol.
CN104115833A discloses an insect and mite killing composition containing pyriproxyfen and cyflumetofen. Effective components of the insect and mite killing composition are pyriproxyfen and cyflumetofen, wherein the weight ratio of pyriproxyfen to cyflumetofen is (30 to 1)-(1 to 30). The insect and mite killing composition has an obvious synergistic interaction effect and can be used for preventing and controlling multiple insects, such as red spiders, aleyrodid, phylloxera, thrips, aphids and test as in agriculture as cyflumetofen is used as miticides. BASF product Sultan™ comprises cyflumetofen, which is used as miticide.
Indian patent application no. IN284/MUM2014, discloses water based (without any organic solvent) suspoemulsion composition of Pyriproxyfen and Diafenthiuron having effective control of whitefly in cotton and Leaf miner; Liriomyza trifolii in tomato plant crop. It is a water based formulation formed through suspension concentrate (SC) and oil-in-water emulsion (EW) technique. This prior formulation is not using (C8-C16) alkyl amide as solvent and also not disclosing the effect of invention to overcome the specific existing problems of mites in plants.
So, there was long felt need to prepare a stable formulation having enhanced efficacy, safe to natural enemies, significant advantages in packaging, ease of handling and safety, without much complex manufacturing process, which is used to eliminate plant mites problem and also delay the development of resistance of plant mites. The present invention provide the solution to problem of plant mites. The present invention of miticidal formulation comprising pyriproxyfen and diafenthiuron along with at least one (C8-C16) alkyl amide as organic solvent, has widen the spectrum of action on the pests control on one hand and on the other hand has more safety upon use. The solvent provides spreadable and translaminar property to the formulation which give excellent synergistic mode of action in effectively control of the target pest due to preventing heterogeneous flocculation in the formulation. The judiciously selected adjuvants has made this invention a stable formulation with composition as described in the invention.

OBJECTIVE AND ADVANTAGES OF THE INVENTION
The main objective of the present invention is to fulfil a necessity of formulation comprising specific insecticides and specific inactive ingredients which overcomes the existing problems of mites in plants and can be prepared easily without much complex manufacturing process along with the following further advantages:
1) The formulation can eliminate plant mite’s problem and also delay the development of resistance by mites. Thus, the main concern of the invention for the development of miticidal formulation, which is on one hand is effective in wider range to control different families of plant mites and on another hand it is highly safe to the environment.
2) The formulation of present invention comprising active ingredients along with the adjuvants in the formulation, is a stable formulation.
3) The formulation of present invention result in synergistic effect of Pyriproxyfen and Diafenthiuron along with at least one (C8-C16) alkyl amide as organic solvent which further has a low VOCs content (Volatile organic compounds content) thus it is safe on use.
4) The formulation of present invention is not having harmful effects on natural enemies
5) The formulation of present invention results in significant grain yield after crop treatment.
SUMMARY OF THE INVENTION
The present invention is related to a synergistic miticidal composition comprising effective amount of Pyriproxyfen and Diafenthiuron along with at least alkyl amide as organic solvent, which is on one hand is effective in wider range to control different families of plant mites and on another hand it is highly safe to the environment upon use.
Present invention is also related to process for preparing the miticidal composition comprising a synergistically effective amount of Pyriproxyfen and Diafenthiuron along with substituted amide as an organic solvent, wherein the amount of organic solvent is present in the range of 1% to 14% by weight in the composition. The formulation of present invention is stable and has a low VOCs content (Volatile organic compounds content) with an enhanced efficacy upon use.

DETAILED DESCRIPTION OF THE INVENTION
The term “pesticide” or “pesticidal” is similar to “insecticide” or “insecticidal” is used for “miticide” or “miticidal” and used interchangeably in this whole specification.
The phrase "pesticidally effective amount" or “effective amount” means the amount of a pesticide needed to achieve an observable effect on a pest and/or activity of a pest in a locus, this effect may come about when pest populations are repulsed from a locus, pests are incapacitated in or around a locus and/or pests are exterminated in or around a locus. Of course, a combination of these effects can occur. Generally, pest populations or activity or both are desirably reduced more than fifty percent, preferably more than 90 percent and most preferably more than 99 percent. The formulation of present invention synergistically acts to have excellent effect on 10 pests thus it has excellent pesticidal utility in control of pest
The phrase “synergistically effective amount “of the formulation means a sufficient amount of the formulation to provide the desired effect. In general, the formulation is employed in amounts that do not cause phytotoxic damage to any part of the plant. The amount of the formulation may vary depending on specific crops and other factors. It is well within an ordinary skill in the art to determine the necessary amount of the formulation.
Synergism is the interaction or cooperation of two or more substances, or agents to produce a combined effect greater than the sum of their individual effects.
As described in the Herbicide Handbook of the Weed Science Society of America, Ninth Edition, 2007, p. 429, “synergism” [is] an interaction of two or more factors such that the effect when combined is greater than the predicted effect based on the response to each factor applied separately. Colby's formula is applied to determine synergistic effect as follows:
E = (X + Y) – ((X × Y)/100)
For Synergy, O/E > 1
Wherein;
X=individual response in percent (%) using (a) Pyriproxyfen
Y= individual response in percent (%) using (b) Diafenthiuron
E=expected effect (in %) of (a) + (b) at application rates a and b.
O=Observed effect (in %) of (a) + (b)
The synergistic composition of present invention is used to control mites of family Tetranychidae (Spider Mite, Sugarcane Red Spider Mite, Fig spider mite, Oriental red mite, Citrus brown mite, Red tea mite, Mango red spider mite, Mango red spider mite, European red mite, Brown wheat mite, White patchy, sugarcane leaf spotted mite, web mite, Red-legged spider mite, Bean spider mite, Red vegetable mite, Two spotted spider mite), Tenuipalpidae/False Mites (Citrus flat mite, Scarlet mite, Reddish black flat mite, Eriophyidae (Leprosis mite, Pineapple flat mite, Bud Gall mite, Pigeon pea sterility mosaic mite, Coconut mite, Litchi erineum mite, Brinjal erineum mite, Tomato erineum mite, Mango bud mite, Jujube gall mite and Tarsonemidae (Citrus silver mite, broad mite, Rice sheath mite, Dahlia mite, yellow tea mite, Pink mite, Purple tea mite.
The synergistic composition of present invention is preferably used for control of mites in Wheat, Barley, Oats, Maize, Sorghum, Sugarcane, Areca catechu (Palm), Fig, Apple, Citrus, Cotton, Cucurbits, Coffee, Mango, Tea, Coriander, Beans, Vegetables, Cucurbits, Ornamental Plants, Bean, Brinjal, Okra, Guava, Papaya, Pineapple, Pigeon pea, Coconut, Litchi, Chilli, Jute, Potato, Rice, Almond, Castor, Jujube, Red Date, Golden Rain Tree, Lemon, Litchi, Golden Shower Tree, Gourds, Sweet Potato, Garlic, Onion, Marigold, Jasmine, Chrysanthemums, Areca, Coconut palms.
A miticidal composition of the present invention is formulated in suspo-emulsion (SE) formulation i.e. Suspo-Emulsion formulation of present invention comprises the desired said miticidal composition. Suspoemulsion (SE) formulations are normally made by combining two active ingredients with very different physical properties into one formulation. Mostly they are combination of suspension concentrate (SC) and concentrated aqueous emulsion (EW) technologies. While, formulation of the present invention is a combination of suspension concentrate (SC) and emulsifiable concentrate (EC) widening the spectrum of activity and eliminating the disadvantage of tank-mix incompatibility, creaming (or sedimentation), flocculation, Ostwald ripening, coalescence and phase inversion.
The active combination according to the present invention comprises Pyriproxyfen and Diafenthiuron preferably in a ratio of between 1:20 and 20:1, especially between 10:1 and 1:10, more preferably between 5:1 and 1:5. These ratios are to be understood as meaning, on the one hand, weight ratios, and on the other hand molar ratios. Further, according to the present invention the ingredients are present in composition or formulated in the said formulation in an amount percent weight by weight of composition or formulation. The formulation of present invention has heat and hydrolysis stability and as well as low VOCs content (volatile organic compounds content).
The leaf cuticle functions as a barrier that can inhibit absorption, penetration and transport of foliar-applied pesticides into the leaf. The leaf cuticle is very lipophilic (an affinity for dissolving in lipids), which can impact penetration of pesticides into the leaf. The permeability of the leaf cuticle is an important factor that can influence penetration and subsequently movement through leaf tissues, and varies depending on the presence of cuticular waxes on the leaf surface. Leaf cuticle permeability can differ among plant species and cultivars, therefore, reduced penetration and movement through the leaf tissues may indirectly impact suppression of pests with pesticides.
An effective amount of (C8-C16) alkyl amide as organic solvent in the present invention leads the pesticides to enter the plant leaf after application of formulation with penetration occurring primarily through the leaf cuticle. The mechanism involved in penetration and movement into leaves via the leaf cuticle is by diffusion.
Further, the solvent of present invention provides spreadable and translaminar property to the formulation which give excellent synergistic mode of action in effectively control of the target pest due to preventing heterogeneous flocculation in the formulation. Here heterogeneous flocculation is an aggregation of two dissimilar particle types, for example, a solid particle aggregating with emulsified oil droplets.
Preferably, the miticidal compositions of the present invention comprises effective amount of (C8-C16) alkyl amide as organic solvent which is selected from the group comprising N,N-Dimethyl heptanamide, N,N-diethyl heptanamide, N,N-Dimethyl octanamide, N,N-Diethyl octanamide, N,N-dimethyl nonanamide, N,N-Diethyl nonanamide, N, N-Dimethyl decanamide, N,N-Diethyl decanamide, N,N-Dimethyl undecanamide, N,N-Diethyl undecanamide, N,N-Dimethyl dodecanamide, N,N-Diethyl dodecanamide or a mixture/or blend thereof. In accordance with one preferred embodiment of the present invention, the solvent used are N, N-Dimethyl decanamide or N,N-Diethyl octanamide or commercially available RHODIASOLV®(blend of N,N-Dimethyl octanamide and N,N-Dimethyl decanamide) or a mixture thereof, which preferably between the range of about 1% to 14% by weight, most preferably in the range of 8% to 14% weight by weight, providing the characteristic of more than 95% pourability to the said formulation.
An adjuvant is any material that is added to an agrochemical solution to enhance or modify the performance of the solution. An agriculturally acceptable adjuvants are generally described as any substance that are added to an agricultural chemical product to alter its physico-chemical properties and/or improve its efficacy. In the present invention preferably, the miticidal compositions an adjuvants which comprises emulsifier, anti-freezing agent, dispersing agent, antifoaming agent, suspending agent and thickener. The formulation of this invention may also comprises anti-microbial agent, water and combinations thereof, providing stability and compatibility with respect to the synergism of active ingredients along with safety to the environment upon use. The adjuvants are present in percent weight by weight. The term “adjuvants” is similar to “inactive excipients” and used interchangeably in this whole specification. In accordance with the present invention, the synergistic composition further comprises one or more agriculturally acceptable adjuvants.
Emulsifier used in the present invention is selected from the group comprising of calcium (linear and branched) alkyl benzene sulfonate in 2 ethyl hexanol solvent, calcium salts of alkyl (4C10-14 derivatives) benzene sulfonic acid, sodium dioctyl sulfosuccinate, ethoxylated fatty glyceride, thiophosphoro succinate salt, taurine derivatives (in particular alkyl taurate), commercially available emulsifier having trade name GERONOL FF/6E® (a mixture of calcium dodecylbenzene sulphonate, ethoxylated polyarylphenol and solvent petroleum naphtha) or a mixture thereof. According to one of the embodiment, emulsifier used most preferably in the range of 3% to 12% weight by weight.
Dispersing agent used in the present invention is selected from the group comprising of commercially available dispersing agents having trade name Agnique® BP NP-4030 EO-PO Poly, Agnique® CP 72 L, Agnique® CSO 40-U, Agnique® CSO-20, Agnique® CSO-36 Ethox Castor Oil, Agnique® DDL Dispersant, IG Surf® 2370 SC, IG Surf® 2380. In accordance with a preferred embodiment of the present invention preferred one is Agnique® CP 72 L (Oxirane, 2-methyl-, polymer with oxirane, mono (2-propylheptyl) ether) and IG Surf® 2380 (Polyoxyethylenated Triglycerides, fatty Alcohol Ethoxylate). Dispersing agent used in the formulation of present invention is improving the separation of particles and helping to prevent settling or clumping in the formulation which ultimately enhances the stability of formulation. According to one of the embodiment dispersing agent used most preferably in the range of 0.5% to 3% weight by weight.
Anti-freezing agent used in the present invention is selected from the group comprising propylene glycols, polypropylene glycols, polyethylene glycols, ethylene glycols and glycerin most preferably in the range of 7% to 10% weight by weight.
Anti-foaming agent to prevent formation of foam as used in the present invention is selected from the group comprising silicon defoamer, polydimethylsiloxane, polymethylhydrosiloxane and cyclomethicones. The antifoaming agent may enable the wetting agent and the dispersant, when included, to function properly within the mixture, and may facilitate spraying of insecticide while reducing the chances of the sprayer becoming clogged with foam or entrained air. In accordance with a preferred embodiment of the present invention preferred one is silicon defoamer and polydimethylsiloxane used in the formulation most preferably in the range of 0.25% to 0.5% weight by weight.
Optionally, the present invention comprises suspending agent silica or fumed silica.
Optionally, the present invention comprises anti-microbial agent selected from the group comprising of benzisothiazolinone, methylisothiazolinone, copper pyrithione, zinc pyrithione, commercially available with trade name PROXEL GXL®, which is a 20% aqueous dipropylene glycol solution of 1,2-benzisothiazolin-3-one.
Optionally, thickener as used in the present invention which can be selected from the group comprising of xanthan gum, agar agar and arabic gum. The problems of long shelf life of agrochemical formulations can be minimized through the use of rheology modifiers or additives that promote, for example, the inhibition of sediment in the active ingredients in a given formulation. Such additives increase the viscosity of the agrochemical formulation, providing greater stability and physical efficiency, and enabling its storage for a longer period. These additives are usually called swelling agents, anti-settling agents, stabilizing agent or thickeners and may be present alone or in the form of a composition.
According to one of the preferred embodiment, optionally the stabilizing agent selected from group comprising Colloidal silicon dioxide, Bentonite and/or mixture thereof, is used in the present invention in an amount ranging from 0.25% to 3% by weight.
The following examples are intended to illustrate, but in no way limit the scope of, the present invention.

EXAMPLES
Example 1: General procedure for the preparation of Suspo Emulsion (SE) formulation
Step 1: Preparation of Pyriproxyfen Emulsifiable Concentrate (EC)
In a pre-mix vessel, (C8-C16) alkyl amide (8-14% parts by weight) organic solvent was charged. Pyriproxyfen (8-8.6% parts by weight) as active ingredient and emulsifier (10%) was added under stirring, alternatively at 25oC to 35oC. High rate stirring was further continued for 30 minutes at 25oC to 35oC to obtain clear transparent solution. Prepared solution was kept for next step.
Step 2: Preparation of Diafenthiuron Suspension Concentrate (SC)
In a separate pre-mix vessel, Diafenthiuron (29-31% parts by weight) as active ingredient, defoamer (0.25-0.5% parts by weight), suspending agent (0.5%), stabilizing agent (0.25%-1.0 %) & water (quantity substantive) was mixed under stirring for 30 minutes 25oC to 35oC to obtain homogeneous mixture. After mixing, grind of the mass was done twice through bead mill to obtain particles size below 10 micron (D90). Prepared solution was kept for next step.
Step 3: Preparation of Pyriproxyfen and Diafenthiuron Suspo Emulsion (SE)
The homogenized transparent Pyriproxyfen Emulsifiable Concentrate (EC) of Step 1 is transferred to the milled Diafenthiuron Suspension Concentrate (SC) of Step 2 under stirring in pre-mix vessel. Homogenization with a high speed homogenizer at 1000RPM was done for 1hours. Add appropriate parts by weight as per Table 1, Xanthum gum & biocide and optionally stabilizer to the mass and continued homogenization for further 30 minutes to obtain final Pyriproxyfen and Diafenthiuron Suspoemulsion (SE) formulation.
Compositions of preferred Suspo Emulsion (SE) formulations prepared by above procedure comprising various ingredients are shown in Table 1:
Table 1
Ingredients
Percent Weight/Weight
8% solvent* 10% solvent** 12% solvent* 14% solvent*
Pyriproxyfen content 8.0 8.0 8.0 8.6
Diafenthiuron content 29.0 30.0 30.0 31.0
N,N- Dimethyl decanamide* 8 - 12 14
Blend of N,N-Dimethyl octanamide and N,N-Dimethyl decanamide** - 10 - -
Mixture of calcium salts of alkyl (4C10-C14 derivatives) benzene sulfonic acid, sodium dioctyl sulfosuccinate 4.0 - 4.0 4.0
a mixture of calcium dodecylbenzene sulphonate, ethoxylated polyarylphenol and solvent petroleum naphtha - 10 - -
Propylene Glycol 8.0 - 8.0 8.0
Polyoxyethylenated Triglycerides, fatty Alcohol Ethoxylate - 1.2 - -
Agnique® CP 72 L 2.0 - 2.0 2.0
IG Surf ® 2370 SC - 0.91 - -
Silicon defoamer 0.5 0.25 0.5 0.5
Silica 0.5 - 0.5 0.5
Colloidal silicon dioxide and Bentonite Mixture (4:1) - 2.5 - -
Xanthum Gum Powder 0.04 0.10 0.04 0.04
Benzisothiazolinone 0.002 - 0.002 0.002
20% aqueous dipropylene glycol solution of 1,2-benzisothiazolin-3-one - 0.15 - -
Water 39.958 36.890 34.958 31.358
Total 100.0 100.0 100.0 100.0

A miticidal composition of the present invention is a stable formulation. Stability study of composition has done by procedure according to CIPAC test method MT 46.3. The results are listed in Table 2. Formulation 1 and Formulation 2, as listed in Table 2 are prepared by using solvent N, N-dimethyldecanamide and blend of N,N-dimethyl octanamide and N,N-dimethyl decanamid, respectively.

Table 2:
Test Parameter Specification Formulation 1 Formulation 2
0 Days @ 54±2 °C for 14 days 0 Days @ 54±2 °C for 14 days
Active Content w/w % Diafenthiuron 29.0 - 31.0 29.93 29.33 30.32 30.51
Pyriproxyfen 8.0 – 8.6 8.08 8.19 8.23 8.59
pH 5.5-7.5 6.80 6.78 6.82 6.6
Pourability (CIPAC test method MT 148.1) 1.0 % Max. 0.5% 0.5% 0.5% 0.5%
Creaming 0 hrs. NIL NIL NIL NIL NIL
0.5 hrs. NIL NIL NIL NIL NIL
2 hrs. Any separation of cream or sediment shall not exceed more than 2.0 ML 0.3 ml 0.5 ml 0.2 ml 0.4 ml

EXAMPLE 2: FIELD EFFICACY STUDY
Objective: The objective of field efficacy study was to explore synergistic miticidal effect of composition comprising Pyriproxyfen 8% + Diafenthiuron 30% and at least one (C8-C16) alkyl amide as organic solvent on crops Chilli and Brinjal. The field efficacy study was recorded as Trial 1 and Trial 2 on Chilli and Brinjal crops respectively.
Trial Study-1: Experiment on Chilli (Capsicum annum)
Methodology: The experiment was conducted as per the Randomized block design. 15 plants were selected randomly and tagged in each replication. The mite population on the surface of the upper, middle and lower leaves were recorded with the help of a hand lens before and after spray. The pooled data was then analyzed and the percent control and synergy was worked out.
The experiment was conducted at Research farm Ambala. Experiment was laid out with a set of 8 treatments having treatment replications (R1, R2 and R3) each.
The spray was conducted on Chilli at the emergence of pest. 200 liter of water was used to spray 1 Acre area. The spray was conducted with the help of Battery operated Knapsack sprayer. The parameter’s for an experiment is represented in Table as below.
S.No. Parameter Detail
1 Variety Pusa Jwala
2 Spacing 45-45 cm Plant to Plant and Row to row distance, depth 3-4 cm
3 Seed Rate 300 gm /acre
4 Duration 65 – 70 Days

The result after treatment obtained were listed in Table 3. These results reveals that this formulation has synergistic effect on mites in Chilli plant.
Table 3: Result of efficacy trial of formulation on Chilli (Capsicum annum)
Effect on Mites 7 DAS
Treatment Dose/ ha Observed Value Expected Value (Colby Value ) Ratio (Observed over Expected)
Synergy
Pyriproxyfen 8% + Diafenthiuron 30% SE + 8% Solvent 1000 68.18 70.24 0.97 No
Pyriproxyfen 8% + Diafenthiuron 30% SE + 10% Solvent 1000 72.57 70.24 1.03 Yes
Pyriproxyfen 8% + Diafenthiuron 30% SE + 12% Solvent 1000 80.79 70.24 1.15 Yes
Pyriproxyfen 8% + Diafenthiuron 30% SE + 14% Solvent 1000 81.79 70.24 1.16 Yes
Pyriproxyfen 10%EC + Diafenthiuron 50% WP (Tank Mix) 400 + 240 68.83 70.24 0.98 No
Pyriproxyfen 10%EC 400 4.76
Diafenthiuron 50% WP 240 68.75
Control NA 0.00
*ha. = Hectare; DAS= Days After Treatment
Crop Yield
The yield of chili was increased by using formulation of present invention, the yield were recorded in Quintal/Acre and tabulated in Table 4
Table 4
S.No. Treatments Yield of R1 Yield of R2 Yield of R3 Average Yield
1 Pyriproxyfen 8% + Diafenthiuron 30% SE + 8% Solvent 5.18 5.51 5.42 5.27
2 Pyriproxyfen 8% + Diafenthiuron 30% SE + 10% Solvent 5.46 5.50 5.40 5.45
3 Pyriproxyfen 8% + Diafenthiuron 30% SE + 12% Solvent 5.59 5.33 5.40 5.88
4 Pyriproxyfen 8% + Diafenthiuron 30% SE + 14% Solvent 5.55 5.32 5.48 5.95
5 Pyriproxyfen 10%EC + Diafenthiuron 50% WP (Tank Mix) 5.33 5.24 5.54 5.37
6 Pyriproxyfen 10%EC 5.33 5.28 5.14 5.25
7 Diafenthiuron 50% WP 5.39 5.18 5.48 5.35
8 Control 5.14 5.18 5.28 4.89
* R1, R2 and R3 are three replications
The formulation of present invention was safe to natural enemies present in Chilli plant eco-system. The result was taken from 1 meter2 area of sampling and tabulated in Table 5.
Table 5
Treatments No. of Spider No. of Coccinela Septumpunctata
Pre-count 5 Days 10 Days 15 Days Pre-count 5 Days 10 Days 15 Days
Pyriproxyfen 8% + Diafenthiuron 30% SE + 8% Solvent 3 2 3 4 1 2 2 2
Pyriproxyfen 8% + Diafenthiuron 30% SE + 10% Solvent 4 2 3 4 2 2 1 2
Pyriproxyfen 8% + Diafenthiuron 30% SE + 12% Solvent 3 3 2 3 2 1 2 1
Pyriproxyfen 8% + Diafenthiuron 30% SE + 14% Solvent 3 3 3 3 1 2 2 1
Pyriproxyfen 10%EC + Diafenthiuron 50% WP (Tank Mix) 2 3 2 2 1 2 1 2
Pyriproxyfen 10%EC 4 2 2 4 2 1 2 2
Diafenthiuron 50% WP 3 2 4 4 2 1 2 2
Control 4 3 4 3 1 1 2 1

Phytotoxicity
As per the standard testing no phytotoxicity was observed with the use of formulation of present invention, the result is shown in Table 6
Table 6: Phytotoxicity result of present invention in Chilli crop eco-system
S.No. Treatments Hyponasty Necrosis Vein Clearing Wilting
1 Pyriproxyfen 8% + Diafenthiuron 30% SE + 8% Solvent 0 0 0 0
2 Pyriproxyfen 8% + Diafenthiuron 30% SE + 10% Solvent 0 0 0 0
3 Pyriproxyfen 8% + Diafenthiuron 30% SE + 12% Solvent 0 0 0 0
4 Pyriproxyfen 8% + Diafenthiuron 30% SE + 14% Solvent 0 0 0 0
5 Control 0 0 0 0

Trial-2: Experiment on Brinjal (S. melongena)
The experiment was conducted at Research farm Ambala. Experiment was laid out with a set of 8 treatments having 3 replications (R1, R2 and R3) each.
The spray was conducted on Brinjal at the emergence of pest. 200 liter of water was used to spray 1 Acre area. The spray was conducted with the help of Battery operated Knapsack sprayer. The parameter’s for an experiment is represented in below table.

S.No. Parameter Detail
1 Variety Pusa Purple Long
2 Spacing 45-50 cm
3 Seed Rate 200 gm /Acre
4 Duration 110-115 days

The result after treatment obtained were listed in Table 7. These results reveals that this formulation has synergistic effect on mites in Brinjal plant.
Table 7: Result of efficacy trail of formulation on Brinjal (S. melongena)
Effect on mite 7 DAS
Treatment Dose/ ha Observed Expected Ratio Synergy
Pyriproxyfen 8% + Diafenthiuron 30% SE + 8% Solvent 1000 68.18 70.24 0.97 No
Pyriproxyfen 8% + Diafenthiuron 30% SE + 10% Solvent 1000 77.56 70.24 1.10 Yes
Pyriproxyfen 8% + Diafenthiuron 30% SE + 12% Solvent 1000 80.79 70.24 1.15 Yes
Pyriproxyfen 8% + Diafenthiuron 30% SE + 14% Solvent 1000 81.79 70.24 1.16 Yes
Pyriproxyfen 10%EC + Diafenthiuron 50% WP (Tank Mix) 400 + 240 68.83 70.24 0.98 No
Pyriproxyfen 10%EC 400 4.76
Diafenthiuron 50% WP 240 68.75
Control NA 0.00
*ha. = Hectare; DAS= Days After Treatment
Crop Yield
The yield of Brinjal was increased on using formulation of present invention, the yield were recorded in Quintal/Acre and tabulated in Table 8
Table 8
S.N.O Treatments Yield of R1 Yield of R2 Yield of R3 Average Yield
1 Pyriproxyfen 8% + Diafenthiuron 30% SE + 8% Solvent 60.72 59.67 59.97 60.10
2 Pyriproxyfen 8% + Diafenthiuron 30% SE + 10% Solvent 61.92 60.44 61.12 61.16
3 Pyriproxyfen 8% + Diafenthiuron 30% SE + 12% Solvent 61.59 60.63 61.44 61.22
4 Pyriproxyfen 8% + Diafenthiuron 30% SE + 14% Solvent 60.61 60.44 62.55 61.20
5 Pyriproxyfen 10%EC + Diafenthiuron 50% WP (Tank Mix) 59.73 60.47 60.26 60.15
6 Pyriproxyfen 10%EC 60.44 59.70 60.23 60.12
7 Diafenthiuron 50% WP 60.41 60.95 59.06 60.14
8 Control 62.51 59.51 58.31 59.67
* R1, R2 and R3 are three replications
The formulation of present invention is safe on natural enemies in Brinjal crop eco-system. The result taken from 1 meter2 area of sampling and tabulated in Table 9.
Table 9
Treatments No. of Chrysoperla carnea No. of Coccinela Septumpunctata
Pre-count 5 Days 10 Days 15 Days Pre-count 5 Days 10 Days 15 Days
Pyriproxyfen 8% + Diafenthiuron 30% SE + 8% Solvent 0 0 1 1 2 2 1 2
Pyriproxyfen 8% + Diafenthiuron 30% SE + 10% Solvent 1 1 0 1 3 2 2 2
Pyriproxyfen 8% + Diafenthiuron 30% SE + 12% Solvent 1 1 1 1 3 3 2 3
Pyriproxyfen 8% + Diafenthiuron 30% SE + 14% Solvent 0 1 0 1 2 3 3 3
Pyriproxyfen 10%EC + Diafenthiuron 50% WP
(Tank Mix) 0 0 1 1 2 3 3 2
Pyriproxyfen 10%EC 1 1 1 0 3 2 2 3
Diafenthiuron 50% WP 2 1 0 1 0 2 3 3
Control 1 1 1 1 2 2 1 2

Phytotoxicity
As per the standard testing no phytotoxicity was observed with the use of formulation of present invention, the results are listed in Table 10.

Table 10: Phytotoxicity result of present invention in Brinjal crop eco-system
S.N.O Treatments Hyponasty Necrosis Vein Clearing Wilting
1 Pyriproxyfen 8% + Diafenthiuron 30% SE + 8% Solvent 0 0 0 0
2 Pyriproxyfen 8% + Diafenthiuron 30% SE + 10% Solvent 0 0 0 0
3 Pyriproxyfen 8% + Diafenthiuron 30% SE + 12% Solvent 0 0 0 0
4 Pyriproxyfen 8% + Diafenthiuron 30% SE + 14% Solvent 0 0 0 0
5 Control 0 0 0 0

While this invention has been described in detail with reference to certain preferred examples, it should be appreciated that the present invention is not limited to those precise examples rather, in view of the present disclosure, which describes the current best mode for practicing the invention, many modifications and variations, would present themselves to those skilled in the art without departing from the scope and spirit of this invention. This invention is susceptible to considerable variation in its practice within the spirit and scope of the appended claims.

We Claim:
1. A synergistic miticidal composition comprising effective amount of:
i) Pyriproxyfen
ii) Diafenthiuron
iii) At least one (C8-C16)alkyl amide as organic solvent
Wherein the amount of organic solvent is present in an amount ranging from about 1 to about 14 percent weight by weight, and
iv) Agriculturally acceptable adjuvants
2. A synergistic miticidal composition as claimed in claim 1, wherein a synergistically effective amount of Pyriproxyfen and Diafenthiuron are present in a ratio between1:5 and 5:1.
3. A synergistic miticidal composition as claimed in claim 1, wherein an effective amount of (C8-C16)alkyl amide organic solvent is selected from the group comprising of N,N-Dimethyl heptanamide, N,N-diethyl heptanamide, N,N-Dimethyl octanamide, N,N-Diethyl octanamide, N,N-dimethyl nonanamide, N,N-Diethyl nonanamide, N, N-dimethyl decanamide, N,N-diethyl decanamide, N,N-dimethyl undecanamide, N,N-diethyl undecanamide, N,N-dimethyl dodecanamide, N,N-diethyl dodecanamide or a mixture thereof
4. A synergistic miticidal composition as claimed in claim 1, wherein an effective amount of (C8-C16) alkyl amide organic solvent is selected from the group comprising of N, N-Dimethyl decanamide, N,N-Dimethyl octanamide or a blend thereof, wherein said solvent is present in an amount ranging from about 8 to 14 percent weight by weight.
5. A synergistic miticidal composition as claimed in claim 1, wherein said agriculturally acceptable adjuvants include emulsifier, anti-foaming agent and/or stabilizing agent in combination thereof.
6. A synergistic miticidal composition as claimed in claim 5, wherein the emulsifier is selected from the group comprising calcium dodecylbenzene sulphonate, ethoxylated polyarylphenol in solvent petroleum naphtha, benzenesulphonic acid derivatives calcium salt, sodium dioctyl sulfosuccinate, thiophosphoro succinate salt, taurine derivatives (in particular alkyl taurate), ethoxylated fatty glyceride or a mixture thereof, wherein said emulsifier is present in an amount ranging from 3 to 12 percent weight by weight.
7. A synergistic miticidal composition as claimed in claim 5, wherein the anti-foaming agent is selected from the group comprising Polydimethylsilioxane, Polymethylhydrosiloxane, cyclomethicones or a mixture thereof, wherein said anti-foaming agent is present in an amount ranging from 0.25-0.8 percent weight by weight.
8. A synergistic miticidal composition as claimed in claim 5, wherein the stabilizing agent is selected from the group comprising of colloidal silicon dioxide, bentonite and/or mixture thereof, wherein said stabilizing agent is present in an amount ranging from 0.25 to percent weight by weight.
9. A synergistic miticidal composition as claimed in claim 1, wherein said composition is effective against Spider Mite, Sugarcane Red Spider Mite, Fig spider mite, Oriental red mite, Citrus brown mite, Red tea mite, Mango red spider mite, Mango red spider mite, European red mite, Brown wheat mite, White patchy, sugarcane leaf spotted mite, web mite, Red-legged spider mite, Bean spider mite, Red vegetable mite, Two spotted spider mite, Citrus flat mite, Scarlet mite, Reddish black flat mite, Leprosis mite, Pineapple flat mite, Ber gall mite, Pigeonpea sterility mosaic mite, Coconut mite, Litchi erineum mite, Brinjal erineum mite, Tomato erineum mite, Mango bud mite, Jujube gall mite, Eriophyid mite, Citrus silver mite, broad mite, Rice sheath mite, Dahlia mite, yellow tea mite, Pink mite and Purple tea mite.
10. A synergistic miticidal composition as claimed in claim 1, wherein said composition is effective against at least one mite of said plurality of mites found in Wheat, Barley, Oats, Maize, Sorghum, Sugarcane, Areca catechu (Palm), Fig, Apple, Citrus, Cotton, Cucurbits, Coffee, Mango, Tea, Coriander, Beans, Vegetables, Cucurbits, Ornamental Plants, Bean, Brinjal, Okra, Guava, Papaya, Pineapple, Pigeon pea, Coconut, Litchi, Chilli, Jute, Potato, Rice, Almond, Castor, Jujube, Red Date, Golden Rain Tree, Lemon, Litchi, Golden Shower Tree, Gourds, Sweet Potato, Garlic, Onion, Marigold, Jasmine, Chrysanthemums, Areca, Coconut palms.

Dated this 19th day of November 2018

Mr. Vikram Anand
For Parijat Industries (India) Private Limited
To,
The Controller of Patents
The Patent Office, at New Delhi