DESC:FIELD OF THE INVENTION:

The present invention relates to synergistic herbicidal composition comprising Tefuryltrione and at least one co-herbicide selected from Dichlorophenoxyacetic acid (2,4-D), Anilofos, Azimsulfuron, Bentazon, Bispyribac, Ethoxysulfuron, Pendimethalin, Pyraclonil, Pyrazosulfuron and their agrochemically acceptable salts thereof which are standard in agriculture or mixture thereof. The present invention also relates to process for preparing the said composition comprising of bioactive amounts of Tefuryltrione and at least one co-herbicide selected from Dichlorophenoxyacetic acid (2,4-D), Anilofos, Azimsulfuron, Dichlorophenoxyacetic acid (2,4-D), Anilofos, Azimsulfuron, Bentazon, Bispyribac, Ethoxysulfuron, Pendimethalin, Pyraclonil, Pyrazosulfuron and their agrochemically acceptable salts thereof which are standard in agriculture or mixture thereof and one or more inactive excipients.

BACKGROUND OF THE INVENTION

The control of undesired vegetation is extremely important in order to achieve high crop efficiency. In many cases, herbicides have an effect against a spectrum of weeds; however, these herbicides may not be effective against certain type of other weeds, which may also be present in the crop to be protected. Therefore, there is a strong need for composition of two or more herbicides.

Herbicidal compositions of the present invention have several advantages over the use of a single herbicide including (a) an increase in the spectrum of weeds controlled or an extension of weed control over a longer period of time, (b) an improvement in crop safety by using minimum doses of selected herbicides applied in combination rather than a single high dose of one herbicide and (c) a delay in the appearance of resistant weed species to selected herbicides.

Herbicide(s), also commonly known as weed killers, are chemical substances used to control unwanted plants. In some cases, herbicidal active ingredients have been shown to be more effective in combination than when applied individually and this is referred to as "synergism." As described in the Herbicide Handbook of the Weed Science Society of America, Seventh Edition, 1994, p. 318, "'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 of each factor applied separately."

The present invention is based on the herbicidal composition comprising synergistic bioactive amounts of Tefuryltrione and at least one co-herbicide selected from Dichlorophenoxyacetic acid (2,4-D), Anilofos, Azimsulfuron, Dichlorophenoxyacetic acid (2,4-D), Bentazon, Bispyribac, Ethoxysulfuron, Pendimethalin, Pyraclonil, Pyrazosulfuron and the salts thereof which are standard in agriculture or mixture thereof herbicidal efficacy, display a synergistic effect when applied in combination.

The effectiveness of herbicides depends inter alia on the nature of the herbicide employed, its application rate, the preparation, the respective to the harmful plants, the climatic and soil conditions and the like. Another criterion is the duration of the action, or the degradation rate of the herbicide. Considerations include if appropriate, changes in the sensitivity of harmful plants to an active compound which may occur on prolonged use or geographically limited. Such changes manifest themselves as more or less pronounced loss in activity and can be only partially offset by higher herbicide application rates.

Because of the large number of possible influencing factors, there is virtually no individual active compound which, combined the desired properties for different requirements, in particular with regard to the harmful plants and the climatic zones in itself. Then there is the constant need to achieve the effect with ever lower herbicide application rates. A lower application rate reduces not only the required for the application amount of a drug, but usually reduces the amount of formulation auxiliaries required. Both reduce the economic expense and improve the ecological compatibility of the herbicide treatment.

Tefuryltrione was first disclosed in US 6376429 B1 and chemically known as 2-{2-chloro-4- mesyl-3- [(RS)-tetrahydro-2- furylmethoxymethyl] benzoyl} cyclohexane -1,3-dione and having chemical structure as below

US20030104940, US20030104941 and WO2004105482 describe herbicidal compositions comprising tefuryltrione for use in rice crops. However, in practice, there are disadvantages associated with the use of the herbicidal compositions known from these documents.

US8728977B2 and 8746/CHENP/2011 relates to herbicidal compositions comprising A) tefuryltrione and Component B) at least one compound selected from the group consisting of the herbicides cyclosulfamuron, flucetosulfuron, orthosulfamuron, penoxsulam, pyroxasulfone, pyroxsulam, and 3-chloro-N -[(4,6-dimethoxypyrimidin-2-yl) carbamoyl]-1-methyl-4-(5-methyl-5,6-dihydro-1,4,2-dioxazin-3-yl)-1H-pyrazole-5-sulfonamide

WO2008155027 and 7411/CHENP/2009 relates to crop-tolerated combinations of herbicides tefuryltrione or tembotrione and benzoylcyclohexane-dione group for application in rice growing. Herbicidal combinations comprising herbicides selected from the group consisting of benzoylcyclohexanediones are bensulfuron-methyl, benzobicyclon, bromobutide, cyhalofop-butyl, ethoxysulfuron, fenoxaprop-P-ethyl, fentrazamide, pyrazolynate, pyrimisulfan, sulcotrione, tefuryltrione, tembotrione and, if appropriate, isoxadifen-ethyl.

US 20140073506 A1 relates to herbicidal compositions containing (a) aminopyralid or an agriculturally acceptable salt or ester thereof and (b) propanil. The compositions provide synergistic weed control of undesirable vegetation.

EP 2755488 A1 relates to synergistic herbicidal mixtures comprising a herbicidally effective amount of (a) penoxsulam and (b) pretilachlor. The compositions may also contain an agriculturally acceptable adjuvant or carrier.

CN 103340208 A relates to weeding composition containing oxaziclomefone and pyrazosulfuron-ethyl. The weeding composition comprises the effective components: penoxsulam, pyribenzoxim, and the balance being pesticide auxiliary agents.

CN 103081937 A relates to weeding composition consists of pretilachlor and pyrazosulfuron-ethyl. The compound granules containing the pretilachlor and pyrazosulfuron-ethyl can be applied at one time, the weeding spectrum is expanded, the application uniformity is improved, the effect is improved, the lasting period is prolonged, the consumption and the using cost are reduced, and environmental pollution caused by application is reduced at the same time.

CN 104106577 A relates to weeding composition containing metazachlor and oxadiargyl, weeding composition comprises an effective component metazachlor and an effective component oxadiargyl, with the balance being pesticide auxiliary agents.

CN 103931631 A relates to weeding composition containing fenoxaprop-P-ethyl and pyroxsulam. The composition comprises active components, and the balance pesticide aid, the active components comprise fenoxaprop-P-ethyl and pyroxsulam.

However still there is a need for an herbicidal composition of Tefuryltrione in combination of at least one co-herbicide with synergistic effect 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 synergistic herbicidal composition of Tefuryltrione and at least one co-herbicide as described herein in can provide solution to the above mentioned problems.

SUMMARY OF THE INVENTION

Accordingly, in a first aspect of the present invention provides a synergistic herbicidal composition comprising bioactive amounts of Tefuryltrione and at least one co-herbicide selected from Dichlorophenoxyacetic acid (2,4-D), Anilofos, Azimsulfuron, Bentazon, Bispyribac, Ethoxysulfuron, Pendimethalin, Pyraclonil, Pyrazosulfuron and their agrochemically acceptable salts thereof with at least one inactive excipient..

Accordingly, in a second aspect, the present invention provides a method of preparing synergistic herbicidal composition comprising bioactive amounts of Tefuryltrione and at least one co-herbicide selected from Dichlorophenoxyacetic acid (2,4-D), Anilofos, Azimsulfuron, Bentazon, Bispyribac, Ethoxysulfuron, Pendimethalin, Pyraclonil, Pyrazosulfuron and their agrochemically acceptable salts thereof with at least one inactive excipient..

Accordingly, in a third aspect, the present invention provides a method of protecting a plant propagation material, a plant, parts of a plant and/or plant organs that grow at a later point in time against pathogenic damage or pest damage by applying to the plant propagation material a composition comprising a formulated mixture defined in the first aspect.

Accordingly, in a fourth aspect the said composition is to be developed in suitable formulations selected from Suspension concentrate (SC), Oil dispersion (OD), Emulsion concentrate (EC), Wettable Powder (WP), Soil Appplied Granules (SAG) and Jumbo ball formulation comprising Tefuryltrione and at least one co-herbicide selected from Dichlorophenoxyacetic acid (2,4-D), Anilofos, Azimsulfuron, Bentazon, Bispyribac, Ethoxysulfuron, Pendimethalin, Pyraclonil, Pyrazosulfuron and the salts thereof which are standard in agriculture or mixture thereof; and optionally one or more customary formulation adjuvants such as a) dispersant b) wetting agent c) anti-foaming agent d) biocides e) anti freezing agent f) suspending agent g) thickener h) coating agent and i) buffering agent.

According to another aspect of the present invention there is provided a stable formulation comprising of Tefuryltrione and at least one co-herbicide selected from Dichlorophenoxyacetic acid (2,4-D), Anilofos, Azimsulfuron, Bentazon, Bispyribac, Ethoxysulfuron, Pendimethalin, Pyraclonil, Pyrazosulfuron and the salts thereof which are standard in agriculture or mixture thereof.

According to another aspect of the present invention is to provide an jumbo formulation processes of composition mixture of Tefuryltrione and at least one co-herbicide comprising packing the water-insoluble granular materials into the porous bag whose outer surface is laminated with water-soluble film, absorbing liquid composition mixture of Tefuryltrione and one more co-herbicide into the bag, and sealing the above.

According to another aspect of the present invention is to provide the jumbo formulation processes of composition mixture of Tefuryltrione and at least one co-herbicide comprising packing the water-insoluble granular materials into the porous bag, sealing the bag, inserting the above sealed bag into the water-soluble bag, absorbing liquid composition mixture of Tefuryltrione and one more co-herbicide, and sealing the above.

According to another aspect of the present invention is to provide the jumbo formulation processes of composition mixture of Tefuryltrione and at least one co-herbicide comprising preparing the block-shaped porous carrier by binding the water-insoluble granular materials with adhesives, inserting the porous carrier into the water- soluble bag, absorbing liquid composition mixture of Tefuryltrione and at least one co-herbicide, sealing the bag, inserting the bag again into the aluminum envelope, and sealing the above.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides a novel composition comprising synergistic bioactive amounts of Tefuryltrione and at least one co-herbicide with one or more inactive excipients. Further the co-herbicide is selected from Dichlorophenoxyacetic acid (2,4-D), Anilofos, Azimsulfuron, Bentazon, Bispyribac, Ethoxysulfuron, Pendimethalin, Pyraclonil, Pyrazosulfuron and the salts thereof which are standard in agriculture or mixture thereof.

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

The herbicidal compositions of the present invention can be prepared in a variety of ways using formulation adjuvants, such as carriers (e.g. liquid or solid carrier), solvents and/or surface-active substances. Therefore, preferably, the herbicidal composition of the present invention is a formulation comprising a carrier (e.g. liquid or solid carrier), a solvent and/or a surface-active substance.

The formulation can be in various physical forms, for example in the form of a dustable powder (DP), a gel, a wettable powder (WP), a granule (GR) (such as an emulsifiable granule (EG) or more particularly a water-dispersible granule (WG)), a water-dispersible tablet (WT), an emulsifiable concentrate (EC), a micro- emulsifiable concentrate, an oil-in-water emulsion (EW), an oil flowable (e.g. a spreading oil (SO)), an aqueous dispersion (e.g. aqueous suspension concentrate (SC)), an oily dispersion (OD), a suspo-emulsion (SE), a capsule suspension (CS), a soluble liquid, a water-soluble concentrate (with water or a water-miscible organic solvent as carrier), an impregnated polymer film, or jumbo formulation.

Preferably, the formulation is in the form of a jumbo formulation, wettable powder (WP), a granule (GR) (such as an emulsifiable granule (EG) or more particularly a water-dispersible granule (WG)), an emulsifiable concentrate (EC), a microemulsifiable concentrate, an oil-in-water emulsion (EW), an oil flowable (e.g. a spreading oil (SO)), an aqueous dispersion (e.g. aqueous suspension concentrate (SC)), an oily dispersion (OD), a soluble liquid, or a water-soluble concentrate (wherein the water-soluble concentrate is with water or a water-miscible organic solvent as carrier). More preferably, the formulation is in the form of an emulsifiable concentrate (EC).

The herbicidal compositions of the present invention formulation can be classified as below:

Jumbo Granules: These are large granules and much bigger than the conventional granular or tableting formulation and thus called Jumbo granules. These formed by suitable tableting or granulation techniques as sphere, discs, tablets or blocks. Often a coating or agglomeration process is included to produce spherical (golf ball) granules. The granules are applied by hand directly to rice paddy water plots and are particularly favored in some countries like Japan. They are designed to disperse rapidly and evenly to give uniform distribution of active ingredient over the target area. These are herbicide, special granules which are designed for direct application to rice paddy water, releasing active ingredient away from root zones, primarily at the water surface as floating oil.

In a typical example, an active ingredient is dissolved or dispersed in a low volatile oil or solvent and the resulting liquid is then incorporated into a release the active ingredient contained in the oil, which floats to the water surface. This effectively controls various weeds, insect pests, and plant diseases in a broad wetland such as paddy fields, ponds, and lakes.

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.
In one of the embodiment of the present invention comprises Jumbo formulation of the composition comprising of Tefuryltrione and at least one co-herbicide. The invention relates to a Jumbo herbicidal formulation with high active ingredient content which spreads rapidly over the surface of water, efficiently releasing herbicidal active ingredients throughout the water surface, thereby saving labor load of farmers, storage volume during distribution as well as production costs thereof to a large extent.
Due to the water filling of paddy fields, it is not easy to apply herbicides in such a manner that they are scattered uniformly over the surface of water. As a result, if a farmer desires to uniformly apply herbicides, it is in principle necessary for him to enter the paddy field and scatter herbicides changing the position from which the farmer applies herbicides, demanding lots of works. Driven by the motivation to reduce labor load of farmers, the so-called Jumbo formulations have drawn attention among herbicide manufacturers. The Jumbo formulations have three aspects in common: (1) they float, (2) spread and (3) release herbicidal active ingredients on the surface of water. The Jumbo formulations comprising a liquid active ingredient retained, adsorbed or fixed on a carrier allowing reduction in the amount of application, in the production costs while being environmentally friendly.
It is of substantial importance to increase the amounts of active ingredients in Jumbo formulations since it enables the reduction in amounts of formulation to be applied, the storage volume during distribution as well as the production costs thereof. Another prerequisite for a successful Jumbo formulation is a satisfactorily large spreadability, which together with the sufficient active ingredient content contributes to the above effects. Without sufficient spreadability, the amount of application cannot be reduced, eventually leading to the necessity in large storage amounts and high production costs. Therefore, sufficiently high active ingredient content and a satisfactorily large spreadability are the most important factors for the production of advantageous Jumbo formulation. In addition to these factors, it is also important to consider environmental aspects.
Jumbo formulations are generally finished in such a manner that they are packed in water-soluble bags made of water-soluble polymers e. g. polyvinyl alcohol, which are directly applied to the surface of water. After the bags have dissolved in the water, particles of the Jumbo formulation spread on the surface of water releasing active ingredients.
When the jumbo formulations prepared as above are applied to paddy fields, they are floated on the paddy water or sedimented on the paddy soil depending on the bulk density of the formulations, although they contain liquid pesticide mixture whose specific gravity is less than 1.
As soon as the water-soluble bag is dissolved in water, liquid pesticide mixture from the porous carrier is gradually released to or near the water surface. Concurrently, the liquid pesticide mixture is emulsified, spread, and dispersed to a broad area, resulting in the even distribution of active ingredients within 24 hours in the treated area. In case that the pesticides are highly water-soluble, their dispersability can be enhanced by floating the jumbo formulations being exposed to the air. Reversely, in case that the pesticides are barely soluble in water and their emulsion stability is high enough, accumulation of the pesticides in a certain area can be avoided by sedimenting the jumbo formulations and thereby not influenced by wind.
The active ingredients of the present jumbo formulations are easily dispersed and evenly distributed in water, and thus their efficacy is seldom reduced, unless the surface of the treated paddy water is completely covered with rice straw, moss, or aquatic weeds such as duckweed.
In one of the embodiment of the present invention comprise Jumbo Granules formulations. The carrier used as absorbing materials for liquid pesticide mixture is the porous pack densely packed into the porous bag with powdery or granular materials which are practically insoluble in water or in organic solvents. These powdery or granular materials have few fine pores inside and have the diameter of larger than 0.1 mm. The carrier is organic or inorganic carrier. The inorganic carrier minerals are sea sand, hollow microsphere, calcium carbonate, dolomite, baked granular bentonite, zeolite, kaolin, talc, pyrophyllite, powdery or granular polymers of polyethylene, polypropylene, polyvinyl chloride. The organic carriers are sawdust, rice husk, granular charcoal, cereal, etc. Any of the above illustrated materials could be used depending on the pesticides. Generally, sea sand, calcium carbonate, dolomite, pyrophyllite, talc, hollow microsphere and polyvinyl chloride are suitable to use. Preferably most suitable carrier materials are sea sand, hollow microsphere, calcium carbonate, dolomite, pyrophyllite, and talc. The most preferable carriers are organic or inorganic carrier having characteristic of smooth outer surface, low absorption capacity to organic liquids, high affinity to water and organic solvents, excellent degradability in nature, and high environmental safety.
In one of the embodiment of the present invention comprises Jumbo Granules formulations wherein organic solvents are having a boiling point of more than 60 °C and specific gravity of less than 1 can preferably be used in the present jumbo formulation. In addition, the specific gravities of liquid pesticide mixtures vary with the organic solvents used. Considering that the specific gravities of active ingredients are usually more than 1, the organic solvents having lower specific gravity can preferably be used for preparing highly concentrated liquid pesticides.
In one of the embodiment of the present invention comprises Jumbo Granules formulations solvents selected from the group are xylene, liquid paraffins, cyclohexanone, cyclohexane, cyclohexanol, methyl naphthalene, Solvesso 100, Solvesso 150 Solvesso 200, N-methyl pyrrolidone, N-butyl pyrrolidone, diethyl benzene, triethyl benzene, ketones (e.g., methylethyl ketone), polyalkyl glycols, and alcohols (e.g., methanol) . Although the nonpolar organic solvents are used as a major solvent, water-soluble solvents can also be used as co- solvents for the active ingredients of pesticides.
In one of the embodiment of the present invention comprise Jumbo Granules formulations wherein surfactants are used for better emulsifiability and dispersability to pesticides. The surfactants are added to liquid pesticide mixture as emulsifiers, solubilizers, or dispersants.
In one of the embodiment of the present invention comprises Jumbo Granules formulations wherein surfactants are non-ionic and anionic surfactants.. The non-ionic surfactants are polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene styryl aryl ethers, polyoxyethylene polyoxypropylene block polymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, glyceric fatty acid esters, polyoxyethylene glyceric fatty acid esters, acetylene glycols, and acetylene alcohols. The anionic surfactants are calcium alkylbenzene sulfonates, sodium alkyl sulfosuccinates, and sodium polyoxyethylene alkyl aryl ether sulfate esters. In addition to the above illustrated surfactants, no particular limitation is imposed on the surfactants being used in the present jumbo formulation, if they can be used for either emulsifiable concentrates or spreadable oil formulations. The surfactants added in the liquid pesticide mixtures are in the range of 5 to 15% of the total weight, but more preferably 10%.
In one of the embodiment of the present invention comprises Jumbo Granules formulations wherein thickeners or gelling agents are selected from but not limited to ethyl cellulose, methyl cellulose; sodium carboxymethyl cellulose (SCMC); hydroxyethyl cellulose (HEC) or mixtures thereof can be added for controlling the viscosity of the liquid pesticide mixture.
In one of the embodiment of the present invention comprise Jumbo Granules formulations wherein anti-decomposition agents or stabilizers such as epichlorohydrin, soybean oil, phosphoric acid, can also be added to the liquid pesticide mixture for stabilizing the physico-chemical properties of the jumbo formulations during the prolonged storage. When the jumbo formulations are applied to the paddy water, Tefuryltrione and co-herbicide active ingredients from the jumbo formulations should be released within a day.
The term WDG, DG, WSG and SG are synonyms and can be used inter changeably and convey the same meaning.

In one of the embodiment of the present invention the method of application of the formulation comprising of Tefuryltrione and at least one co-herbicide are by broadcasting in standing water by manual or by machine. Broadcasting can be done as direct granules broadcasting or mixing with sand or mixing with fertilizer, spraying with manual or machine operated knapsack sprayer, back pack sprayer, jumbo ball application, and Shaker bottle application. The formulation of the present invention can be in any of the form described above.

In one of the embodiment of the present invention on method of application of the formulation comprising of Tefuryltrione and at least one co-herbicide the time of application or formulations are applied before or after paddy sowing or transplanting, or before weed germination or after weed germination.

Herbicidal composition comprising of Tefuryltrione and at least one co-herbicide which are bio active ingredient for the present formulation are present in ratio of 25: 1 to 1: 10.

In one of the embodiment of the present invention the composition comprising of Tefuryltrione and at least one co-herbicide is effective for management of Paddy (Oryza sativa L.) including Indica, Japonica and Javanica race. GMO Paddy. It can be applied in nursery as well as main field after sowing or transplanting.

In one of the embodiment of the present invention the composition comprising of Tefuryltrione and at least one co-herbicide is effective for control of weed selected form the group but not limited to it, Aeschynomene aspera, Aeschynomene indica, Ageratum conyzoides, Alternanthera sessilis, Alternanthera philoxeroides, Amaranthus spinosus, Amaranthus viridis, Ammania baccifera, Cynodon dactylon, Dactyloctenium aegyptium, Digitaria ciliaris, Digitaria setigera, Ischaemum rugosum, Echinochloa colona, Echinochloa crus-galli, Echinochloa glabrescens, Echinochloa crus-pavonis, Echinochloa esculenta, Echinochloa frumentacea, Echinochloa muricata, Echinochloa oryzoides, Echinochloa paludigena, Eleocharis kuruguwai, Laptochloa chinensis, Eleusine indica, Eclipta alba, Eclipta prostate, Imperata cylindrical, Leersia hexandra, Leptochloa chinensis, Oryza sativa, Panicum repens, Paspalum distichum, Paspalum scrobiculatum, Rottboellia cochinchinensis, Setaria glauca, Bolboschoenus maritimus, Bergia capensis, Commelina benghalensis, Commelina diffusa, Cyanotis axillaris, Eclipta alba, Eclipta prostrate, Eichhornia crassipes, Ipomoea aquatic, Ludwigia adscendens, Ludwigia hyssopifolia, Ludwigia octovalvis, Ludwigia parviflora, Marsilea minuta, Marsilea quadrifoliata, Mimosa diplotricha, Monochoria vaginalis, Pistia stratiotes, Polygonum hydropiper, Portulaca oleracea, Sagittaria milliacea, Sagittaria sagittifolia, Sphenoclea zeylanica, Trianthema portulacastrum, Typha spp., Isachne globosa, Paspalum distichum, Cyperus difformis, Cyperus haspen, Cyperus iria, Cyperus rotundus, Fimbristylis dichotoma, Fimbristylis miliacea, Scirpus juncoides, Scirpus nipponicus, Scirpus planiculmis, Scirpur royelei, Scirpus juncoides.

The composition of the present invention comprising of Tefuryltrione and at least one co-herbicide selected from Dichlorophenoxyacetic acid (2,4-D), Anilofos, Azimsulfuron, Dichlorophenoxyacetic acid (2,4-D), Anilofos, Azimsulfuron, Bentazon, Bispyribac, Ethoxysulfuron, Pendimethalin, Pyraclonil, Pyrazosulfuron and the salts thereof which are standard in agriculture or mixture thereof further optionally 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. Tristyrylphenolethoxylate phosphate esters are also used. Nonionics such as alkylarylethylene oxide condensates and EO-PO block copolymers are sometimes combined with anionics as dispersants for suspension concentrates. In recent years, new types of very high molecular weight polymeric surfactants have been developed as dispersants. These have very long hydrophobic ‘backbones’ and a large number of ethylene oxide chains forming the ‘teeth’ of a ‘comb’ surfactant. These high molecular weight polymers can give very good long-term stability to suspension concentrates because the hydrophobic backbones have many anchoring points onto the particle surfaces. Examples of dispersants used herein include but not limited to sodium lignosulphonates; sodium naphthalene sulphonate formaldehyde condensates; tristyrylphenolethoxylate 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 dioctylsulphosuccinate; alkyl phenol ethoxylates; and aliphatic alcohol ethoxylates and the salts thereof which are standard in agriculture 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, polysaccharides such as starch and cellulose derivatives, vinylalcohol, vinylacetate and vinylpyrrolidone polymers and copolymers, polyethers, epoxy, phenolic and melamine resins, polyolefins and define copolymersand mixtures thereof. Examples of preferred polymers are acrylate polymers such as poly(methacrylate), poly(ethyl methacrylate), poly(methylmethacrylate), acrylate copoylmers and styrene-acrylic copolymers as defined herein below, poly(styrene-co maleic anhydride), cellulosic polymers such as ethyl cellulose, cellulose acetate, cellulose acetatebutyrate, acetylated mono, di, and triglycerides, poly(vinylpyrrolidone), vinyl acetate polymers and copolymers, poly(alkylene glycol), styrene butadiene copolymers, poly(orthoesters), alkyd resins, and mixtures of two or more of these. Polymers that are biodegradable are also useful in the present invention. As used herein, a polymer is biodegradable if is not water soluble, but is degraded over a period of several weeks when placed in an application environment. Examples of biodegradable polymers that are useful in the present invention include biodegradable polyesters, starch, polylactic acid starch blends, polylactic acid, poly(lactic acid-glycolic acid) copolymers, polydioxanone, cellulose esters, ethyl cellulose, cellulose acetate butyrate, starch esters, starch esteraliphatic polyester blends, modified corn starch, polycaprolactone, poly(namylmethacrylate), wood rosin, polyanhydrides, polyvinylalcohol, polyhydroxybutyratevalerate, biodegradable aliphatic polyesters, and polyhydroxybutyrate or mixtures thereof.

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

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

The wettable dry granules (WDG) can be applied after disintegration and dispersion in water. Water dispersible granules can be formed by a) agglomeration, b) spray drying, or c) extrusion techniques.

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 add Tefuryltrione and at least one co-herbicide selected from Dichlorophenoxyacetic acid (2,4-D), Anilofos, Azimsulfuron, Bentazon, Bispyribac, Ethoxysulfuron, Pendimethalin, Pyraclonil, Pyrazosulfuron and the salts thereof which are standard in agriculture or mixture thereof is added slowly under continuous stirring at 30 minute 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 hr. to obtain homogeneous formulation.
The Jumbo formulation can be prepared by below described
In one of the embodiment of the present invention, formulations comprising of Tefuryltrione and one more co-herbicide mixture are mixed with solvent and is homogenized with other surfactants and stabilizers. Thereafter, this mixture is applied to adsorbing material in a coating pan followed by mixing at a rotating speed of 25 rpm for 10 min, thereby obtaining a granular agrochemical formulation. Optionally it is sprayed on adsorbing porous carrier and then extruded in jumbo granules by using extrusion technique.
The process for preparing the present novel synergistic composition can be modified accordingly by any person skilled in the art based on the knowledge of the manufacturing the formulation. However all such variation and modification is still covered by the scope of present invention.

EXAMPLES
Example 1: Tefuryltrione 25% + 2,4 D Sodium salt 40% WG
Composition %
Terfuryltrione (97%) 25.97
2,4 D Sodium salt (95%) 42.31
Alkylated naphtalene sulfonate, sodium salt 3
Sodium Polycarboxylate 8
Sodium Lauryl Sulfate 2
Silicone antifoam 0.5
Polyvinyl pyrrolidone 0.5
Lactose anhydrous 5
Sodium Sulfate anhydrous 3
China Clay 9.72
TOTAL 100

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 analysed. 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 Fluidised 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 requied pack sizes.

Example 2: Tefuryltrione 50% + Pyrazosulfuron Ethyl 3% WG
Composition %
Terfuryltrione (97%) 51.75
Pyrazosulfuron Ethyl (96%) 3.33
Alkylated naphtalene sulfonate, sodium salt 3
Sodium Polycarboxylate 8
Sodium Lauryl Sulfate 2
Silicone antifoam 0.3
Polyvinyl pyrrolidone 0.5
Lactose anhydrous 5
Sodium SulfateAnhydrous 3
China Clay 23.12
TOTAL 100

Procedure: As per Example 1
Example 3: Tefuryltrione 50% + Ethoxysulfuron Ethyl 3% WG
Composition %
Terfuryltrione (97%) 51.75
Ethoxysulfuron Ethyl (95%) 3.37
Alkylated naphtalene sulfonate, sodium salt 3
Sodium Polycarboxylate 8
Sodium Lauryl Sulfate 2
Silicone antifoam 0.3
Polyvinyl pyrrolidone 0.5
Lactose anhydrous 5
Sodium SulfateAnhydrous 3
China Clay 23.08
TOTAL 100

Procedure: As per Example 1
Example 4: Terfuryltrione 50% + Bispyribac Sodium 4% WG
Composition %
Terfuryltrione (97%) 51.75
Bispyribac Sodium (93%) 4.52
Alkylated naphtalene sulfonate, sodium salt 3
Sodium Polycarboxylate 8
Sodium Lauryl Sulfate 2
Silicone antifoam 0.3
Polyvinyl pyrrolidone 0.5
Lactose anhydrous 5
Sodium SulfateAnhydrous 3
China Clay 21.93
TOTAL 100

Procedure: As per Example 1

Example 5: Tefuryltrione 50% + Pyrazosulfuron Ethyl 3% WP
Composition %
Terfuryltrione (97%) 51.75
Pyrazosulfuron Ethyl (96%) 3.33
Alkylated naphtalene sulfonate, sodium salt 9
Sodium Lauryl Sulfate 5
Silicone antifoam 0.5
Silica 15
China Clay 15.42
TOTAL 100

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 analysed. After getting approval from QC dept. material is unloaded into 25 kg. HDPE bag with LDPE liner inside.

Example 6: Tefuryltrione 25% + Ethoxysulfuron Ethyl 1.5% SC
Composition %
Terfuryltrione (97%) 25.98
Ethoxysulfuron Ethyl (95%) 1.79
Ethylene oxide propylene oxide copolymer 0.2
Nonionic polyalkylene glycol ether 2
Acrylic graft copolymer 3
Alkylated naphtalene sulfonate, sodium salt 0.5
Silicone antifoam 0.3
Benzisothiazoline 0.1
Glycol 5
Polysaccharides 0.15
D.M. Water 40.75
TOTAL 100

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/deye 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 Finally add gum solution to this formulation and send to QC for quality check

Example 7: Tefuryltrione 25% + Bispyribac Sodium 2% SC
Composition %
Terfuryltrione (97%) 25.98
Bispyribac Sodium (93%) 2.36
Ethylene oxide propylene oxide copolymer 0.2
Nonionic polyalkylene glycol ether 2
Acrylic graft copolymer 3
Alkylated naphtalene sulfonate, sodium salt 0.5
Silicone antifoam 0.3
Benzisothiazoline 0.1
Glycol 5
Polysaccharides 0.15
D.M. Water 40.75
TOTAL 100

Procedure: As per Example 6

Example 8: Storage Stability Data
Comparison of the stability of formulations
The stability of each of the formulation of Example 1 to Example 7 were tested for 1 month to 24 months stability at room temperature and at elevated temperature study under the following conditions: Heat stability study at 54 + 2 0C for 14 days and Cold storage stability at 0 + 2 0C for 14 days. The required parameters studied are active content, pH, Wettability, Wet Sieve(45 micron), Bulk Density, Moisture Content, Persistent Foaming, Suspensibility, Pourability and Viscosity was studied Respective amounts were measured using different instruments and parameters. The results are shown in the Table below of Examples 1 to 7. The results were found satisfactory and this formulation is passing in all physicochemical properties.

8.1: Storage stability Study-Tefuryltrione and co-herbicide 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 Beige coloured granules Complies Complies Complies
Terfuryltrione content 23.75 - 26.25 Complies Complies Complies
co-herbicide content 38 - 42 Complies Complies Complies
Terfuryltrione suspensibility Mini 70% Complies Complies Complies
co-herbicide suspensibility Mini 70% Complies Complies Complies
pH 6.5 to 7.5 Complies Complies Complies
Wettability Max 30 s Complies Complies Complies
Wet Sieve (45 micron) Mini 98.5% Complies Complies Complies
Bulk Density 0.45-0.85 Complies Complies Complies
Moisture Content Max 2.0% Complies Complies Complies

Room temperature storage data
Specification Study Duration
Parameters In House 1 month 3 month 6 month 12 months 18 months 24 months
Description Beige coloured granules Complies Complies Complies Complies Complies Complies
Terfuryltrione content 23.75 - 26.25 Complies Complies Complies Complies Complies Complies
co-herbicide content 38 - 42 Complies Complies Complies Complies Complies Complies
Terfuryltrione suspensibility Mini 70% Complies Complies Complies Complies Complies Complies
co-herbicide suspensibility Mini 70% Complies Complies Complies Complies Complies Complies
pH 6.5 to 7.5 Complies Complies Complies Complies Complies Complies
Wettability Max 30 s Complies Complies Complies Complies Complies Complies
Wet Sieve(45 micron) Mini 98.5% Complies Complies Complies Complies Complies Complies
Bulk Density 0.45-0.85 Complies Complies Complies Complies Complies Complies
Moisture Content Max 2.0% Complies Complies Complies Complies Complies Complies

8.5: Storage stability Study- Terfuryltrione 25% + Ethoxysulfuron Ethyl 1.5% 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 White colour flowable liquid Complies Complies Complies
Terfuryltrione content 23.75 - 26.25 Complies Complies Complies
co-herbicide content 1.425 - 1.65 Complies Complies Complies
Terfuryltrione suspensibility Mini 80% Complies Complies Complies
co-herbicide suspensibility Mini 80% Complies Complies Complies
pH 7.0-9.0 Complies Complies Complies
Particle size D50 <3, D90 <10 Complies Complies Complies
Pourability 95 % min Complies Complies Complies
Specific gravity 1.05 – 1.15 Complies Complies Complies
Viscosity 350 -900 cps Complies Complies Complies

Room temperature storage data
Specification Study Duration
Parameters In House 1 month 3 month 6 month 12 months 18 months 24 months
Description coloured liquid Complies Complies Complies Complies Complies Complies
Description White colour flowable liquid Complies Complies Complies Complies Complies Complies
Terfuryltrione content 23.75 - 26.25 Complies Complies Complies Complies Complies Complies
co-herbicide content 1.425 - 1.65 Complies Complies Complies Complies Complies Complies
Terfuryltrione suspensibility Mini 80% Complies Complies Complies Complies Complies Complies
co-herbicide suspensibility Mini 80% Complies Complies Complies Complies Complies Complies
pH 7.0-9.0 Complies Complies Complies Complies Complies Complies
Particle size D50 <3, D90 <10 Complies Complies Complies Complies Complies Complies
Pourability 95 % min Complies Complies Complies Complies Complies Complies
Specific gravity 1.05 – 1.15 Complies Complies Complies Complies Complies Complies
Viscosity 350 -900 cps Complies Complies Complies Complies Complies Complies

co-herbicide selected from Dichlorophenoxyacetic acid (2,4-D), Anilofos, Azimsulfuron, Bentazon, Bispyribac, Ethoxysulfuron, Pendimethalin, Pyraclonil, Pyrazosulfuron

Example 9: Bio efficacy trials
Field experiments of inventive mixtures of Tefuryltrione+2,4-D Sodium salt, Tefuryltrione + Pyrazosulfuron Ethyl, Tefuryltrione+ Azimsulfuron, Tefuryltrione+ Ethoxysulfuron and Tefuryltrione+ Bispyribac sodium, were carried on Rice crop to evaluate their phytotoxicity and Bioefficacy against different weed flora existing in Rice field.
Trial 1 Phytotoxicity on Rice (Oryza sativa L.) crop
Experiment 1
The field experiment was conducted on Rice and experimental details as below:
Crop & Variety: Rice, MTU 1010
Experimental design: Randomized block design (R.B.D)
Replications: Three
No. of Treatments: Fourteen
Plot size: 30 sq. mt.
Application Time: 15 DAS (Days after sowing)
Observations: at 5, 10 and 15 and 20 DAA (Days after Application)
Spray Volume: 375 liter water per hectare
Application Equipment: Manually operated knap sack sprayer fitted with flat fat nozzle
Experimental Methodology:
Rice crop was raised as per the standard agronomic practices in the field to conduct a trial to assess phytotoxicity of different inventive mixtures of Tefuryltrione with 2, 4-D Sodium salt, Pyrazosulfuron Ethyl, Azimsulfuron, Ethoxysulfuron and Bispyribac sodium. The trial was laid out in Randomized Block Design (RBD) with fourteen treatments including untreated check (UTC), replicated three times. For each treatment plot size of 30 sq. mt was maintained. The application of different treatments with prescribed doses was done with manually operated knapsack sprayer fitted with flat fan nozzle. The spray volume was used at 375 l/h for spraying. The Untreated check plot was sprayed with water alone. Observations on phytotoxicity viz., leaf scorching was recorded at 5, 10 and 15 days after spraying, by adopting 0-10 rating scale as below:
0= No phytotoxicity, 1 =1-10% leaf scorching, 2=11-20% leaf scorching, 3=21-30% leaf scorching, 4=31-40% leaf scorching, 5=41-50% leaf scorching, 6=51-60% leaf scorching, 7=61-70% leaf scorching, 8=71-80% leaf scorching, 9=81-90% leaf scorching, 10=91-100% leaf scorching.
Percent phytotoxicity was calculated by following formula:
Sum of all scores
% Phytotoxicity = ------------------------------------------------------------- X 100
Number of samples x highest rating scale

Table 1: Phytotoxicity on rice crop
Treatment Details Application Rate (per hectare) Yellowing (%)
5 DAA 10 DAA 15 DAA
Tefuryltrione 25% + 2,4-D Sodium salt 40% WG 1000 g 7.3 0.0 0.0
Tefuryltrione 50% + Pyrazosulfuron Ethyl 3% WG 500 g 0.0 0.0 0.0
Tefuryltrione 50% + Azimsulfuron 6% WG 500 g 7.2 0.0 0.0
Tefuryltrione 25% + Ethoxysulfuron 1.5%, SC 1000 ml 6.3 0.0 0.0
Tefuryltrione 50% + Ethoxysulfuron 3% WG 500 g 5.6 0.0 0.0
Tefuryltrione 25% + Bispyribac Sodium 2% SC 1000 ml 0.0 0.0 0.0
Tefuryltrione 50% + Bispyribac Sodium 4% WG 500 g 0.0 0.0 0.0
Tefuryltrione 50% WG 500 g 0.0 0.0 0.0
2,4-D Sodium Salt 80% WP 500 g 0.0 0.0 0.0
Pyrazosulfuron Ethyl 10% WP 200 g 0.0 0.0 0.0
Azimsulfuron 30% WDG 100 g 0.0 0.0 0.0
Ethoxysulfuron 15% WDG 100 g 0.0 0.0 0.0
Bispyribac Sodium 10% SC 200 ml 0.0 0.0 0.0
Untreated Check (UTC) _ 0.0 0.0 0.0

The results of the field trial presented in above table indicates that the inventive mixtures of Tefuryltrione+2,4-D Sodium salt, Tefuryltrione+ Azimsulfuron and Tefuryltrione+ Ethoxysulfuron shows marginal leaf scorching (<10%) on 5th days after application which was completely recovered on 10th day without affecting normal plant growth. The inventive mixture of Tefuryltrione+ Pyrazosulfuron Ethyl and Tefuryltrione+ Bispyribac sodium were found safe to the rice crop.

Trial 2 Bioefficacy evaluation on Rice (Oryza sativa L.) crop
A synergistic effect exists wherever the action of a combination (tank-mix or ready mix) of active ingredient is greater than the sum of the action of each of the components alone. Therefore a synergistically effective amount or an effective amount of a synergistic composition or combination is an amount that exhibits greater herbicidal activity than the sum of the herbicidal activities of the individual components.
In the field of agriculture, it is often understood that the term “synergy” is as defined by Colby S.R. in an article entitled “ Calculation of the synergistic and antagonistic responses of herbicide combinations” published in the journal Weeds, 1967, 15, p.20-22, incorporated herein by reference in its entirety. The action expected for a given combination of two active components can be calculated as follows:
XY
E = X + Y - -----------
100

in which E represents the expected percentage of herbicidal control for the combination of the two herbicide at defined dose (for example equal to x and y respectively), X is the percentage of herbicidal control observed by active ingredient I at defined dose (equal to X) and Y is the percentage of herbicidal control observed by Active Ingredient II (equal to Y). When the percentage of herbicidal control observed for the combination is greater than the expected percentage, there is a synergistic effect.
The synergistic herbicidal action of the inventive mixtures can be demonstrated by the experiments below.
Field trials were conducted using the tank mix combination of Tefuryltrione with 2, 4-D Sodium Salt, Pyrazosulfuron ethyl, Azimsulfuron, Ethoxysulfuron and Bispyribac sodium. The trials were laid out in Randomized Block design (RBD) with sixteen (16) treatments, replicated three times. For each treatment plot size of 40 sq. mt. was maintained. To raise the crops all the agronomic practices were followed as usually adopted. The treatments were applied as per the calculated dosages, using manually operated knap sack sprayer, fitted with flat fan nozzle. The spray volume was used at 375 l/ha for application of all herbicidal treatments. Species wise weed count recorded at 15 and 30 DAA (Days After Application) by using 0.25 m2 quadrant treatment wise in minimum 3 places randomly selected in the plot per replication. The average of each variable was used together with the sum of all the variables per plot to calculate the percentage of control.

% Weed Control =

Mean weed count in – Mean weed control
Untreated plot in treated plot
1- ------------------------------------------------------- X 100
Mean weed count in Untreated plot

The % weeds control data used in Colby’s formula to calculate the synergism between two herbicide.
Experiment 2
Crop & Variety: Rice, Sona Masuri
Experimental design: Randomized block design (R.B.D)
Replications: Three
No. of Treatments: Fifteen
Plot size: 50 sq. mt.
Application Time: 24 DAS (Days after transplanting)
Observations: 15 and 30 DAA (Days after Application)
Spray Volume: 400 liter water per hectare
Table 2: Efficacy of tank mix of Tefuryltrione + 2, 4-D Sodium Salt
Treatment Details Application Rate (ml or g per h) Active Ingredient (g/h) % Weed Control Observed % Weed Control Expected Colby Ratio o/e
15 DAA 30 DAA 15 DAA 30 DAA 15 DAA 30 DAA
Tefuryltrione 50% WP 400 200 46.23 51.28
Tefuryltrione 50% WP 500 250 52.80 57.92
Tefuryltrione 50% WP 600 300 56.26 62.16
2,4-D Sodium Salt 80% WP 375 300 33.82 38.63
2,4-D Sodium Salt 80% WP 500 400 40.73 47.90
2,4-D Sodium Salt 80% WP 625 500 45.62 52.16
Tefuryltrione 50% WP + 2,4-D Sodium alt 80% WP(tank mix) 400+375 200+300 77.92 81.63 64.42 70.10 1.21 1.16
Tefuryltrione 50% WP + 2,4-D Sodium alt 80% WP(tank mix) 400+500 200+400 80.26 84.72 68.13 74.62 1.18 1.14
Tefuryltrione 50% WP + 2,4-D Sodium alt 80% WP(tank mix) 400+625 200+500 84.63 87.56 70.76 76.69 1.20 1.14
Tefuryltrione 50% WP + 2,4-D Sodium alt 80% WP(tank mix) 500+375 250+300 82.56 85.63 68.76 74.18 1.20 1.15
Tefuryltrione 50% WP + 2,4-D Sodium alt 80% WP(tank mix) 500+500 250+400 86.26 90.63 72.02 78.08 1.20 1.16
Tefuryltrione 50% WP + 2,4-D Sodium alt 80% WP(tank mix) 500+600 250+500 90.37 92.36 74.33 79.87 1.22 1.16
Tefuryltrione 50% WP + 2,4-D Sodium alt 80% WP(tank mix) 600+375 300+300 84.46 89.72 71.05 76.78 1.19 1.17
Tefuryltrione 50% WP + 2,4-D Sodium alt 80% WP(tank mix) 600+500 300+400 90.26 94.17 74.08 80.29 1.22 1.17
Tefuryltrione 50% WP + 2,4-D Sodium alt 80% WP(tank mix) 600+625 300+500 93.57 96.36 76.21 81.90 1.23 1.18

WP Wettable Powder
Weed flora in trial plot -GRASSES- Echinochloa colonum, Leptochloa chinensis, BROAD LEAF WEEDS – Sphenoclea zeylanica, Eclipta alba, Ludwigia parviflora, Alter nanthera sessile, SEDGES- Cyperus difformis, and Cyperus iria.

The field trial results shows that combination of Tefuryltrione+2,4-D Sodium salt shows the significantly superior Bioefficacy against mixed weed flora in rice crop as compared to their individual application.

Experiment 3
Crop & Variety: Rice, PR 1121
Experimental design: Randomized block design (R.B.D)
Replications: Three
No. of Treatments: Fifteen
Plot size: 35 sq. mt.
Application Time: 22 DAS (Days after transplanting)
Observations: 15 and 30 DAA (Days after Application)
Spray Volume: 400 liter water per hectare
Table 3: Efficacy of tank mix of Tefuryltrione + Pyrazosulfuron Ethyl
Treatment Details Application Rate (ml or g per h) Active Ingredient (g/h) % Weed Control Observed % Weed Control Expected Colby Ratio o/e
15 DAA 30 DAA 15 DAA 30 DAA 15 DAA 30 DAA
Tefuryltrione 50% WP 400 200 51.36 53.18
Tefuryltrione 50% WP 500 250 53.40 54.72
Tefuryltrione 50% WP 600 300 57.60 59.22
Pyrazosulfuron Ethyl 10% WP 100 10 38.82 54.40
Pyrazosulfuron Ethyl 10% WP 150 15 50.48 55.90
Pyrazosulfuron Ethyl 10% WP 200 20 54.62 58.66
Tefuryltrione 50% WP + Pyrazosulfuron Ethyl 10% WP (tank mix) 400+100 200+10 87.20 91.84 70.24 78.65 1.24 1.17
Tefuryltrione 50% WP + Pyrazosulfuron Ethyl 10% WP (tank mix) 400+150 200+15 89.14 92.68 75.91 79.35 1.17 1.17
Tefuryltrione 50% WP + Pyrazosulfuron Ethyl 10% WP (tank mix) 400+200 200+20 90.64 95.48 77.93 80.64 1.16 1.18
Tefuryltrione 50% WP + Pyrazosulfuron Ethyl 10% WP (tank mix) 500+100 250+10 93.82 97.76 71.49 79.35 1.31 1.23
Tefuryltrione 50% WP + Pyrazosulfuron Ethyl 10% WP (tank mix) 500+150 250+15 96.80 98.20 76.92 80.03 1.26 1.23
Tefuryltrione 50% WP + Pyrazosulfuron Ethyl 10% WP (tank mix) 500+200 250+20 96.84 98.86 78.85 81.28 1.23 1.22
Tefuryltrione 50% WP + Pyrazosulfuron Ethyl 10% WP (tank mix) 600+100 300+10 96.88 98.92 74.06 81.40 1.31 1.22
Tefuryltrione 50% WP + Pyrazosulfuron Ethyl 10% WP (tank mix) 600+150 300+15 97.54 98.84 79.00 82.02 1.23 1.21
Tefuryltrione 50% WP + Pyrazosulfuron Ethyl 10% WP (tank mix) 600+200 300+20 98.20 98.90 80.76 83.14 1.22 1.19
Weed flora in trial plot -GRASSES- Echinochloa colonum, BROAD LEAF WEEDS – Sphenoclea zeylanica, Eclipta alba, Ludwigia parviflora, Monochoria vaginalis, Sagittaria milliacea, SEDGES- Cyperus difformis, Fimbristylis miliacea, Scirpur royelei.

The tank mix combination of Tefuryltrione+Pyrazosulfuron Ethyl shows synergistic weed control of mixed weed flora in rice crop compared to their individual application.

Experiment 4
Crop & Variety: Rice, Mahamaya
Experimental design: Randomized block design (R.B.D)
Replications: Three
No. of Treatments: Fifteen
Plot size: 48 sq. mt.
Application Time: 18 DAS (Days after Sowing)
Observations: 15 and 30 DAA (Days after Application)
Spray Volume: 375 liter water per hectare
Table 4: Efficacy of tank mix of Tefuryltrione + Ethoxysulfuron
Treatment Details Application Rate (ml or g per h) Active Ingredient (g/h) % Weed Control Observed % Weed Control Expected Colby Ratio o/e
15 DAA 30 DAA 15 DAA 30 DAA 15 DAA 30 DAA
Tefuryltrione 50% WP 400 200 46.82 49.72
Tefuryltrione 50% WP 500 250 52.38 56.26
Tefuryltrione 50% WP 600 300 54.82 60.82
Ethoxysulfuron 15% WDG 66.7 10 36.62 40.28
Ethoxysulfuron 15% WDG 100 15 43.58 52.38
Ethoxysulfuron 15% WDG 133.3 20 48.28 56.42
Tefuryltrione 50% WP + Ethoxysulfuron 15% WDG (tank mix) 400+66.7 200+10 72.83 80.48 66.29 69.97 1.10 1.15
Tefuryltrione 50% WP + Ethoxysulfuron 15% WDG (tank mix) 400+100 200+15 77.86 85.36 70.00 76.06 1.11 1.12
Tefuryltrione 50% WP + Ethoxysulfuron 15% WDG (tank mix) 400+133.3 200+20 78.16 87.46 72.50 78.09 1.08 1.12
Tefuryltrione 50% WP + Ethoxysulfuron 15% WDG (tank mix) 500+66.7 250+10 80.82 92.58 69.82 73.88 1.16 1.25
Tefuryltrione 50% WP + Ethoxysulfuron 15% WDG (tank mix) 500+100 250+15 86.48 95.38 73.13 79.17 1.18 1.20
Tefuryltrione 50% WP + Ethoxysulfuron 15% WDG (tank mix) 500+133.3 250+20 88.26 97.72 75.37 80.94 1.17 1.21
Tefuryltrione 50% WP + Ethoxysulfuron 15% WDG (tank mix) 600+66.7 300+10 89.52 98.48 71.36 76.60 1.25 1.29
Tefuryltrione 50% WP + Ethoxysulfuron 15% WDG (tank mix) 600+100 300+15 90.72 98.14 74.51 81.34 1.22 1.21
Tefuryltrione 50% WP + Ethoxysulfuron 15% WDG (tank mix) 600+133.3 300+20 91.26 99.10 76.63 82.93 1.19 1.20
Weed flora in trial plot -GRASSES- Echinochloa colonum, Echinochloa crus-galli, BROAD LEAF WEEDS – Eclipta alba, Ludwigia parviflora, Marsilea quadrifoliata, Bergia capensis, Ammania baccifera, Monochoria vaginalis, Sagittaria milliacea, Alter nanthera sessile, SEDGES- Cyperus iria, Fimbristylis miliacea.

Synergistic control of mixed flora in rice crop was observed with tank mix of Tefuryltrione + Ethoxysulfuron.

Experiment 5
Crop & Variety: Rice, MTU 1010
Experimental design: Randomized block design (R.B.D)
Replications: Three
No. of Treatments: Fifteen
Plot size: 40 sq. mt.
Application Time: 15 DAS (Days after sowing)
Observations: 15 and 30 DAA (Days after Application)
Spray Volume: 375 liter water per hectare
Table 5: Efficacy of tank mix of Tefuryltrione + Bispyribac Sodium
Treatment Details Application Rate (ml or g per h) Active Ingredient (g/h) % Weed Control Observed % Weed Control Expected Colby Ratio o/e
15 DAA 30 DAA 15 DAA 30 DAA 15 DAA 30 DAA
Tefuryltrione 50% WP 400 200 50.30 53.18
Tefuryltrione 50% WP 500 250 52.94 54.72
Tefuryltrione 50% WP 600 300 54.28 59.22
Bispyribac Sodium 10% SC 150 15 48.26 54.40
Bispyribac Sodium 10% SC 200 20 49.50 55.90
Bispyribac Sodium 10% SC 250 25 51.48 58.66
Tefuryltrione 50% WP + Bispyribac Sodium 10% SC (tank mix) 400+150 200+15 86.24 92.66 74.29 78.65 1.16 1.18
Tefuryltrione 50% WP + Bispyribac Sodium 10% SC (tank mix) 400+200 200+20 87.82 93.16 74.90 79.35 1.17 1.17
Tefuryltrione 50% WP + Bispyribac Sodium 10% SC (tank mix) 400+250 200+25 88.28 94.26 75.89 80.64 1.16 1.17
Tefuryltrione 50% WP + Bispyribac Sodium 10% SC (tank mix) 500+150 250+15 94.56 98.42 75.65 79.35 1.25 1.24
Tefuryltrione 50% WP + Bispyribac Sodium 10% SC (tank mix) 500+200 250+20 95.26 97.88 76.23 80.03 1.25 1.22
Tefuryltrione 50% WP + Bispyribac Sodium 10% SC (tank mix) 500+250 250+25 95.20 97.64 77.17 81.28 1.23 1.20
Tefuryltrione 50% WP + Bispyribac Sodium 10% SC (tank mix) 600+150 300+15 93.28 95.92 76.34 81.40 1.22 1.18
Tefuryltrione 50% WP + Bispyribac Sodium 10% SC (tank mix) 600+200 300+20 94.90 97.88 76.91 82.02 1.23 1.19
Tefuryltrione 50% WP + Bispyribac Sodium 10% SC (tank mix) 600+250 300+25 96.62 98.68 77.82 83.14 1.24 1.19
Weed flora in trial plot -GRASSES- Echinochloa colonum, Echinochloa crus-galli, Leptochloa chinensis, Panicum spp., BROAD LEAF WEEDS –Eclipta alba, Ammania baccifera, Sagittaria milliacea, Alter nanthera sessile, SEDGES- Cyperus difformis, Cyperus iria, Fimbristylis miliacea, Scirpur royelei.

Superior weed control of all kind of weeds has been observed with tank mix combination of Tefuryltrione + Bispyribac Sodium in rice crop.
,CLAIMS:We claim;
[Claim 1] A synergistic herbicidal composition comprising bioactive amounts of Tefuryltrione and at least one co-herbicide selected from Dichlorophenoxyacetic acid (2,4-D), Anilofos, Azimsulfuron, Bentazon, Bispyribac, Ethoxysulfuron, Pendimethalin, Pyraclonil, Pyrazosulfuron and their agrochemically acceptable salts thereof with at least one inactive excipient.
[Claim 2] The synergistic herbicidal composition as claimed in claim 1 wherein the ratio of Tefuryltrione and at least one co-herbicide selected from Dichlorophenoxyacetic acid (2,4-D), Anilofos, Azimsulfuron, Bentazon, Bispyribac, Ethoxysulfuron, Pendimethalin, Pyraclonil, Pyrazosulfuron is 25: 1 to 1: 10
[Claim 3] The synergistic herbicidal composition according to claim 1, 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.
[Claim 4] The synergistic herbicidal composition as claimed in claim 1, wherein the composition are selected from jumbo formulation, wettable powder (WP), a granule (GR) (such as an emulsifiable granule (EG) or more particularly a water-dispersible granule (WG)), an emulsifiable concentrate (EC), a microemulsifiable concentrate, an oil-in-water emulsion (EW), an oil flowable (e.g. a spreading oil (SO)), an aqueous dispersion (e.g. aqueous suspension concentrate (SC)), an oily dispersion (OD).
[Claim 5] The synergistic herbicidal composition as claimed in any of the preceding claims, wherein the said formulation is used for control of weed selected form the group but not limited to it, Aeschynomene aspera, Aeschynomene indica, Ageratum conyzoides, Alternanthera sessilis, Alternanthera philoxeroides, Amaranthus spinosus, Amaranthus viridis, Ammania baccifera, Cynodon dactylon, Dactyloctenium aegyptium, Digitaria ciliaris, Digitaria setigera, Ischaemum rugosum, Echinochloa colona, Echinochloa crus-galli, Echinochloa glabrescens, Echinochloa crus-pavonis, Echinochloa esculenta, Echinochloa frumentacea, Echinochloa muricata, Echinochloa oryzoides, Echinochloa paludigena, Eleocharis kuruguwai, Laptochloa chinensis, Eleusine indica, Eclipta alba, Eclipta prostate, Imperata cylindrical, Leersia hexandra, Leptochloa chinensis, Oryza sativa, Panicum repens, Paspalum distichum, Paspalum scrobiculatum, Rottboellia cochinchinensis, Setaria glauca, Bolboschoenus maritimus, Bergia capensis, Commelina benghalensis, Commelina diffusa, Cyanotis axillaris, Eclipta alba, Eclipta prostrate, Eichhornia crassipes, Ipomoea aquatic, Ludwigia adscendens, Ludwigia hyssopifolia, Ludwigia octovalvis, Ludwigia parviflora, Marsilea minuta, Marsilea quadrifoliata, Mimosa diplotricha, Monochoria vaginalis, Pistia stratiotes, Polygonum hydropiper, Portulaca oleracea, Sagittaria milliacea, Sagittaria sagittifolia, Sphenoclea zeylanica, Trianthema portulacastrum, Typha spp., Isachne globosa, Paspalum distichum, Cyperus difformis, Cyperus haspen, Cyperus iria, Cyperus rotundus, Fimbristylis dichotoma, Fimbristylis miliacea, Scirpus juncoides, Scirpus nipponicus, Scirpus planiculmis, Scirpur royelei, Scirpus juncoides.
[Claim 6] The synergistic herbicidal composition as per claim 5, wherein the composition is effective for management of control of weeds of Paddy (Oryza sativa L.) including Indica, Japonica and Javanica race. GMO Paddy.
[Claim 7] The synergistic herbicidal composition as per claim 1, which is to be applied as Pre-emergence (before weed germination) to late post emergence (after weed germination).
[Claim 8] A synergistic herbicidal composition of Tefuryltrione and at least one co-herbicide as claimed in any of the preceding claims and exemplified with working examples as disclosed.