Description:FIELD OF INVENTION:
The present invention relates to a formulated synergistic granular herbicidal composition with polyalkyleneoxide modified heptamethyl trisiloxane as a wetting agent. More particularly the present invention relates to a formulated synergistic granular herbicidal composition comprising the bioactive amount of (a) Metamifop present in an amount of 3% to 10% w/w; (b) Bentazone present in an amount of 25% to 60% w/w; (c) an herbicide selected from halosulfuron methyl, chlorimuron ethyl or metsulfuron methyl present in an amount of 0.05% to 4% w/w along with polyalkyleneoxide modified heptamethyl trisiloxane as a wetting agent present in an amount of 1.0%-6.0%w/w and other formulation excipients.

BACKGROUND OF THE INVENTION:
Weeds are a nuisance in most crops, plantation crops, landscapes, orchards and sometimes the herbicides used to control the weeds end up injuring crops, useful plants, some of the ornamental plants. Herbicides are pesticides useful for killing or controlling unwanted plants. Generally, there are two kinds of herbicides- selective and non-selective. Selective herbicides kill certain target weeds while leaving the desired crop relatively unharmed while non-selective herbicides kill both the weeds and crops. Profitable crop production depends on effective weed control. The weeds can reduce field crop yields by competing for water, sunlight, and nutrients. In today’s crop production systems, starting with a good burn-down program is a must as it helps to achieve maximum initial crop growth and reduce weed interference during the early stages of the crop cycle. Since the weed-crop competition is critical during the early stages of the crop cycle, the weed interference at the early stage has a direct impact on the yield of the crop.
The term for plant damage is “phytotoxicity” and it can be caused by pesticides, nutrients, or physical and environmental damage (wind, sun, hail, etc.). Often the identity of the herbicide symptoms on the plants.
Symptoms can be divided into 5 main categories: leaf spotting, leaf and shoot malformations, root and shoot stunting, leaf chlorosis (yellowing), and leaf necrosis (death).
Herbicide injury is observed after the application of herbicide in terms of stunting, yellowing, scorching, epinasty, hyponasty, germination loss, poor plant population stand in a field and even loss of crop or plant yield. It normally happens while not following the directions on the label as carefully as one should. Farmers tend to use more herbicides than the label instructs or can be careless and spray during windy conditions or wave the wand around so that the spray drifts onto non-target plants.
Effective weed control can be achieved by the usage of herbicides appropriately. The activity of herbicides can be enhanced in various ways to achieve the maximum benefit. One of the ways is to use combinations. However, identifying appropriate combinations, which will reduce the toxicity at the same time due to the application of herbicides on the crop, their agrochemical application rates, and the ratio of the combinations is essential to achieve efficacious control, which is not straightforward. The selection of a particular formulation type is more cumbersome for an agrochemical combination.
The efficacy of these herbicides against harmful weeds in the crop plants depends on the application rate, the formulation ingredients, the harmful weeds to be controlled, the climatic conditions, and the soil conditions.
Farmers are applying more than one active ingredient or applying high use rate to control different types of weeds at a time, to control multiple generations of weeds in fields, to control troublesome weeds, and to get residual control. Such practices increase the chances of herbicidal injury or phytotoxicity to the target crops.
There are many herbicides used in combination that creates characteristic phytotoxic injuries in plants like malformed, distorted leaves and shoots, stunted shoots and roots, chlorotic, necrotic, or spotted leaves.
However, there remains a great need for improved broadleaf, sedges and grassy weed control compositions and a method of controlling such noxious vegetation in pre and post-emergence without adversely affecting desirable plants and which reduces the amount of chemical herbicidal agent necessary to obtain the acceptable weed control along with reducing the undesirable post-treatment toxic effect or injury of the herbicides on crops.
Metamifop ((R)-2-[4-(6-chloro-1,3-benzoxazol-2-yloxy0phenoxy]-2’-fluoro-N-methylpro pion- anilide) is a new herbicide developed by Dongbu Hannong Chemical, Korea. It is used for post-emergence control of annual and perennial grass weeds in rice. The mode of action of Metamifop is the inhibitor of acetyl-CoA carboxylase (ACCase). The inhibition of ACCase leads to the interruption of lipid biosynthesis and results in death of the plant. In most cases, these herbicides effectively control weeds at a very low rate with limited or no toxicities to non-target species.

Bentazone (2, 2-dioxo-3-propan-2-yl-1H-2?6, 1, 3-benzothiadiazin-4-one) was manufactured by BASF. Bentazone is a contact herbicide used for controlling weeds in winter and spring cereals. Bentazone is not chemically reactive and no highly reactive species have been identified during its metabolism.

Halosulfuron-methyl (3-chloro-5-(4, 6-dimethoxypirimidin2-ylcarbamoylsulfamoyll-l-methyl-pyrasole-4-carboxylate) is the active ingredient in a new class of herbicide products by Monsanto which are used for the control of broadleaf and sedge weeds in corn, turf, sugarcane, and other crops. The metabolic basis for the corn and wheat selectivity of halosulfuron-methyl was studied using cell suspension cultures and young seedlings.

Suspension concentrate (SC) formulation contains tiny particles of active ingredient suspended in a liquid (usually water) and milled to reduce the average particle size. SC (suspension concentrate) typically have a higher viscosity are thicker than water because of the presence of thickners/suspension aids. The commonly-used adjuvants for SC formulations are alkoxylate, nonionic surfactants, which could either be simple ethoxylates or ethylene oxide/propylene oxide (EO/PO) block copolymers there is improved wetting and spreading properties.
Emulsifiable concentrate (EC) is a solvent-based oil system that contains active ingredients dissolved in a solvent and emulsifiers. ECs are solvent-based, the physical properties can vary widely depending on the solvent system used. The solvent type can affect product qualities such as odor, viscosity, flammability and potential for phytotoxicity.
Suspoemulsion (SE) are mixtures of suspensions and emulsions that are applied in many formulations such as paints, personal care products and agrochemicals. Suspoemulsion (SE) is a water-based product that contains both suspended solids (like SC) and emulsion droplets (like EC after dilution). As with SCs, suspension aids are needed to prevent setting of the solids or creaming of the emulsion droplets. Suspoemulsion have viscosities much higher than water. Suspoemulsion has good spreading properties.
Soluble liquids (SL) are usually water-based product that contain a dissolved active ingredient. This is one of the formulation types that actually contains dissolved molecules, not suspended particles. SLs can contain the salt form of an active ingredient, the overall salt concentration in the spray tank can be higher than for other formulations. This can sometimes lead to flocculation of other tank-mix partners such as SCs or ECs.

CN112314610A patent relates to weeding composition containing metamifop, halosulfuron-methyl and butachlor. The invention relates a weeding composition containing metamifop, halosulfuron-methyl and butachlor, wherein the active ingredients comprise the metamifop, the halosulfuron-methyl and butachlor, and the mass ratio of the metamifop, the halosulfuron-methyl and the butachlor is 5-25:1-20: 1-60. The weeding composition can be used for preventing and removing annual weeds in the paddy field and has obvious synergistic effect.
CN104585205 patent relates to Herbicide composition containing metamifop, cyhalofop-butyl and halosulfuron-methyl. The invention relates to an herbicide composition containing metamifop, cyhalofop-butyl and halosulfuron-methyl. The herbicide composition contains active ingredients of the metamifop, the cyhalofop-butyl and the halosulfuron-methyl, wherein the metamifop accounts for 1-20wt% of the composition, the cyhalofop-butyl accounts for 1-30wt% of the composition and the halosulfuron-methyl accounts for 1-20wt% of the composition. The herbicide composition disclosed by the invention has a synergetic effect; in the control and removal of annual weeds in a paddy field, the effect of the herbicide composition is significantly better than that of various single agent in independent use; the herbicide composition can be used for widening a weeding spectrum, and the herbicide composition can be also used for reducing the use quantity of pesticides, reducing weed resistance risks, relieving environment pollution and delaying the generation of weed resistance.
CN104304297A relates to weeding composition containing metamifop. The invention relates to an herbicide composition, and particularly relates to a weeding composition containing chlorpromazine sulfometuron methyl and metamifop as active ingredients for preventing and removing weeds of a paddy field. The weight ratio of the active ingredients chlorpromazine sulfometuron methyl to metamifop in the composition is (1:40) to (32:5); and the percent content of the active ingredients in the composition is 1-80%. The weeding composition is reasonable in components, and good in weed effect; the herbicide controlling spectrum is expanded; the drug delivery times is reduced; the prevention and control cost is reduced; the weed insecticide resistance is delayed; and the weeding composition is safe to rice and is an ideal herbicide.
Stable pesticidal composition such as wettable granule or wettable powder (WP) and water dispersible or soluble granules (WG/SG) containing combination of agriculture actives with different mode of action can be difficult to produce and store due to tendency to physically degrade and agglomerate to cake when subject to range of temperature and shear stress normally encountered during processing and storage. In addition, these compositions may suffer from poor dispersion in water and poor delivery of the active ingredient to the locus of the pests requiring control of elimination.
Stable wettable granule are generally defined as those that are stable physically and chemically to the environment in which they are produced and stored and deliver acceptable level of biological efficacy when used with in different period of time.
However still there is a need for a synergistic herbicidal composition which overcomes some of the existing problems and can be prepares easily without much complex manufacturing process.
Inventors of the present invention have found that the novel synergistic herbicidal composition comprising of (A) Metamifop (B) Bentazone (C) One herbicide selected from halosulfuron methyl, chlorimuron ethyl or metsulfuron methyl or combination thereof can provide solution to the above-mentioned problems. All the components of present invention has different mode of action.

SUMMARY OF INVENTION:
The present invention relates to a formulated synergistic granular herbicidal composition comprising polyalkyleneoxide modified heptamethyl trisiloxane as a wetting agent. More particularly the present invention relates to a formulated synergistic granular herbicidal composition comprising polyalkyleneoxide modified heptamethyl trisiloxane as a wetting agent, herbicidal compounds and other formulation excipients.
The present invention more particularly relates to a formulated synergistic granular herbicidal composition comprising polyalkyleneoxide modified heptamethyl trisiloxane as a wetting agent present in an amount of 1.0%-6.0%w/w along with bioactive amount of compound (A) Metamifop present in an amount of 3% to 10% w/w; compound (B) Bentazone present in an amount of 25% to 60% w/w; and compound (C) one herbicide selected from halosulfuron methyl, chlorimuron ethyl or metsulfuron methyl present in an amount of 0.05% to 4% w/w and other formulation excipients.
The present invention further relates to selection of suitable formulation excipients, process of preparation of the said wettable granule formulation and composition thereof and its application in the field of agriculture
Further aspect of the present invention is to provide wettable granule (WG) formulation that exhibits synergistic activity and stable over wide range of the conditions.
A further aspect of the invention the inactive formulation excipients are used in Wettable granule formulation may be selected from dispersing agent, wetting agent, antifoaming agent, carrier, humectant.
Yet another object of the present synergistic herbicidal wettable granule formulation composition comprising bioactive amount of (A) Metamifop present in an amount of 3% to 10% w/w; (B) Bentazon present in an amount of 25% to 60% w/w; (C) One herbicide selected from halosulfuron methyl, chlorimuron ethyl or metsulfuron methyl present in an amount of 0.05% to 4% w/w that controls harmful weeds.
Further aspect of the present invention is to provide herbicidal Wettable granule (WG) formulation comprising at least one active ingredient shows synergistic activity and stability over wide range of the conditions.

DETAILED DESCRIPTION OF THE INVENTION:
Formulation technology in the field of an agriculture is now seen as an “enabling technology” which can provide safe and effective products which are convenient to use. It can also modify the toxicity of active ingredients and improve their ability to target a specific pest. At a time when the discovery of new agrochemical compounds is more difficult and certainly a high risk and expensive operation, formulation technology can extent the useful patent life of an active ingredient. It can also provide a competitive edge by improving product quality of existing.
The term "synergistic", as used herein, refers the combined action of two or more active
agents blended together and administered conjointly that is greater than the sum of their
individual effects.
"Bioactive amounts” as mentioned herein means that amount which, when applied treatment of crops, is sufficient to effect such treatment.
Therefore an aspect of the present invention relates to a formulated synergistic granular herbicidal composition comprising polyalkyleneoxide modified heptamethyl trisiloxane as a wetting agent.

More particularly the present invention relates to a formulated synergistic granular herbicidal composition comprising polyalkyleneoxide modified heptamethyl trisiloxane as a wetting agent, herbicidal compounds and other formulation excipients.

In an aspect of the present invention provides a synergistic herbicidal wettable granule formulation composition comprising polyalkyleneoxide modified heptamethyl trisiloxane as a wetting agent and bioactive amount of compound (A) Metamifop; compound (B) Bentazone; and compound (C) an herbicide selected from halosulfuron methyl, chlorimuron ethyl or metsulfuron methyl; along with formulation excipients.
Further compound (C) may be selected from Halosulfuron methyl, metsulfuron methyl, chlorimuron ethyl, pyrazosulfuron ethyl, azimsulfuron, bensulfuron-methyl, chlorsulfuron, cyclosulfamuron, ethoxysulfuron, flucetosulfuron, imazosulfuron, iodosulfuron-methyl-Na, mesosulfuron-methyl, nicosulfuron, orthosulfamuron, propyrisulfuron, prosulfuron, pyrazosulfuron-ethyl, rimsulfuron, sulfosulfuron, triasulfuron, tribenuron-methyl, thifensulfuron-methyl, trifloxysulfuron-Na, triflusulfuron-methyl, tritosulfuron as all the compounds belongs to Sulfonylureas group herbicide and have similar mode of action i.e. ALS (acetolactate synthase) inhibitors and may give similar results.
In another preferred embodiment of the invention, synergistic Weed controlled according to the method of the invention.
In another aspect of the present invention, an herbicide are selected from, halosulfuron methyl, chlorimuron ethyl or metsulfuron methyl.
In another aspect of the present invention, the amount of the herbicide wettable granule applied vary with the nature of the weeds. The composition used for control the growth of weeds. This present invention, to control the growth of weeds without causing substantial permanent damage to the crop.
Wettable granule (WG) are dry formulation consist of large particles and much less dusty. After dispersion in water, they form a suspension of solids. WG has poor spreading properties compare to Emulsifiable concentrate (EC), Suspoemulsion (SE), soluble liquids (SL), Suspension concentrate (SC) liquid formulations.
In the present invention, application of polyalkyleneoxide modified heptamethyl trisiloxane as a wetting agent is an organosilicon wetting agent improves spreading and penetrating properties of the formulation.
Examples of wetting agent used herein for wettable granule (WG) formulation include but not limited to organosilicons includes trisiloxane ethoxylate, polydimethylsiloxane, polyoxyethylene methyl polysiloxane, polyoxyalkylene methyl polysiloxane, polyether polymethyl siloxane copolymer, trisiloxane heptamethyl, Polyalkyleneoxide modified heptamethyl trisiloxane, polyether modified polysiloxane, may or may not be in modified form, may be liquid or powder form or mixture thereof.
In the present invention, the most preferred wetting agent is polyalkyleneoxide modified heptamethyl trisiloxane. It enhances wetting and absorption of the active ingredient. This will improve a spray application by modifying the wetting and spreading characteristics, the result being a more uniform spray deposit. It also ensures thorough coverage without excessive runoff of the spray.
Polyalkyleneoxide Modified Heptamethyltrisiloxane:
Polyalkyleneoxide Modified Heptamethyltrisiloxane is an organic silicone surfactant with super ability of spreading. It makes the water surface tension at the lower concentration. It is to enhance the performance of agricultural chemicals, especially water-soluble broadleaf herbicides, insecticides, fungicides and plant growth regulators

Polyalkyleneoxide modified Heptamethyltrisiloxane is a modified trisiloxane silicone surfactant with a special structure. It has super properties of wetness and expansion as well as stomatal penetration rate. It can improve the prevention effect of pesticides and reduce the spray volume, widely used in the fields of pesticides herbicides, insecticides, acaricides, fungicides, plant growth regulating agents, and other aspects. It has physical inertia, no harm to human beings or the environment.
Polyalkyleneoxide Modified Heptamethyltrisiloxane is an agricultural wetting and super-spreading agent, which can be added to pesticide formulations or tank-mixed sprays. At very less concentration, the surface tension of water can be reduced by identifiable value. After mixing with the pesticide solution in a certain proportion, the contact angle between the spray liquid and the leaves can be reduced, thereby increasing the coverage of the spray, and Polyalkyleneoxide Modified Heptamethyltrisiloxane spreading agent can absorb the pesticides through the stomata of the leaves, which is helpful for improving the efficacy and reducing the pesticides. It is very effective to reduce the number of pesticides, save costs, and reduce environmental pollution caused by pesticides.
More preferred range for the wetting agent polyalkyleneoxide modified heptamethyl trisiloxane. 1.0%-6.0%w/w of the present formulated synergistic granular herbicidal composition.
Most preferred range for the wetting agent polyalkyleneoxide modified heptamethyl trisiloxane. 2.0%-5.0%w/w of the present formulated synergistic granular herbicidal composition.
More preferred range of the biological active compounds for the present formulated synergistic granular herbicidal composition is compound (A) Metamifop present in an amount of 3% to 10% w/w; compound (B) Bentazone present in an amount of 25% to 60% w/w; and compound (C) one herbicide selected from halosulfuron methyl, chlorimuron ethyl or metsulfuron methyl present in an amount of 0.05% to 4% w/w and other formulation excipients.
Most preferred range of the biological active compounds for the present formulated synergistic granular herbicidal composition is compound (A) Metamifop present in an amount of 4% to 5% w/w; compound (B) Bentazone present in an amount of 40% to 50% w/w; and compound (C) one herbicide selected from halosulfuron methyl, chlorimuron ethyl or metsulfuron methyl present in an amount of 0.5% to 4% w/w and other formulation excipients.

Further most preferred combination of the biological active compounds for the present formulated synergistic granular herbicidal composition is compound (A) Metamifop and compound (B) Bentazone and compound (C) halosulfuron methyl; compound (A) Metamifop and compound (B) Bentazone and compound (C) chlorimuron ethyl; compound (A) Metamifop and compound (B) Bentazone and compound (C) metsulfuron methyl.
An herbicidal synergistic composition of present invention controls all kind of monocots, dicots and sedges weeds. The present synergistic herbicidal combinations also controls annual and perennial weeds. The most common weeds controlled by present inventions are Abutilon indicum, Acalypha indica, Acanthospermum hispidum, Achyranthes aspera, Aerva tomentosa, Ageratum conyzoides, Alhagi camelorum, Amaranthus hybridus, Amaranthus spinosus, Amaranthus viridis, Ammania baccifera, Anagallis arvensis, Argemone mexicana, Artemisia nilagiricia, Asphodelus tenuifolius, Avena fatua, Avena ludoviciana, Bidens pilosa, Boerhaavia diffusa, Boerhavia repanda, Brachiaria mutica, Brassica kaber, Bromus tectorum, Calotropis gigantea, Cannabis sativa, Carthamus axyacantha, Cassia tora, Celosia argentea, Centella asiatica, Chenopodium album, Chenopodium murale, Chloris barbata, Chrozophora rottlerii, Cichorium intybus, Cirsium arvense, Clitoria ternatea, Cnicus arvensis, Commelina benghalensis, Commelina communis, Convolvulus arvensis, Conyza canadensis, Corchorus acutangulus, Coronopus didymus, Crotalaria serice, Cucumis callosus, Cuscuta campestris, Cuscuta chinensis, Cynodon dactylon, Cyanotis axillaris, Cyperus esculenthus, Cyperus iria, Cyperus difformis, Cyperus rotundus, Dactyloctenium aegyptium, Datura stramonium, Daucus carota, Digera arvensis, Digitaria sanguinalis, Dinebra retroflexa, Echinochola colona, Echinochola crusgalli, Eclipta alba, Eichhornia crassipes, Elephantopus scaber, Eleusine indica, Eragrostis major, Euphorbia geniculata, Euphorbia hirta, Fimbristylis miliacea, Fumaria indica, Gynandropsis gynandra, Heliotropium indicum, Indigofera glandulosa, Ipomea aquatica, Lantana camara, Lathyrus aphaca, Launaea asplenifolia, Launaea nudicaulis, Leptochloa chinensis, Leucas aspera, Ludwigia parviflora, Marsilea quadrifoliata, Medicago denticulate, Mimosa pudica, Melilotus alba, Melilotus indica, Ocimum canum, Oenothera biennis, Opuntia dillenil, Orobanche ramosa, Oryza longistaminata, Oxalis corniculata, Oxalis latifolia, Parthenium hysterophorus, Paspalum sanguinale, Phalaris minor, Phyllanthus niruri, Physalis minima, Polypogon monspeliensis, Portulaca oleracea, Prosopis juliflora, Rumex dentatus, Saccharum spontaneum, Stearia glauca, Seteria viridis, Sida spinosa, Silene antirrhina, Sisymbrium irio, Solanum nigrum, Solanum surattense, Sonchus oleraceous, Sorghum halepense, Spergula arvensis, Sphenocleazeylanica Gaertn, Striga asiatica, Tagetes minuta, Trianthema monogyna, Trianthema portulacastrum, Tribulus terrestris, Trigonelia polycerata, Vernonia cinerea, Vicia sativa and Xanthium strumarium.
In a further aspect of the present invention synergistic herbicidal wettable granule formulation composition comprising bioactive amount of (A) Metamifop (B) Bentazone (C) One herbicide selected from halosulfuron methyl, chlorimuron ethyl or metsulfuron methyl; along with formulation excipients. The combination of the present invention allows for the control of grass and broadleaved weeds in a wide range of crops. The broad spectrum of the present combination also provides a solution for preventing the development of resistance.
The synergistic herbicidal mixture has very advantageous curative, preventive and systemic herbicidal properties for protecting cultivated plants. As has been mentioned, said active ingredient composition can be used to inhibit the weed growth or to completely kill the weeds. The synergistic agrochemical composition of specific active ingredient has the special advantage of being highly effective to kill the weeds.
In another aspect of the present invention, the synergistic herbicidal composition maybe used to control the target weeds among the crops such as Rice/Paddy (Oryza sativa), Sugarcane (Saccharum officinarum), Soybean (Glycin max), Peanut (Arachis hypogaea), Linseed (Linum usitatissimum), Green gram (Vigna radiata), Black gram (Vigna mungo), Chickpea (Cicer aritinum), Cowpea (Vigna unguiculata), Redgram (Cajanus cajan), Frenchbean (Phaseolus vulgaris), Indian bean (Lablab purpureus), Horse gram (Macrotyloma uniflorum), Field pea (Pisum sativum), Cluster bean (Cyamopsis tetragonoloba), Lentils (Lens culinaris).
Crops are to be understood as also including those crops which have been rendered tolerant to herbicides or classes of herbicides (e.g. ALS-, GS-, EPSPS-, PPO-, ACCase- and HPPD-inhibitors) by conventional methods of breeding or by genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding is Clearfield® summer rape (canola). Examples of crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®.
Crops are also to be understood as being those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt soybean (resistant to lepidopteran and coleopteran pests) Plant crops or seed material thereof can be both resistant to herbicides and, at the same time, resistant to insect feeding (“stacked” transgenic events). For example, seed can have the ability to express an insecticidal Cry3 protein while at the same time being tolerant to glyphosate.
Crops are also to be understood to include those which are obtained by conventional methods of breeding or genetic engineering and contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavour).
Other useful plants include turf grass for example in golf-courses, lawns, parks and roadsides, or grown commercially for sod, and ornamental plants such as flowers or bushes.
The present invention of synergistic herbicidal combinations can be also used to control unwanted vegetation in plantation crops, orchards, fallow lands, water bodies, field bunds etc.
In a further aspect of the present invention a synergistic herbicidal wettable granule formulation composition comprising bioactive amount of (A) Metamifop present in an amount of 3% to 10% w/w; (B) Bentazon present in an amount of 25% to 60% w/w; (C) One herbicide selected from halosulfuron methyl, chlorimuron ethyl or metsulfuron methyl present in an amount of 0.05% to 4% w/w that controls harmful weeds.
The composition of the present invention in addition to bioactive amounts of active ingredients further comprises inactive excipients including but not to limited to dispersing agent, wetting agent, antifoaming agent, carrier, and humectant.
Examples of dispersing agent used herein for wettable granule (WG) formulation include but not limited to alkylated naphthalene sulfonate sodium salt, sodium polycarboxylate, naphthalene sulfonic acid, sodium salt condensates with formaldehyde, polyalcoxylated alkylphenol, naphthalene sulfonic acid formaldehyde condensate, methyl naphthalene-formaldehyde-condensate sodium salt, naphthalene condensates, lignosulfonates, sodium lignosulfonate, calcium lignosulfonate.
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 antifoaming agent used herein for wettable granule (WG) formulation include but not limited to polydimethylsiloxane.
Examples of carrier used herein for wettable granule (WG) formulation include but not limited to china clay, silica, lactose anhydrous, ammonium sulfate, sodium sulfate anhydrous, corn starch, urea, EDTA, urea formaldehyde resin, diatomaceous earth, kaolin, bentonite, kieselguhr, fuller's earth, attapulgite clay, bole, loess, talc, chalk, dolomite, limestone, lime, calcium carbonate, powdered magnesia, magnesium oxide, magnesium sulphate, sodium chloride, gypsum, calcium sulphate, pyrophyllite, silicates and silica gels; fertilizers such as, for example, ammonium sulphate, ammonium phosphate, ammonium nitrate and urea; natural products of vegetable origin such as, for example, grain meals and flours, bark meals, wood meals, nutshell meals and cellulosic powders; and synthetic polymeric materials such as, for example, ground or powdered plastics and resins, bentonites, zeolites, titanium dioxide, iron oxides and hydroxides, aluminium oxides and hydroxides, or organic materials such as bagasse, charcoal, or synthetic organic polymers.
Examples of humectant used herein for wettable granule (WG) formulation include but not limited to humic acid, glycerol, lactose, Sodium sulphate anhydrous.
The present invention a formulated synergistic granular herbicidal composition comprising polyalkyleneoxide modified heptamethyl trisiloxane as a wetting agent, (A) Metamifop (B) Bentazone (C) One herbicide selected from halosulfuron methyl, chlorimuron ethyl or metsulfuron methyl; along with formulation excipient has following benefits as:
• One shot weed control in soybean and rice
• Excellent weed control of grassy, broad leaf weeds and sedges
• Excellent bio-efficacy against tough to kill weeds like, Leptochloa chinensis, Eleusine. indica in rice and Acalypha indica in soybean
• Residual weed control
• Crop safety to rice and soybean
• Increases yield attributing parameters.
• Improve leaf penetration of spray droplets, retard evaporation loss and enhance the absorption of active ingredients
• Increase spreading properties on leaf surfaces, better wetting of waxy leaf surfaces
• Improve rain fast properties.
• WG is safer formulation to the applicator.
While the foregoing written description of the invention enables one of ordinary skill to make and use what is considered presently to be the best mode thereof, those of ordinary skill will understand and appreciate he existence of variations, combinations, and equivalents of the specific embodiment, method, and examples, but by all embodiments and methods within the scope and spirit of the invention. The invention shall now be described concerning the following specific examples. It should be noted that the example(s) appended below illustrate rather than limit the invention and that those skilled in the art will be able to design many alternative embodiments without departing from the scope of the present invention.
These and other aspects of the invention may become more apparent from the examples set forth herein below examples are provided merely as illustrations of the invention and are not intended to be construed as a limitation thereof.
Procedure: Manufacturing process for Wettable Granule formulation.
Step 1 Before starting the process, check the cleanliness of all equipment’s in plant and get approval by QC department.
Step 2 Check the electrical connection and standardize the weighing balance.
Step 3 Take exact weight of active ingredients (technical) in blender and then add required quantity of binder & surfactants and mix it till its complete homogenization.
Step 4 Mill this homogenized mixture till required wet sieve and post blend again for homogeneity.
Step 5 Pass the above homogenous material through extruder for granulation.
Step 6 Now transfer the granules through fluid bed dryer to remove excess moisture.
Step 7 Transfer these granules to vibro shifter.
Step 8 Collect the final material from the vibro shifter into drum.
Step 9 Finally send the sample to QC for approval.
Step 10 After approval by QC, transfer the material into different size of drums.

Example 1: Metamifop 4%+Bentazone 40%+Halosulfuron methyl 3% WG
Table 1.1: Metamifop 4%+Bentazone 40%+Halosulfuron methyl 3% WG with organosilicone surfactant-Polyalkyleneoxide modified heptamethyltrisiloxane
Ingredients Percent (w/w)
Metamifop a.i. 4.00
Bentazone a.i. 40.00
Halosulfuron methyl a.i. 3.00
Alkylated naphthalene sulfonate, sodium salt [dispersing agent] 3.00
Polyacrylate polymer sodium salt 6.00
Polyalkyleneoxide modified heptamethyl trisiloxane
[wetting agent] 3.00
Polydimethyl siloxane [anti foaming agent] 0.50
Sodium sulphate anhydrous [humectant] 6.00
Urea formaldehyde resin [carrier] 15.00
China Clay [carrier] 19.50
Total 100.00

Storage stability- Metamifop 4%+Bentazone 40%+Halosulfuron methyl 3% WG
Laboratory storage stability for 14 days
Parameters specification (in house) Initial At 54±2 0C At 0±2 0C
Metamifop content percent by mass 3.80 to 4.40 4.20 4.17 4.19
Bentazone content percent by mass 38.00 to 42.00 40.30 40.18 40.29
Halosulfuron methyl content percent by mass 2.85 to 3.30 3.20 3.13 3.19
Metamifop suspensibility percent min. 70 97.75 95.02 97.52
Bentazone suspensibility percent min. 70 95.36 94.15 94.56
Halosulfuron methyl suspensibility percent min. 70 95.75 93.11 94.25
pH range (1% aq. Suspension) 6.5 to 8.5 7.5 7.6 7.5
wettability sec. max. 60 8 9 9
wet sieve (45 micron) percent by mass min. 98.5 99.5 99.2 99.3
bulk density (g/ml) 0.45 to 0.65 0.5 0.5 0.5
moisture content percent by mass max. max. 3% 2.5 2.6 2.5
Room temperature storage stability up to 12 months
Parameters Specification (in house) 1 month 6 months 12 months
Metamifop content percent by mass 3.80 to 4.40 4.20 4.20 4.19
Bentazone content percent by mass 38.00 to 42.00 40.30 4.30 40.29
Halosulfuron methyl content percent by mass 2.85 to 3.30 3.20 3.20 3.19
Metamifop suspensibility percent min. 70 97.9 97.7 97.52
Bentazone suspensibility percent min. 70 95.36 94.15 94.56
Halosulfuron methyl suspensibility percent min. 70 95.75 93.11 94.25
pH range (1% aq. Suspension) 6.5 to 8.5 7.5 7.5 7.55
wettability sec. max. 60 8 9 9
wet sieve (45 micron) percent by mass min. 98.5 99.5 99.2 99.3
bulk density (g/ml) 0.45 to 0.65 0.5 0.5 0.5
Moisture content percent by mass max. max. 3% 2.5 2.5 2.5
The storage stability study of Metamifop 4%+Bentazone 40%+Halosulfuron methyl 3% WG with Organosilicone surfactant-Polyalkyleneoxide modified heptamethyltrisiloxane meets the all in-house specifications like active ingredient content, pH, wettability, wet sieve, bulk density and moisture content criteria of laboratory storage and room temperature storage (up to 12 months).
Example 2: Metamifop 4%+Bentazone 40%+Halosulfuron methyl 3% WG
Table 2.1: Metamifop 4%+Bentazone 40%+Halosulfuron methyl 3% WG without organosilicone surfactant-Polyalkyleneoxide modified heptamethyltrisiloxane
Ingredients Percent (w/w)
Metamifop a.i. 4.00
Bentazone a.i. 40.00
Halosulfuron methyl a.i. 3.00
Alkylated naphthalene sulfonate, sodium salt 3.00
Polyacrylate polymer sodium salt 6.00
Sodium Lauryl sulfate 3.00
Polydimethyl siloxane 0.50
Sodium sulphate anhydrous 6.00
Urea formaldehyde resin 15.00
China Clay 19.50
Total 100.00
The storage stability study of Metamifop 4%+Bentazone 40%+Halosulfuron methyl 3% WG without organosilicone surfactant-Polyalkyleneoxide modified heptamethyltrisiloxane meets the all in-house specifications like active ingredient content, pH, wettability, wet sieve, bulk density and moisture content criteria of laboratory storage and room temperature storage (up to 12 months).
Examples: Metamifop 4%+Bentazone 40%+Halosulfuron methyl 3% WG
Ingredients Percent (w/w)
Example 3 Example 4 Example 5
Metamifop a.i. 4.00 4.00 4.00
Bentazone a.i. 40.00 40.00 40.00
Halosulfuron methyl a.i. 3.00 3.00 3.00
Alkylated naphthalene sulfonate, sodium salt 4.00 2.50 2.00
Polyacrylate polymer sodium salt 6.00 6.00 6.00
Polyalkyleneoxide modified heptamethyltrisiloxane 2.00 4.00 5.00
Polydimethyl siloxane 0.50 0.50 0.50
Sodium sulphate anhydrous 6.00 6.00 6.00
Urea formaldehyde resin 16.00 14.00 13.00
China Clay 18.50 20.00 20.50
Total 100.00 100.00 100.00
The storage stability study of all the recipes of Metamifop 4%+Bentazone 40%+Halosulfuron methyl 3% WG (Example 3, Example 4 and Example 5) meets the all in-house specifications like active ingredient content, pH, wettability, wet sieve, bulk density and moisture content criteria of laboratory storage and room temperature storage (up to 12 months).
Example 6: Metamifop 5%+Bentazone 50%+Halosulfuron methyl 4% WG
Ingredients Percent (w/w)
Metamifop a.i. 5.00
Bentazone a.i. 50.00
Halosulfuron methyl a.i. 4.00
Alkylated naphthalene sulfonate, sodium salt 3.00
Polyacrylate polymer sodium salt 6.00
Polyalkyleneoxide modified heptamethyltrisiloxane 4.00
Polydimethyl siloxane 0.50
Sodium sulphate anhydrous 6.00
Urea formaldehyde resin 15.50
China Clay 6.00
Total 100.00
The storage stability study of Metamifop 5%+Bentazone 50%+Halosulfuron methyl 4% WG meets the all in-house specifications like active ingredient content, pH, wettability, wet sieve, bulk density and moisture content criteria of laboratory storage and room temperature storage (up to 12 months).
Examples: Metamifop 5%+Bentazone 50%+Halosulfuron methyl 4% WG
Ingredients Percent (w/w)
Example 7 Example 8 Example 9
Metamifop a.i. 5.00 5.00 5.00
Bentazone a.i. 50.00 50.00 50.00
Halosulfuron methyl a.i. 4.00 4.00 4.00
Alkylated naphthalene sulfonate, sodium salt 3.00 3.00 3.00
Polyacrylate polymer sodium salt 6.00 6.00 6.00
Polyalkyleneoxide
modified heptamethyltrisiloxane 3.00 4.50 5.00
Polydimethyl siloxane 0.50 0.50 0.50
Sodium sulphate anhydrous 6.00 6.00 6.00
Urea formaldehyde resin 16.00 15.00 14.50
China Clay 6.50 6.00 6.00
Total 100.00 100.00 100.00
The storage stability study of all the recipes of Metamifop 5%+Bentazone 50%+Halosulfuron methyl 4% WG (Example 7, Example 8 and Example 9) meets the all in-house specifications like active ingredient content, pH, wettability, wet sieve, bulk density and moisture content criteria of laboratory storage and room temperature storage (up to 12 months).
Example 10: Metamifop 5%+Bentazone 50%+Chlorimuron ethyl 0.5% WG
Table 10.1: Metamifop 5%+Bentazone 50%+Chlorimuron ethyl 0.5% WG with organosilicone surfactant-Polyalkyleneoxide modified heptamethyltrisiloxane
Ingredients Percent (w/w)
Metamifop a.i. 5.00
Bentazone a.i. 50.00
Chlorimuron ethyl a.i. 0.50
Alkylated naphthalene sulfonate, sodium salt 3.50
Polyacrylate polymer sodium salt 6.50
Polyalkyleneoxide modified heptamethyltrisiloxane 2.50
Polydimethyl siloxane 0.50
Sodium sulphate anhydrous 7.00
Urea formaldehyde resin 12.00
China Clay 12.50
Total 100.00
The storage stability study of Metamifop 5%+Bentazone 50%+Chlorimuron ethyl 0.5% WG (with polyalkyleneoxide modified heptamethyltrisiloxane) meets the all in-house specifications like active ingredient content, pH, wettability, wet sieve, bulk density and moisture content criteria of laboratory storage and room temperature storage (up to 12 months).
Example 11: Metamifop 5%+Bentazone 50%+Chlorimuron ethyl 0.5% WG
Table 11.1: Metamifop 5%+Bentazone 50%+Chlorimuron ethyl 0.5% WG without organosilicone surfactant-Polyalkyleneoxide modified heptamethyltrisiloxane
Ingredients Percent (w/w)
Metamifop a.i. 5.00
Bentazone a.i. 50.00
Chlorimuron ethyl a.i. 0.50
Alkylated naphthalene sulfonate, sodium salt 3.50
Polyacrylate polymer sodium salt 6.50
Sodium Lauryl sulfate 2.50
Polydimethyl siloxane 0.50
Sodium sulphate anhydrous 7.00
Urea formaldehyde resin 12.00
China Clay 12.50
Total 100.00
The storage stability study of Metamifop 5%+Bentazone 50%+Chlorimuron ethyl 0.5% WG (without polyalkyleneoxide modified heptamethyltrisiloxane) meets the all in-house specifications like active ingredient content, pH, wettability, wet sieve, bulk density and moisture content criteria of laboratory storage and room temperature storage (up to 12 months).
Biological Examples:
The field experiments of present invention were carried out to study the biological effects on various crops like rice (Oryza sativa) and soybean (Glycine max). Rice and soybean are very important crops in India and world. Weeds (unwanted plants) alone causes about 30% yield loss in both crops. The weeds mainly comprises of grassy weeds (monocots, narrow leaf), broad leaf (dicots) and sedges. Its very important to control or manage the weeds during early crop stage. Farmers apply chemicals (herbicides) to control weeds. The continuous uses of herbicides with single mode of action, leads to development of resistance, which causes severe yield loss and increased cost of cultivations. Metamifop (Inhibitor of Acetyl CoA Carboxylase) is grass killer herbicide applied as post emergence, bentazone is selective herbicide, applied to control broad leaf weeds and sedges in soybean, peanut, rice, maize etc. Halosulfuron methyl is sulfonyl urea group herbicide, controls broad leaf weeds and sedges. The efficacy of metamifop, bentazone and halosulfuron methyl has not been studied in rice/paddy and soybean crop. Keeping the above facts in view, the present investigation was carried out to adjudge the effect of herbicidal mixture on weed indices and yield attributes of rice and soybean by an innovative ternary pre-mix herbicide mixture.

Experiment 1: Weed control in rice/paddy, Oryza sativa
Crops: Rice (transplanted)
No. of Treatments: 15
Plot size: 24 sq. mt.
Application Time: 15 DATP (Days after transplanting)
Spray Volume: 375 liter water per hectare
Application Equipment: Manually operated knapsack sprayer fitted with flat fat nozzle
Weed control(%): Species wise weed count recorded at 15 DAA (Days after Application) by using 0.25 m2 (50 cm x 50 cm) quadrant treatment wise in minimum 4 places randomly selected in the plot. The species wise weed count further grouped in to Grasses and Broad Leaf weeds (BLW) and sedges. The average of each variable was used together with the sum of all the variables per plot to calculate the percentage of control.

The % weed control (observed value) data used in Colby’s formula to calculate the synergism.
A synergistic effect exists wherever the action of a combination of active ingredient is greater than the sum of the action of each of the components alone. Therefore, a synergistically effective amount or an effective amount of a synergistic composition or combination is an amount that exhibits greater pesticidal activity than the sum of the pesticidal activities of the individual components.

Phytotoxicity: The observations on crop safety i.e. phytotoxicity or adverse effect of treatments were recorded at regular interval. All the visual phytotoxicity symptoms like plant yellowing, leaf scorching, tip burning, bleaching, necrosis, stunting, crinkling, epinasty, hyponasty recorded by rating (0 to 10 score) the entire plot in comparison with untreated control (UTC) plot. Following rating were adopted. Score 0=No injury, Score 1=1 to 10%, Score 2=11 to 20%, Score 3=21 to 30%.......Score 10=91 to 100% Phytotoxicity.
Table 1: Bio-efficacy against mixed weed flora in rice crop
Treatments Application Rate (gai/h) Weed control (%) observed Weed control (%) expected Colby's ratio Synergism (Y/N)
T1-Metamifop 3%+Bentazone 30%+Halosulfuron methyl 3% WG 60+600+60 92.8 89.17 1.04 Y
T2-Metamifop 4%+Bentazone 30%+Halosulfuron methyl 3% WG 80+600+60 95.4 91.44 1.04 Y
T3-Metamifop 3%+Bentazone 40%+Halosulfuron methyl 3% WG 60+800+60 96.2 92.47 1.04 Y
T4-Metamifop 4%+Bentazone 40%+Halosulfuron methyl 3% WG 80+800+60 100.0 94.05 1.06 Y
T5-Metamifop 3%+Bentazone 30%+Halosulfuron methyl 4% WG 60+600+80 96.2 91.81 1.05 Y
T6-Metamifop 4%+Bentazone 30%+Halosulfuron methyl 4% WG 80+600+80 100.0 93.53 1.07 Y
T7-Metamifop 3%+Bentazone 40%+Halosulfuron methyl 4% WG 60+800+80 98.2 94.31 1.04 Y
T8-Metamifop 4%+Bentazone 40%+Halosulfuron methyl 4% WG 80+800+80 100.0 95.51 1.05 Y
T9-Metamifop 10% EC 60 56.2
T10-Metamifop 10% EC 80 65.4
T11-Bentazone 48% SL 600 52.8
T12-Bentazone 48% SL 800 67.2
T13-Halosulfuron methyl 75% WG 60 47.6
T14-Halosulfuron methyl 75% WG 80 60.4
T15-UTC (Untreated Check) 0 0.0
T1 to T8-innovative novel WG formulation with polyalkyleneoxide modified heptamethyltrisiloxane, T9 to T14- market available products.
Weed flora composition in trial plot- Grassy weeds (Echinochloa colona, Leptochloa chinensis), Broad leaf weeds (Eclipta alba, Ammania baccifera), Sedges (Cyprus irria, Cyperus difformis).
All the innovative treatments (T1 to T8) provides synergistic weed control.
Experiment 2: Bio-efficacy comparison of different recipes
Crops: Rice (direct seeded)
No. of Treatments: 7
Plot size: 30 sq. mt.
Application Time: 16 DATP (Days after transplanting)
Spray Volume: 375 liter water per hectare
Application Equipment: Manually operated knapsack sprayer fitted with flat fat nozzle
Weed control (%): as given experiment 1.

Table 2: bio efficacy comparison of different recipes in rice crop
Treatments Application Rate (gai/h) Weed control (%) at 15 DAA Increase in weed control over Recipe B Increase in weed control over tank mixes
T1-Metamifop 4%+Bentazone 40%+Halosulfuron methyl 3% WG (Recipe A)-2000 g 80+800+60 100.0 6.2 9.4
T2-Metamifop 4%+Bentazone 40%+Halosulfuron methyl 3% WG (Recipe B)-2000 g 80+800+60 94.2
T3-Metamifop 10% EC+Bentazone 48% SL+Halosulfuron methyl 75% WG (800 ml+1666.67 ml+80 g)- tank mixes 80+800+60 91.4
T4-Metamifop 4%+Bentazone 40%+Halosulfuron methyl 3% WG (Recipe A)-1600 g 64+640+48 92.6 13.2 20.9
T5-Metamifop 4%+Bentazone 40%+Halosulfuron methyl 3% WG (Recipe B)-1600 g 64+640+48 81.8
T6-Metamifop 10% EC+Bentazone 48% SL+Halosulfuron methyl 75% WG (640 ml+1333.33 ml+64 g)- tank mixes 64+640+48 76.6
T7-UTC (Untreated Check) 0 0.0
Recipe A - innovative WG formulation with polyalkyleneoxide-modified heptamethyltrisiloxane, Recipe B-conventional WG formulation without polyalkyleneoxide modified heptamethyltrisiloxane.
Weed flora composition in trial plot- Grassy weeds (Echinochloa colona, Eleusine indica), Broad leaf weeds (Portulaca oleracea), Sedges (Cyperus irria, Fimbristylis miliacea).
Both the doses of Recipe-A provides higher weed control as compared to Recipe-B and tank mixes. Higher dose of Recipe A provides 6.2% and 9.4% higher weed control as compared to higher dose of Recipe B and their tank mixes respectively, where as lower dose of Recipe A provides 13.2% and 20.9% higher weed control as compared to lower dose of Recipe B and their tank mixes respectively.
Experiment 3: Weed control in direct seeded rice
Crops: Rice (direct seeded)
No. of Treatments: 12
Plot size: 30 sq. mt.
Application Time: 20 (Days after sowing)
Spray Volume: 400 liter water per hectare
Application Equipment: Manually operated knapsack sprayer fitted with flat fat nozzle
Weed control(%): as given in experiment 1.
Table 3: Treatment details
Treatment number Treatments Formulation per hectare (ml or g) Application Rate (gai/h)
T1 Metamifop 5%+Bentazone 50%+Halosulfuron methyl 4% WG, 1500 g 1500 g 75+750+60
T2 Metamifop 5%+Bentazone 50%+Chlorimuron ethyl 0.15% WG, 1500 g 1500 g 75+750+2.25
T3 Metamifop 5%+Bentazone 50%+Metsulfuron methyl 0.15% WG, 1500 g 1500 g 75+750+2.25
T4 Metamifop 10% EC+Bentazone 48% SL+Halosulfuron methyl 75% WG 750 ml+1562.5 ml+80 g 75+750+60
T5 Metamifop 10% EC+Bentazone 48% SL+Chlorimuron ethyl 25% WP 750 ml+1562.5 ml+9 g 75+750+2.25
T6 Metamifop 10% EC+Bentazone 48% SL+Metsulfuron methyl 20% WP 750 ml+1562.5 ml+11.25 g 75+750+2.25
T7 Metamifop 5%+Cyhalofop butyl 5%+Halosulfuron methyl 8% OD 1000 ml 50+50+80
T8 Metamifop 12.5%+Bispyribac sodium 5%+Pyrazosulfuron ethyl 5% SE 400 ml 50+20+20
T9 Metamifop 10%+Halosulfuron methyl 8% OD 1000 ml 100+80
T10 Metamifop 10%+Bispyribac sodium 4% SE 1000 ml 100+40
T11 Penoxsulam 1%+Bentazone 36% OD 2000 ml 20+720
T12 UTC (Untreated Check) 0
T1 to T3-innovative WG formulation, T4 to T6-tank mix of market available formulation, T7 to T11-conventional ready mix formulations

Table 4: Weed control and yield attributes
Treatment number % Weed control Average number of productive tillers/sq.mt. Increase(a%) in productive tillers over UTC Plant height (cm) Increase(%) in plant height over UTC
15 DAA 30 DAA
Grassy weeds Broad leaf weeds Sedges Grassy weeds Broad leaf weeds Sedges
T1 100.0 100.0 100.0 97.2 100.00 99.20 216.7 24.4 108.5 15.7
T2 100.0 100.0 98.4 96.8 100.00 98.00 213.5 22.6 107.2 14.3
T3 100.0 100.0 98.0 97.2 100.00 97.60 212.8 22.2 107.4 14.5
T4 94.2 96.8 97.4 89.6 92.40 85.20 202.3 16.1 102.3 9.1
T5 91.6 94.6 90.2 87.4 90.20 83.40 201.7 15.8 101.5 8.2
T6 90.8 92.4 91.2 86.2 88.80 81.20 200.6 15.2 101.3 8.0
T7 98.6 62.8 97.6 93 50.80 90.40 196.3 12.7 101.2 7.9
T8 94.6 42.8 71.6 87.6 35.20 54.60 195.8 12.4 100.8 7.5
T9 93.8 48.4 96.8 85.4 44.20 91.20 193.2 10.9 100.5 7.1
T10 97.4 36.8 40.6 91.8 30.40 34.80 190.7 9.5 100.3 6.9
T11 58.2 86.2 68.6 45.6 74.20 56.20 187.5 7.6 100.7 7.4
T12 0.0 0.0 0.0 0.0 0.0 0.0 174.2 0.0 93.8 0.0

Ready-mix innovative formulations (T1 to T3) provides excellent weed control and higher yield attributes (plant height and number of productive tillers) as compared to their tank mixes and other conventional ready mix combinations.

Experiment 4: Weed control in soybean, Glycine max
Crops: Soybean
No. of Treatments: 7
Plot size: 24 sq. mt.
Application Time: 18 DAS (Days after sowing)
Spray Volume: 400 liter water per hectare
Application Equipment: Manually operated knapsack sprayer fitted with flat fat nozzle
Weed control(%): same as given in experiment 1.
Table 5: bio efficacy comparison of different recipes in rice crop
Treatments Application Rate (gai/h) Weed control(%) at 15 DAA Increase in weed control over Recipe D Increase in weed control over tank mixes
T1-Metamifop 5%+Bentazone 50%+Chlorimuron ethyl 0.5% WG (Recipe C)-1500 g 75+750+7.5 100.0 6.8 5.5
T3-Metamifop 5%+Bentazone 50%+Chlorimuron ethyl 0.5% WG (Recipe D)-1500 g 75+750+7.5 93.6
T5-Metamifop 10% EC+Bentazone 48% SL+Chlorimuron ethyl 25% WP (750 ml+1562.5 ml+30 g)-tank mixes 75+750+7.5 94.8
T2-Metamifop 5%+Bentazone 50%+Chlorimuron ethyl 0.5% WG (Recipe C)-1250 g 62.5+625+6.25 93.0 9.2 13.1
T4-Metamifop 5%+Bentazone 50%+Chlorimuron ethyl 0.5% WG (Recipe D)-1250 g 62.5+625+6.25 85.2
T6-Metamifop 10% EC+Bentazone 48% SL+Halosulfuron methyl 75% WG (625 ml+1302 ml+25 g)-tank mixes 62.5+625+6.25 82.2
T7-UTC (Untreated Check) 0 0.0
Recipe C-innovative ready mix WG formulation with polyalkyleneoxide modified heptamethyltrisiloxane, Recipe D-conventional WG formulation without polyalkyleneoxide modified heptamethyltrisiloxane.
Weed flora composition in trial plot- Grassy weeds (Echinochloa colona), Broad leaf weeds (Commelina communis, Acalypha indica, Euphorbia hirta), Sedges (Cyperus rotundus).
Both the doses of Recipe-C provides higher weed control as compared to Recipe-D and tank mixes. Higher dose of Recipe C provides 6.8% and 5.5% higher weed control as compared to higher dose of Recipe-D and their tank mixes respectively, whereas lower dose of Recipe C provides 9.2% and 13.1% higher weed control as compared to lower dose of Recipe D and their tank mixes respectively.
Experiment 5: Weed control in soybean, Glycine max
Crops: Soybean
No. of Treatments: 9
Plot size: 24 sq. mt.
Application Time: 24 DAS (Days after sowing)
Spray Volume: 400 liter water per hectare
Application Equipment: Manually operated knapsack sprayer fitted with flat fat nozzle
Weed control (%): same as given in experiment 1.
Table 6: Treatment details
Treatment number Treatments Formulation per hectare (ml or g) Application Rate (gai/h)
T1 Metamifop 5%+Bentazone 50%+Chlorimuron ethyl 0.5% WG (innovative ready mix formulation) 1000 ml 50+500+5
T2 Metamifop 10% EC+Bentazone 48% SL+Chlorimuron ethyl 25% WP (tank mix of market products) 500 ml+1041.7 ml+20 g 50+500+5
T3 Metamifop 4%+Bentazone 20% ME 2000 ml 80+400
T4 Quizalofop 12%+Fomesafen 3% SC 1500 ml 45+180
T5 Clodinafop propargyl 8%+Sodium Acifluorfen 16.5% EC 1000 ml 80+165
T6 Metamifop 10% EC 500 ml 50
T7 Bentazone 48% SL 1041.7 ml 500
T8 Chlorimuron ethyl 25% WP 20 g+ 0.2% NIS 5+0.2% NIS
T9 UTC (Untreated Check) - -
T1-innovative ready mix formulation, T2-tank mix of market available products, T3 to T5-ready mix conventional combinations.

Table 7: Weed control in soybean crop.
Treatment number % Weed control Average number of pods/plant Increase(%) in productive tillers over UTC Plant height (cm) Increase(%) in plant height over UTC
15 DAA 30 DAA
Grassy weeds Broad leaf weeds Sedges Grassy weeds Broad leaf weeds Sedges
T1 100.0 100.0 100.0 98.6 100.0 100.0 45.6 112.1 47.2 20.4
T2 97.4 98.6 99.2 95.2 96.8 97.2 42.8 99.1 46.4 18.4
T3 99.8 80.6 68.4 98.0 69.6 62.4 42.6 98.1 45.8 16.8
T4 94.2 96.8 58.2 85.4 88.6 34.2 42.7 98.6 46.2 17.9
T5 96.2 94.2 50.8 80.6 78.6 26.8 41.9 94.9 46.2 17.9
T6 98.6 0.0 12.8 90.4 0.0 8.6 38.7 80.0 44.3 13.0
T7 10.8 94.2 92.2 7.6 88.6 80.4 38.5 79.1 43.9 12.0
T8 0.0 68.4 64.2 0 62.6 58.2 36.3 68.8 44.6 13.8
T9 0.0 0.0 0.0 0.0 0.0 0.0 21.5 0.0 39.2 0.0

Ready mix innovative formulation (T1) provides excellent weed control (grasses, broad leaf weeds and sedges) and also produces higher (>12%) number pods as compared to their tank mixes and other conventional ready mix combinations.

Experiment 6: Crop safety in rice crop
Crop: Rice (direct seeded)
Crop Stage: 15 Days after sowing
Water volume: 375 liter per hectare
Table 8: Phytotoxicity study in rice crop
Treatment number Treatments Application Rate (gai/h) Phytotoxicity observations up to 30 days Plant height (cm) Number of productive tillers per hill
T1 Metamifop 5%+Bentazone 50%+Halosulfuron methyl 4% WG, 1500 g 75+750+60 No visible symptoms 109.1 220.4
T2 Metamifop 4%+Bentazone 40%+Halosulfuron methyl 3% WG (Recipe A)-2000 g 80+800+60 No visible symptoms 108.8 221.1
T3 Metamifop 4%+Bentazone 40%+Halosulfuron methyl 4% WG, 2000 g 80+800+80 Slight tip burining (up to 5%), which recovers within 10 days 108.3 219.8
T4 Metamifop 10% EC+Bentazone 48% SL+Halosulfuron methyl 75% WG (750 ml+1562.5 ml+80 g) 75+750+60 tip burining (up to 10%) and yellowing of leaves, which recovers within 20 days 106.3 212.6
T5 Metamifop 10% EC+Bentazone 48% SL+Halosulfuron methyl 75% WG (800 ml+1666.67 ml+80 g) 80+800+60 tip burining (up to 10%), yellowing of leaves, which recovers within 20 days 104.8 210.5
T6 Metamifop 10% EC+Bentazone 48% SL+Halosulfuron methyl 75% WG (800 ml+1666.67 ml+106.67 g) 80+800+80 tip burining (up to 300%) and drying of upper part of leaves, yellowing of leaves and stunted growth of plant (up to 20%). 101.3 209.7
T7 UTC (Untreated Check) 0 0 107.7 194.6
T1 to T3-innovative ready mix WG formulation, T4 to T6-tank mixes of market available formulations.

All the doses of innovative ready mix WG formulations (T1 to T3) does not causes any significant phytotoxicity to rice crop and does not have any negative impact on yield attributing parameters like plant height and productive tillers, where as their tank mixes (T4 to T6) shows phytotoxicity symptoms and also had lower number of productive tillers.

Experiment 7: Spreading properties study
Method: Spreading properties test conducted by preparing 1% solution (1 g formulation in 100 ml water). Drop the solution on leaf surface and measure the spreading diameter (mm) after 30 seconds. Spreading diameter measured by graph paper.
Table 9: Spreading property study
Recipes Room temperature storage
1 month 6 months 12 months
(Spreading diameter in mm)
Metamifop 4%+Bentazone 40%+Halosulfuron methyl 3% WG (Recipe A) 14 14 13
Metamifop 4%+Bentazone 40%+Halosulfuron methyl 3% WG (Recipe B) 6 6 4

Recipe A of Metamifop+Bentazone+Halosulfuron methyl shows excellent spreading properties as compared to Recipe B. This will improves the bio-efficacy under field condition, by enhancing spreading action and penetration. Also improves the rain-fast properties during rainy days.

The bio efficacy study for the present invention shows:
• an excellent weed control of grassy, broad leaf weeds and sedges
• an excellent bio-efficacy against tough to kill weeds like, Leptochloa chinensis, Eleusine indica in rice and Acalypha indica in soybean
• an optimum Residual weed control
• an excellent crop safety to rice and soybean
• an increases in yield attributing parameters.
, Claims:CLAIMS
We claim;
[CLAIM 1]. A synergistic granular herbicidal composition comprising:
a. metamifop;
b. bentazone;
c. an herbicide compound selected from halosulfuron methyl, chlorimuron ethyl or metsulfuron methyl;
d. wetting agent is polyalkyleneoxide modified heptamethyl trisiloxane;
e. one or more inactive formulation excipients.

[CLAIM 2]. The synergistic granular herbicidal composition as claimed in claim 1, wherein wetting agent Polyalkyleneoxide modified heptamethyl trisiloxane
is present in amount of 1% - 6% w/w.

[CLAIM 3]. The synergistic granular herbicidal composition as claimed in claim 1, wherein preferred range for wetting agent Polyalkyleneoxide modified heptamethyl trisiloxane is 2% - 5% w/w.

[CLAIM 4]. The synergistic granular herbicidal composition as claimed in claim 1, wherein Metamifop is present in amount of 3% - 10 % w/w

[CLAIM 5]. The synergistic granular herbicidal composition as claimed in claim 1, wherein Bentazone is present in amount of 25 % - 60 % w/w

[CLAIM 6]. The synergistic granular herbicidal composition as claimed in claim 1, an herbicide compound selected from halosulfuron methyl, chlorimuron ethyl or metsulfuron methyl present in an amount of 0.05% to 4% w/w.

[CLAIM 7]. The synergistic granular herbicidal composition as claimed in claim 1, wherein the preferred combination of active ingredients for the said composition is selected :
a. Metamifop + Bentazone + halosulfuron methyl;
b. Metamifop + Bentazone + chlorimuron ethyl;
c. Metamifop + Bentazone + metsulfuron methyl.

[CLAIM 8]. The synergistic granular herbicidal composition as claimed in claim 1, wherein formulation for the said composition is Wettable Granule (WG) formulation.

[CLAIM 9]. The synergistic granular herbicidal composition as claimed in claim 1, wherein formulation excipients are selected from the dispersing agent, wetting agent, antifoaming agent, carrier and humectant.

[CLAIM 10]. The synergistic granular herbicidal composition as claimed in claim 9, wherein the dispersing agent is selected from Alkylated naphthalene sulfonate sodium salt, sodium polycarboxylate, naphthalene sulfonic acid, sodium salt condensates with formaldehyde, polyalcoxylated alkylphenol, naphthalene sulfonic acid formaldehyde condensate, methyl naphthalene-formaldehyde-condensate sodium salt, naphthalene condensates, lignosulfonates, , calcium lignosulfonate, lignin sulfonate sodium salt.

[CLAIM 11]. The synergistic granular herbicidal composition as claimed in claim 9, wherein the dispersing agent is present in an amount of 1.0%-6.0%w/w.

[CLAIM 12]. The synergistic granular herbicidal composition as claimed in claim 9, wherein wetting agent is selected from trisiloxane ethoxylate, polydimethylsiloxane, polyoxyethylene methyl polysiloxane, polyoxyalkylene methyl polysiloxane, polyether polymethyl siloxane copolymer, trisiloxane heptamethyl, Polyalkyleneoxide modified heptamethyl trisiloxane, polyether modified polysiloxane, may or may not be in modified form, may be liquid or powder form or mixture thereof.

[CLAIM 13]. The synergistic granular herbicidal composition as claimed in claim 9, wherein wetting agent is present in an amount of 1.0%-6.0%w/w.

[CLAIM 14]. The synergistic granular herbicidal composition as claimed in claim 9, wherein the antifoaming agent is polydimethyl siloxane.

[CLAIM 15]. The synergistic granular herbicidal composition as claimed in claim 9, wherein the antifoaming agent is present in an amount of 0.1%-1.0%w/w.

[CLAIM 16]. The synergistic granular herbicidal composition as claimed in claim 9, wherein the carrier is selected from china clay, silica, lactose anhydrous, ammonium sulfate, sodium sulfate anhydrous, corn starch, urea, EDTA, urea formaldehyde resin, diatomaceous earth, kaolin, bentonite, kieselguhr, fuller's earth, attapulgite clay, bole, loess, talc, chalk, dolomite, limestone, lime, calcium carbonate, powdered magnesia, magnesium oxide, magnesium sulphate, sodium chloride, gypsum, calcium sulphate, pyrophyllite, silicates and silica gels; fertilizers such as, for example, ammonium sulphate, ammonium phosphate, ammonium nitrate and urea; natural products of vegetable origin such as, for example, grain meals and flours, bark meals, wood meals, nutshell meals and cellulosic powders; and synthetic polymeric materials such as, for example, ground or powdered plastics and resins, bentonites, zeolites, titanium dioxide, iron oxides and hydroxides, aluminium oxides and hydroxides, or organic materials such as bagasse, charcoal, or synthetic organic polymers.

[CLAIM 17]. The synergistic granular herbicidal composition as claimed in claim 9, wherein the carrier is present in an amount of 12.0%-22.0%w/w.

[CLAIM 18]. The synergistic granular herbicidal composition as claimed in claim 9, wherein the humectant is selected from humic acid, glycerol, lactose, Sodium sulphate anhydrous.

[CLAIM 19]. The synergistic granular herbicidal composition as claimed in claim 9, wherein the humectant is present in an amount of 4.0%-8.0%w/w.

Dated this 30th day of June, 2022