DESC:FIELD OF THE INVENTION
The present invention relates to synergistic ternary herbicidal compositions comprising Metribuzin and at least one herbicidal compound selected from Halosulfuron-methyl or Fenoxaprop-p-ethyl and at least one herbicidal compound selected from Ametryn or Bentazone/Bentazone sodium, formulation thereof and to a method of controlling undesired vegetation in crops of useful plants.
BACKGROUND OF THE INVENTION
Weeds and other unwanted vegetation inhibiting crop growth is a constantly recurring problem in agriculture. Therefore, the control of weeds or unwanted plants is economically important for the crop productivity. Researchers in the field of synthetic chemistry have produced an extensive variety of chemicals and chemical formulations as solo or in combination of active ingredients for the control of such weeds or unwanted plants. Formulation of chemical herbicides of many types have been disclosed in the literature and a large number of them are in commercial use.
Now a days in order to reduce the risk from increased number of herbicide resistant varieties of weeds, mixtures of different active compounds are employed for controlling weeds or unwanted plants. By combining different active compounds having different mechanism of action, it is possible to ensure successful control of large no. of weeds over a relatively longer period of time and preventing development of resistance. However, this requires continuous development of an effective composition with different active compounds, so as to avoid selection to the particular mechanism of action.
Therefore, there exists a continuous need to develop an herbicidal composition which is compatible and stable, synergistic, broad spectrum, environmentally safe and more effective in control of weeds or undesired plants in crops while using low content of actives. It is highly desirable that herbicidal compositions must show a broader scope of activity to avoid or to control the development of resistant varieties of weeds to the active ingredient (s) or to the mixtures of known active ingredients used by farmer while minimising the doses of chemical products sprayed in the agricultural fields.
As a solution to the above mentioned problems, the inventors of the present invention surprisingly found that composition comprising Metribuzin and at least one herbicidal compound selected from Halosulfuron-methyl or Fenoxaprop-p-ethyl and at least one herbicidal compound selected from Ametryn or Bentazone/Bentazone sodium provides effective control of wide range of weeds or undesired plants with much lesser amounts of actives along with other associated advantages.
SUMMARY OF THE INVENTION
Accordingly, the present invention provides a combination comprising of Metribuzin and at least one herbicidal compound selected from Halosulfuron-methyl or Fenoxaprop-p-ethyl and at least one herbicidal compound selected from Ametryn or Bentazone/Bentazone sodium and agriculturally acceptable additives.

In one aspect, the composition of the present invention comprises Metribuzin in the range of 1-50 % w/w; compound selected from Halosulfuron-methyl in the range of 1-50 % w/w or Fenoxaprop-p-ethyl in the range of 1-50 % w/w; and compound selected from Ametryn in the range of 1-50 % w/w or Bentazone/Bentazone sodium in the range of 1-50 % w/w and agriculturally acceptable additives.

In one other aspect, the composition of the present invention comprises Metribuzin preferably in the range of 1 -50 % w/w; compound selected from Halosulfuron-methyl in the range of 0.5-10% w/w or Fenoxaprop-p-ethyl in the range of 0.5-10 % w/w; and compound selected from Ametryn in the range of 5-50% w/w or Bentazone/Bentazone sodium in the range of 5-50% w/w and agriculturally acceptable additives.

In one another aspect, the composition of the present invention comprises Metribuzin more preferably in an amount of 3.4-24% w/w; compound selected from Halosulfuron-methyl in an amount of 1.4-2.6% w/w or Fenoxaprop-p-ethyl in an amount of 2.0-2.9%; and compound selected from Ametryn in an amount of 13-24 % w/w or Bentazone/Bentazone sodium in an amount of 11.2-24.3% w/w and agriculturally acceptable additives.
In an aspect, the composition of the present invention is formulated as Capsule suspension (CS), Dispersible concentrate (DC), Dustable powder (DP), Emulsifiable granule (EG), Emulsion water-in-oil (EO), Emulsifiable powder (EP), Granules (GR), Oil-dispersion (OD), Oil miscible flowable concentrate (OF), Oil miscible liquid (OL), Oil dispersible powder (OP), Suspension concentrate (SC), Suspension concentrate for direct application (SD), Suspo-emulsion (SE), Water soluble granule (SG), Soluble concentrate (SL), Spreading oil (SO), Water soluble powder (SP), Water soluble tablet (ST), Ultra-low volume (ULV) suspension, Tablet (TB), Ultra-low volume (ULV) liquid, Water dispersible granules (WG), Wettable powder (WP), Water dispersible tablet (WT), a mixed formulation of CS and SC (ZC) or A mixed formulation of CS and SE (ZE), preferably WP and SC.
In another aspect, the composition of the present invention comprises one or more agriculturally acceptable additive selected from the group comprising of dispersing agent(s), wetting agent(s), dispersing cum wetting agent(s), safener(s), defoaming agent(s) / defoamer(s) / antifoaming agent(s) / antifoamer(s), biocide(s)/preservative(s), viscosity modifier(s)/ rheology modifier(s)/ thickener (s), anti-settling agent(s), filler(s) and diluent(s) or a combination thereof and other additives as will be required in a particular type of formulation.
In another aspect, the composition of the present invention comprises the dispersing agent is selected from the group comprising naphthalene sulfonate formaldehyde condensate, sulfonated kraft lignin polymer, polymethyl methacrylate-polyethylene oxide graft copolymer, amine salt of phosphate tristyryl phenol ethoxylated, acrylic copolymer, graft copolymer, salt of naphthalene sulphonate, phosphate ester, salt of polycarboxylate, alcohol block copolymer, ethoxylated polyarylphenol phosphate ester, tristyrylphenol ethoxylate phosphate ester, or a combination thereof and present in an amount in the range from 0.1-5% w/w; the wetting agent is selected from the group comprising sodium isopropyl naphthalene sulfonate, sodium dioctyl sulphosuccinate, a copolymer condensate of ethylene and propylene oxide, sodium alkyl naphthalene sulfonate blend, ethoxylated polyarylphenol phosphate ester, non-ionic ethoxylate, castor oil ethoxylate or a combination thereof and present in an amount in the range from 0.1-5% w/w; the dispersing cum wetting agent is selected from the group comprising proprietary blend of phosphate ester and sodium naphthalene sulfonate formaldehyde condensate, highly sulfonation and low molecular weight kraft lignin polymer, sodium salt of aromatic ring surfactant, ammonium salt of aromatic ring surfactant, sodium salt of naphthalene sulphonic acid condensation, proprietary blend of anionic surfactant, sodium methyl oleoyl taurate, tristyrylphenol ethoxylate phosphate ester or a combination thereof and present in an amount in the range from 2-7% w/w; the safener is mefenpyr-diethyl and present in an amount in the range from 0.01 to 2% w/w; the defoamer is polydimethylsiloxane antifoam emulsion and present in an amount in the range from 0.01 to 1% w/w; the biocide/preservative is selected from the group comprising 20% aqueous dipropylene glycol solution of 1, 2- benzisothiazolin-3-one, formaldehyde, isothiazolinone or a combination thereof and present in an amount in the range from 0.01 to 1% w/w; the viscosity modifier is selected from the group comprising xanthan gum (2% solution), guar gum and present in an amount in the range from 5-15% w/w; the anti-settling agent is selected from the group comprising precipitated silica, organic bentonite, polyolefin particles and fumed silica and present in an amount in the range from 1.5 to 3.5% w/w; the filler is selected from the group comprising silica, sodium bicarbonate, china clay, lactose, bentonite clay, kaolin, diatomaceous earth or a combination thereof and present in an amount quantity sufficient; the diluent is demineralised water and present in an amount quantity sufficient.
DETAILED DESCRIPTION OF THE INVENTION
The definitions provided herein for the terminologies used in the present disclosure are for illustrative purpose only and in no manner limit the scope of the present invention disclosed in the present disclosure.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by a person of ordinary skill in the art to which the invention pertains. Although other methods and materials similar, or equivalent, to those described herein can be used in the practice of the present invention, the preferred materials and methods are described herein.
It is to be noted that, as used in the specification and the appended claims, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to a composition containing “a compound” includes a mixture of two or more compounds. It should also be noted that the term “or” is generally employed in its sense including “and/or” unless the content clearly dictates otherwise.
As used herein, the terms "comprises", "comprising", "includes", "including", “has”, “having”, “contains”, “containing”, “characterized by” or any other variation thereof, are intended to cover a non-exclusive inclusion, subject to any limitation explicitly indicated. For example, a composition, mixture, process or a method that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, mixture, process or method.
The transitional phrase “consisting of” excludes any element, step or ingredient not specified. If in the claim, such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase “consisting of” appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.
As used herein, the terms “composition” or "formulation" can be used interchangeably, unless stated otherwise, is meant to encompass, and are not limited to, compositions or formulations containing the combination of Metribuzin and at least one herbicidal compound selected from Halosulfuron-methyl or Fenoxaprop-p-ethyl and at least one herbicidal compound selected from Ametryn or Bentazone/Bentazone sodium.
As used herein, the term “agriculturally acceptable additive (s)” refers to inert substances and are auxiliary substances added to the processing or use of herbicide preparations and used to improve the physical and chemical properties of formulations. The auxiliaries themselves are essentially free of biological activity, but can affect the control effect.
The expression of various quantities in terms of “% w/w” or “%” means the percentage by weight, relative to the weight of the total solute on or composition unless otherwise specified.
The term “active ingredient” (a.i.) or “active agent” used herein refers to that component of the composition responsible for control of weeds or undesired plants.
As used herein, the term "effective amount" means the amount of the active substances in the compositions to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target weeds. An effective amount of the compositions will also vary according to the prevailing conditions such as desired herbicidal effect and duration, weather, target species, locus, mode of application, and the like.
As used herein, the term “herbicide”, refers to any chemical substance used to destroy/kill, delay, reduce, inhibit or otherwise adversely affect the growth of plants, especially weeds.
As used herein, the term “Metribuzin” encompasses its agrochemically acceptable salt(s), derivative(s) or any other modified form of Metribuzin. Metribuzin having IUPAC name 4-amino-6-tert-butyl-3- methylsulfanyl-1, 2, 4-triazin-5-one belongs to the group of triazinone herbicide. It acts by inhibition of photosystem II. It is a selective systemic herbicide, absorbed predominantly by the roots, but also by the leaves, with acropetal translocation in the xylem. It is used for pre and post-emergence control of grass and broad-leaved weeds in soybeans, potatoes, tomatoes, sugarcane, alfalfa, asparagus, maize and cereals.
As used herein, the term “Halosulfuron-methyl” is a derivative of Halosulfuron and encompasses its agrochemically acceptable salt(s), derivative(s) or any other modified form of Halosulfuron-methyl. Halosulfuron-methyl having IUPAC name methyl 3-chloro-5-(4, 6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl)-1-methylpyrazole-4-carboxylate belongs to pyrazole herbicide or pyrimidinylsulfonylurea herbicide. It shows its action by inhibiting acetolactate synthase (ALS) enzyme.
As used herein, the term “Fenoxaprop-p-ethyl” encompasses its agrochemically acceptable salt(s), acids such as Fenoxaprop, Fenoxaprop-p-ethyl, derivative(s) or any other modified form of Fenoxaprop-p-ethyl. Fenoxaprop-p-ethyl having IUPAC name (R)-2-[4-(6-chloro-1,3-benzoxazol-2-yloxy) phenoxy] propionic acid belongs to the class of aryloxyphenoxy propionate. It acts by acetyl CoA carboxylase inhibition. It is a selective herbicide with contact and systemic action, absorbed principally by the leaves, with translocation both acropetally and basipetally to the roots or rhizomes. It is used for post-emergence control of annual and perennial grass weeds in potatoes, beans, soybeans, beets, vegetables, peanuts, flax, oilseed rape and cotton.
As used herein, the term “Ametryn” encompasses its agrochemically acceptable salt(s), derivative(s) or any other modified form of Ametryn. Ametryn having IUPAC name N2-ethyl-N4-isopropyl-6-(methylthio)-1, 3, 5-triazine-2,4-diamine belongs to the group of triazine herbicide. It acts by binds to the plastoquinone-binding protein in photosystem II, inhibiting electron transport. Ametryn is a thiotriazine selective systematic herbicide absorbed principally through the roots, but also through the foliage, translocated acropetally in the xylem and accumulated in the apical meristems and leaves. It is used in banana, citrus, palm, and coffee and has limited use as a post directed spray on corn. Ametryn is effective against annual broadleaf weeds and grasses and is often used in tank mixes and in prepacks with other products. Ametryn is used for pre-emergence and post-emergence control of both monocotyledonous and dicotyledonous weeds in corn, sugarcane, banana, pineapple, and non-crop areas.
As used herein, the term “Bentazone” encompasses its agrochemically acceptable salt(s) preferably “Bentazone sodium”, derivative(s) or any other modified form of Bentazone. Bentazone having IUPAC name 3-isopropyl-1H-2, 1, 3-benzothiadiazin-4(3H)-one 2,2-dioxide belongs to the group of benzothiadiazinone herbicide. It acts by inhibition of photosystem II. It is a selective contact herbicide. It is used for post-emergence control of broad-leaved weeds in winter and spring cereals, peanuts, maize, peas, Phaseolus beans, rice and soybeans.
In an embodiment, the present invention provides a synergistic ternary herbicidal composition comprising of Metribuzin and at least one herbicidal compound selected from Halosulfuron-methyl or Fenoxaprop-p-ethyl and at least one herbicidal compound selected from Ametryn or Bentazone/Bentazone sodium and agriculturally acceptable additives.
In an embodiment, the present invention provides a synergistic ternary herbicidal compositions of Metribuzin in the range of 1-50 % w/w; compound selected from Halosulfuron-methyl in the range of 1-50 % w/w or Fenoxaprop-p-ethyl in the range of 1-50 % w/w; and compound selected from Ametryn in the range of 1-50 % w/w or Bentazone/Bentazone sodium in the range of 1-50 % w/w and agriculturally acceptable additives.
In an embodiment, the present invention provides a synergistic ternary herbicidal compositions of Metribuzin preferably in the range of 1-50 % w/w; compound selected from Halosulfuron-methyl in the range of 0.5-10% w/w or Fenoxaprop-p-ethyl in the range of 0.5-10 % w/w; and compound selected from Ametryn in the range of 5-50% w/w or Bentazone/Bentazone sodium in the range of 5-50% w/w and agriculturally acceptable additives.
In other embodiment, the present invention provides a synergistic ternary herbicidal compositions of Metribuzin is more preferably present in an amount of 3.4-24% w/w; compound selected from Halosulfuron-methyl is more preferably present in an amount of 1.4-2.6% w/w or Fenoxaprop-p-ethyl is more preferably present in an amount of 2.0-2.9%; and compound selected from Ametryn is more preferably present in an amount of 13-24 % w/w or Bentazone/ Bentazone sodium is more preferably present in an amount of 11.2-24.3% w/w and agriculturally acceptable additives.
In an aspect, the composition of the present invention is formulated as Capsule suspension (CS), Dispersible concentrate (DC), Dustable powder (DP), Emulsifiable granule (EG), Emulsion water-in-oil (EO), Emulsifiable powder (EP), Granules (GR), Oil-dispersion (OD), Oil miscible flowable concentrate (OF), Oil miscible liquid (OL), Oil dispersible powder (OP), Suspension concentrate (SC), Suspension concentrate for direct application (SD), Suspo-emulsion (SE), Water soluble granule (SG), Soluble concentrate (SL), Spreading oil (SO), Water soluble powder (SP), Water soluble tablet (ST), Ultra-low volume (ULV) suspension, Tablet (TB), Ultra-low volume (ULV) liquid, Water dispersible granules (WG), Wettable powder (WP), Water dispersible tablet (WT), a mixed formulation of CS and SC (ZC) or A mixed formulation of CS and SE (ZE), preferably WP and SC.
In an embodiment, the composition of the present invention comprises one or more agriculturally acceptable additive selected from the group comprising of dispersing agent(s), wetting agent(s), dispersing cum wetting agent(s), safener(s), defoaming agent(s) / defoamer(s) / antifoaming agent(s) / antifoamer(s), biocide(s)/preservative(s), viscosity modifier(s)/ rheology modifier(s)/ thickener (s), anti-settling agent(s), filler(s) and diluent(s) or a combination thereof and other additives as will be required in a particular type of formulation.
The composition of present invention uses dispersing agents to prevent agglomeration of solid particles and keep them suspended in fluid. Non-limiting examples of dispersing agent that can be used in the present invention include, but not limited to naphthalene sulfonate formaldehyde condensate, sulfonated kraft lignin polymer, polymethyl methacrylate-polyethylene oxide graft copolymer, amine salt of phosphate tristyryl phenol ethoxylated, acrylic copolymer, graft copolymer, salt of naphthalene sulphonate, phosphate ester, salt of polycarboxylate, alcohol block copolymer, ethoxylated polyarylphenol phosphate ester, tristyrylphenol ethoxylate phosphate ester. One or more dispersing agents may be used in the synergistic composition of the present invention. The dispersing agent is present in the range from 1 to 10 % w/w, preferably 0.1-5% w/w.
The composition of present invention uses wetting agent to facilitate the process of dispersion of the granules in the liquid. Non-limiting examples of wetting agents that can be used in the present invention include, but not limited to, sodium isopropyl naphthalene sulfonate, sodium dioctyl sulphosuccinate, a copolymer condensate of ethylene and propylene oxide, sodium alkyl naphthalene sulfonate blend, ethoxylated polyarylphenol phosphate ester, non-ionic ethoxylate, castor oil ethoxylated. One or more wetting agents may be used in the synergistic composition of the present invention. The wetting agents is present in the range from 0.1-10% w/w, preferably 0.1-5% w/w.
The composition of present invention also uses dispersing cum wetting agent. Non-limiting examples of dispersing cum wetting agent that can be used in the present invention include, but not limited to, proprietary blend of phosphate ester and sodium naphthalene sulfonate formaldehyde condensate, highly sulfonation and low molecular weight kraft lignin polymer, sodium salt of aromatic ring surfactant, ammonium salt of aromatic ring surfactant, sodium salt of naphthalene sulphonic acid condensation, proprietary blend of anionic surfactant, sodium methyl oleoyl taurate, tristyrylphenol ethoxylate phosphate ester. One or more dispersing cum wetting agent may be used in the synergistic composition of the present invention. Dispersing cum wetting agent is present in the range from 1-10% w/w, preferably 2-7 % w/w. Use of dispersing cum wetting agent not only reduce a total cost of formulation but also lower a chemical burden on environment.
A safener is to be understood as meaning a compound which eliminates or reduces the phytotoxic properties of herbicide in respect to useful plants, without substantially reducing the herbicidal activity against harmful plants. Non limiting examples of safeners that can be employed in present invention are mefenpyr, mefenpyr-diethyl, AD67, benoxacor, cloquintocet-mexyl, cyometrinil, cyprosulfamide, dichlormid, dicyclonon, dietholate, fenchlorazole, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen-ethyl, mephenate, metcamifen, naphthalic anhydride, oroxabetrinil, 4-(dichloroacetyl)-1-oxa-4- azaspiro[4.5]decane and 2,2,5-trimethyl-3- (dichloroacetyl)-1,3-oxazolidine or a combination thereof and is present in the range from 0.01 to 5% w/w, preferably 0.01-2 % w/w.
The composition of present invention uses defoaming agent. Suitable defoamer used herein, but not limited to, polydimethylsiloxane antifoam emulsion, silicon emulsion, polysiloxane emulsion, organic fluorine compounds or a combination thereof and present in the range from 0.01 to 5% w/w, preferably 0.01-1% w/w.
The composition of present invention uses biocide/preservatives to prevent the composition from spoilage due to bacteria, yeasts and fungi. Suitable biocide/preservative used herein, but not limited to 20% aqueous dipropylene glycol solution of 1,2- benzisothiazolin-3-one, formaldehyde, potassium sorbate, 4-hydroxybenzoic acid esters, 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one or a combination thereof and present in the range from 0.01 to 5% w/w, preferably 0.01-1% w/w.
The composition of present invention uses viscosity modifier. Suitable viscosity modifier used herein, but not limited water-soluble polymer and inorganic fine powder, wherein water-soluble polymer selected from xanthan gum, polyvinyl alcohol, carboxymethylcellulose, polyvinylpyrrolidone, carboxyvinyl polymer, acrylic polymer, starch derivative or polysaccharide; or an inorganic fine powder selected from high purity silica, bentonite, white carbon or a combination thereof and present in the range from 1-20 % w/w, preferably 5-15% w/w.
The composition of present invention uses anti-settling agent. Suitable anti-settling agent is selected from the group comprising precipitated silica, organic bentonite, polyolefin particles and fumed silica and present in the range from 1 to 5% w/w, preferably 1.5-3.5% w/w.
The composition of present invention uses filler. Suitable fillers that may be used in the composition of the present invention include, but not limited to, silica, sodium bicarbonate, china clay, lactose, bentonite clay, kaolin, diatomaceous earth. The filler may be used in an amount of quantity sufficient to make 100%w/w formulation.
The composition of present invention uses diluents. Suitable diluents that may be used in the composition of the present invention is demineralised water and present in an amount quantity sufficient.
The inventors have surprisingly found that the composition of the present invention showed enhances control over existing compositions.
In another embodiment, the compositions of the present invention are effective in the management of pre-emergent or post-emergent, monocotyledonous and dicotyledonous weeds especially grasses such as Phalaris minor, Avena fatua, Cynadon dactylon, Poa annua, Setaria gluca, Digitaria sanguinalis, Brachiaria spp., Echinocloa spp., Dactyloctenium aegyptium; broad leaved weeds such as Chenopodium album, Cercium arvensis, Melilotus alba/indica, Argemone Mexicana, Fumaria parviflora, Asphodelus tenuifolius, Carthamus oxyacantha, Launea sp., Pluchia lanceolat, Vicia enticulus, Phyllanthus niruri., Lathyrus aphaca, Medicago enticulate, Medicago lupulina, Spergula arvensis, Ipomea spp., Ageratum conyzoides, Tribulus terrestris, Anagalis arvensis, Alternenthera sessalis, Trianthama monogyna, Trianthama portulacastum, Boerhaavia diffusa, Portulaca oleracea, Commelina benghalensis, Parthenium hysterophorus, Euphorbia hirta, Setaria veridis, Amaranthus viridis, Rumex denticulata Convolvulus arvensis, Trianthema monogyna, Euphorbia geniculate, Amaranthus spinosus, Cloeme gynandra, Coccinia indica; sedges such as Cyperus rotundus, Cyperus Iria and Cyperus difformis.
The present invention also provides a process of preparing a composition comprising of Metribuzin and at least one herbicidal compound selected from Halosulfuron-methyl or Fenoxaprop-p-ethyl and at least one herbicidal compound selected from Ametryn or Bentazone/Bentazone sodium and at least one agriculturally acceptable additive.
In an embodiment, the present invention provides a process for the preparation of a WP formulation which comprises: a) weighing and mixing of required active ingredients and other ingredients; b) milling in a suitable air jet mill; c) grinding the material to obtain desired particle size (D90- <10 micron) and d) mixing homogeneously in a blender to obtain the wettable powder formulation.
In another embodiment, the present invention provides a process for the preparation of a SC formulation which comprises: a) diluting and solubilizing a biocide, defoamer, antifreeze agent and anti-settling agent in demineralised water in a mixing vessel and adding dispersing and wetting agent under stirring to get homogeneous mixture; b) adding active ingredients and safener one by one under stirring and mixing till homogeneous slurry obtained; c)wet grinding at suitable temperature till desired particle size obtained, if required water washing done and d) adding previously prepared viscosity modifier solution and stirring to obtain homogeneous mixture.
The composition of the present invention can be applied by spraying using flat-fan or flood-jet nozzles.
The rate of application amount of the prepared compositions varies depending on, for example, the blending ratio of active ingredients, meteorological condition, dosage form, application time, application method, application place, weed to be controlled, and a target crop, in ordinary cases.
In an embodiment of the present invention, combination of Metribuzin + Halosulfuron-methyl + Ametryn and Metribuzin + Halosulfuron-methyl + Bentazone/Bentazone sodium used for the pre-emergence or post-emergence weed control in variety of crops, including but not limited to sugarcane, wheat, potato, fibre crops, plantations and non-crop lands, preferably used in sugarcane, wheat and potato crops. As known to agro community sedges are a biggest problem in sugarcane field and needs to be controlled very effectively. At present Halosulfuron-methyl is widely used to control sedges in sugarcane fields, however its continuous use as a solo product not providing satisfactory results against sedges and further it provides no control on grasses and broad leaved weeds, the occurrence of grasses and broad leaved weeds cannot be overruled in sugarcane filed and in this case farmers have to use other herbicide which gives them cost burden whereas the combination of present invention Metribuzin+ Halosulfuron-methyl + Ametryn and Metribuzin + Halosulfuron-methyl + Bentazone/Bentazone sodium is not only very effective to control the sedges in sugarcane field but additionally it also provides excellent control against grasses and broad leaved weeds. Further due to synergistic nature of composition the much low amount of actives is used which benefitted to farmers as well as environment.
In another embodiment the composition of present invention i.e., Metribuzin + Fenoxaprop-p-Ethyl + Bentazone /Bentazone sodium used for the post-emergence weed control in wheat and potatoes. At present phalaris minor is the major problematic weed in wheat which is resistant to most of the herbicides including fenoxaprop, clodinafop, pinoxaden, sulfosulfuron, etc. secondly to control phalaris minor farmers are compelled to use much higher doses with multiple applications and cocktail of herbicides, even though effective control is not achieved and also suffers losses due to phytotoxicity. In this situation Metribuzin is the only favourably mixing partner to control resistant phalaris minor but results are still not satisfactory. Moreover occurrence of sedges specifically water scarce wheat field and broad leaved weeds cannot be overruled, hence the combination of present invention is effective not only for resistant phalaris minor but in a single shot use to control broad leaved weeds as well as sedges. Further due to synergistic nature of composition the much low amount of actives is used which benefitted to farmers as well as environment.
The synergistic composition of the present invention provides a number of other advantages:
Increased efficacy in comparison to the other formulations tested during the trial.
Is synergistic hence denies the need of sequential application of solo herbicides to control different weed spectra thereby reducing the environmental load of herbicides.
Uses lesser amounts of active ingredients hence considerable reduction in cost, which would benefit farmers.
This composition provided one shot solution to farmers to control broad spectrum weeds (grasses, broad leaved weeds and sedges)
Economically beneficial to the farmers as it provides better yield of the crop with reduction in the number of sprays.
Reduced possibility of hazards to the farmers due to occupational exposure because of reduction in the number of sprays.
Is storage stable.
Is non-phytotoxic.
Environmental friendly.

Thus, from the foregoing description, it will be apparent to one of the person skilled in the art that many changes and modifications can be made thereto without departing from the scope of the invention as set forth in the description. Accordingly, it is not intended that the scope of the foregoing description be limited to the description set forth above, but rather that such description be construed as encompassing such features that reside in the present invention, including all the features and embodiments that would be treated as equivalents thereof by those skilled in the relevant art.

The embodiments of the present invention are more particularly described in the following examples that are intended as illustrations only, since numerous modifications and variations within the scope of the present invention will be apparent to those of skill in the art. Unless otherwise noted, all parts, percentages and ratio reported in the following examples are on a weight basis and all excipients used in the examples were obtained or are available from the chemical suppliers.

EXAMPLES
The synergistic ternary herbicidal composition of the present invention comprising Metribuzin and at least one herbicidal compound selected from Halosulfuron-methyl or Fenoxaprop-p-ethyl and at least one herbicidal compound selected from Ametryn or Bentazone/Bentazone sodium and agriculturally acceptable additives in WP/SC form is provided in example 1 to 21. The unit of each component of the composition are expressed in “% w/w” i.e. the percentage by weight, relative to the weight of the total solution or composition. All the prepared composition of the present invention has been tested for stability/shelf life at accelerated temperature.

Table 1: Examples 1 to 5: Metribuzin + Halosulfuron-methyl + Ametryn (WP)
SN Ingredients RM Description Eg: 1 Eg: 2 Eg: 3 Eg: 4 Eg: 5
% w/w
1 Metribuzin Tech (100% Basis) Active Ingredient 10 13.2 14.8 8.8 4
2 Halosulfuron-methyl Tech (100% Basis) Active Ingredient 2 1.8 1.4 2.6 2.4
3 Ametryn Tech (100% Basis) Active Ingredient 20 16.8 13 13.2 24
4 Mefenpyr-diethyl Safener 1 1 1 1 1
5 Proprietary blend of phosphate ester and Sodium Naphthalene sulfonate formaldehyde condensate Dispersing cum wetting agent 3 3 2.8 2.5 3
6 Sodium Isopropyl Naphthalene Sulfonate Wetting agent 2 2 2 2 2
7 Naphthalene sulfonate formaldehyde condensate Dispersing agent 3.5 3.5 3.3 3.2 3.5
8 China clay Filler 1 55.5 55.7 58.7 63.7 57.1
9 Silica Filler 2 3 3 3 3 3
Total 100 100 100 100 100
Tech=Technical

Table 2: Quantities of active ingredients and raw material charged to prepare the composition of Metribuzin 10%+Halosulfuron-methyl 2%+ Ametryn 20% (WP)
SN Ingredients Qty gm
1 Metribuzin Tech (Purity 97%) 10.30
2 Halosulfuron Methyl Tech (Purity 98%) 2.04
3 Ametryn Tech (Purity 97%) 20.61
4 Mefenpyr-diethyl 1.00
5 Polymeric blend of dispersing agent and wetting agent surfactant 3.00
6 Sodium Isopropyl Naphthalene Sulfonate 2.00
7 Naphthalene sulfonate formaldehyde condensate 3.5
8 China clay 54.55
9 Silica 3.00
Total 100.00

Table 3: Stability studies (Shelf life based on accelerated storage at 54 ± 2°C)
Test parameter FAO Specification ‘0’ day RT 14 days HST at 54 ± 2°C
Metribuzin Content %w/w Min. 10% (±6%) 10.47% 10.02%
Halosulfuron methyl Content %w/w Min. 2% (±25%) 2.07% 2.01%
Ametryn Content %w/w Min. 20% (±6%) 20.34% 19.33%
Metribuzin Suspensibility %w/w Min. 80% 82.21% 78.20%
Halosulfuron methyl Suspensibility %w/w Min. 75% 79.88% 78.2%
Ametryn Suspensibility %w/w Min. 80% 86.11% 80.23%
Wet Sieve Test (75 µm) Max. 98% material pass through test sieve 99.63% 99.64%
pH 1 % (aqueous solution) 6 to 8 6.24 6.34
Persistent foam Max. 60 mL after 1 min. 45 ml 50 ml
Wetting out time Max. 60 sec 23 sec 25 sec

Table 4: Examples 6 to 10: Metribuzin + Halosulfuron-methyl + Bentazone Sodium (WP)
SN Ingredients RM Description Eg: 6 Eg: 7 Eg: 8 Eg: 9 Eg: 10
% w/w
1 Metribuzin Tech (100% Basis) Active Ingredient 24 10 12 7.2 16
2 Halosulfuron-methyl Tech (100% Basis) Active Ingredient 1.8 2 1.4 2.6 1.4
3 Bentazone sodium Tech (100% Basis) Active Ingredient 11.2 19.2 16 14.4 11.2
4 Mefenpyr-diethyl Safener 0.9 0.9 0.9 0.9 0.9
5 Proprietary blend of phosphate ester and Sodium Naphthalene sulfonate formaldehyde condensate Dispersing cum wetting agent 3 2.8 2.8 2.5 2.8
6 Sodium dioctylsulfosuccinate Wetting agent 2 2 2 2 2
7 Naphthalene sulfonate formaldehyde condensate Dispersing agent 3 2.8 2.8 2.5 2.8
8 Sodium bicarbonate Filler 1 4 4 4 4 4
9 China clay Filler 2 45.1 51.3 53.1 58.9 53.9
10 Lactose Filler 3 5 5 5 5 5
Total 100 100 100 100 100

Table 5: Quantities of active ingredients and raw material charged to prepare the composition of Metribuzin 24%+Halosulfuron-methyl 1.8%+ Bentazone sodium 11.2% (WP)
SN Ingredients Qty gm
1 Metribuzin Tech (Purity 97%) 24.7
2 Halosulfuron Methyl Tech (Purity 98%) 1.85
3 Bentazone sodium Tech (Purity 98%) 11.42
4 Mefenpyr-diethyl 0.9
5 Polymeric blend of dispersing agent and wetting agent surfactant 3.00
6 Sodium dioctylsulfosuccinate 2.00
7 Naphthalene sulfonate formaldehyde condensate 3.00
8 Sodium bicarbonate 4.1
9 China clay 44.03
10 Lactose 5.00
Total 100.00

Table 6: Stability studies (Shelf life based on accelerated storage at 54 ± 2°C)
Test parameter FAO Specification ‘0’ day RT 14 days HST at 54 ± 2°C
Metribuzin Content %w/w Min. 24% (±6%) 25.01% 25.17%
Halosulfuron methyl Content %w/w Min. 1.8% (±25%) 2.04% 2.06%
Bentazone sodium Content %w/w Min. 11.2% (±6%) 11.35% 11.34%
Metribuzin Suspensibility %w/w Min. 80% 84% 81%
Halosulfuron methyl Suspensibility %w/w Min. 75% 78% 76%
Bentazone sodium Suspensibility %w/w Min. 80% 89% 88%
Wet Sieve Test (75 µm) Max. 98% material pass through test sieve 99.8% 99.7%
pH 1 % (aqueous solution) 6 to 8 7.8 7.7
Persistent foam Max. 60 mL after 1 min. 45 ml 50 ml
Wetting out time Max. 60 sec 45 sec 40 sec

Table 7: Examples 11 to 15: Metribuzin + Halosulfuron-methyl + Bentazone (WP)
SN Ingredients RM Description Eg:11 Eg:12 Eg:13 Eg:14 Eg:15
%w/w
1 Metribuzin Tech (100% Basis) Active Ingredient 24 10 12 7.2 16
2 Halosulfuron-methyl Tech (100% Basis) Active Ingredient 1.8 2 1.4 2.6 1.4
3 Bentazone Tech (100% Basis) Active Ingredient 11.2 19.2 16 14.4 11.2
4 Mefenpyr-diethyl Safener 0.9 0.9 0.9 0.9 0.9
5 Proprietary blend of phosphate ester and Sodium Naphthalene sulfonate formaldehyde condensate Dispersing cum wetting agent 3 2.8 2.8 2.5 2.8
6 Sodium dioctylsulfosuccinate Wetting agent 2 2 2 2 2
7 Naphthalene sulfonate formaldehyde condensate Dispersing agent 3 2.8 2.8 2.5 2.8
8 China clay Filler 1 49.1 55.3 57.1 62.9 57.9
9 Lactose Filler 2 5 5 5 5 5
Total 100 100 100 100 100

Table 8: Quantities of active ingredients and raw material charged to prepare the composition of Metribuzin 24%+Halosulfuron-methyl 1.8%+ Bentazone 11.2% (WP)
SN Ingredients Qty gm
1 Metribuzin Tech (Purity 97%) 24.7
2 Halosulfuron Methyl Tech (Purity 98%) 1.85
3 Bentazone Tech (Purity 98%) 11.42
4 Mefenpyr-diethyl 0.9
5 Polymeric blend of dispersing agent
and wetting agent surfactant 3.00
6 Sodium dioctylsulfosuccinate 2.00
7 Naphthalene sulfonate formaldehyde condensate 3.00
8 China clay 48.13
9 Lactose 5.00
Total 100.00

Table 9: Stability studies (Shelf life based on accelerated storage at 54 ± 2°C)
Test parameter FAO Specification ‘0’ day RT 14 days HST at 54 ± 2°C
Metribuzin Content %w/w Min. 24% (±6%) 24.5% 24.32%
Halosulfuron methyl Content % w/w Min. 1.8% (±25%) 1.84% 1.82%
Bentazone Content %w/w Min. 11.2% (±6%) 11.40% 11.36%
Metribuzin Suspensibility %w/w Min. 80% 86% 83%
Halosulfuron methyl Suspensibility %w/w Min. 75% 76% 76%
Bentazone Suspensibility %w/w Min. 80% 90% 87%
Wet Sieve Test (75 µm) Max. 98% material
pass through test sieve 99.5% 99.6%
pH 1 % (aqueous solution) 6 to 8 5.4 5.5
Persistent foam Max. 60 mL after 1 min. 33 ml 36 ml
Wetting out time Max. 60 sec 51 sec 55 sec

Table 10: Examples 16 to 20: Metribuzin + Fenoxaprop-p-Ethyl + Bentazone sodium (WP)
SN Ingredients RM Description Eg:16 Eg:17 Eg:18 Eg:19 Eg:20
%w/w
1 Metribuzin Tech (100% Basis) Active Ingredient 6 7.1 5.1 6.4 3.4
2 Fenoxaprop-p-Ethyl Tech (100% Basis) Active Ingredient 2.9 2.6 2.9 2 2.6
3 Bentazone sodium Tech (100% Basis) Active Ingredient 12.9 22.9 20 21.4 24.3
4 Mefenpyr-diethyl Safener 1 1 1 1 1
5 Proprietary blend of phosphate ester and Sodium Naphthalene sulfonate formaldehyde condensate Dispersing cum wetting agent 1 3 3.5 3.5 3.5 3.5
6 Sulfonated kraft lignin polymer Dispersing agent 0.5 1 1 1 1
7 Highly sulfonation and low molecular weight kraft lignin polymer Dispersing cum wetting agent 2 2.5 2.5 2.5 2.5 2.5
8 Sodium bicarbonate Filler 1 5 5 5 5 5
9 China clay Filler 2 61.2 49.4 54 52.2 51.7
10 Lactose Filler 3 5 5 5 5 5
Total 100 100 100 100 100

Table 11: Quantities of active ingredients and raw material charged to prepare the composition of Metribuzin 6%+ Fenoxaprop-p-ethyl 2.9%+ Bentazone sodium 12.9% WP
SN Ingredients Qty gm
1 Metribuzin Tech (Purity 97%) 6.18
2 Fenoxaprop-p-ethyl Tech (Purity 98%) 2.98
3 Bentazone sodium Tech (Purity 97%) 13.29
4 Mefenpyr-diethyl 1.00
5 Polymeric blend of dispersing agent and wetting agent surfactant 3.00
6 Sulfonated kraft lignin polymer 0.5
7 Highly sulfonation and low molecular weight kraft lignin polymer 2.5
8 Sodium bicarbonate 5.00
9 China clay 60.55
10 Lactose 5.00
Total 100.00

Table 12: Stability studies (Shelf life based on accelerated storage at 54 ± 2°C)
Test parameter FAO Specification ‘0’day RT 14 days HST at 54 ± 2°C
Metribuzin Content %w/w Min. 6% (±10%) 6.57% 6.56%
Fenoxaprop-p-ethyl Content % w/w Min. 2.9% (±10%) 2.94% 2.91%
Bentazone sodium Content % w/w Min. 12.9% (±6%) 13.27% 13.22%
Metribuzin Suspensibility % w/w Min. 80% 92.5% 90.5%
Fenoxaprop-p-ethyl suspensibility %w/w Min. 75% 77.90% 76.76%
Bentazone sodium Suspensibility %w/w Min. 80% 90% 88%
Wet Sieve Test (75 µm) Max. 98% material pass through test sieve 99.6% 99.6%
pH 1 % (aqueous solution) 6 to 8 7.5 7.3
Persistent foam Max. 60 mL after 1 min. 43 ml 52 ml
Wetting out time Max. 60 sec 42 sec 37 sec

Table 13: Examples 21 to 25: Metribuzin + Fenoxaprop-p-Ethyl + Bentazone (WP)
SN Ingredients RM Description Eg:21 Eg:22 Eg:23 Eg:24 Eg:25
%w/w
1 Metribuzin Tech (100% Basis) Active Ingredient 6 7.1 5.1 6.4 3.4
2 Fenoxaprop-p-Ethyl Tech (100% Basis) Active Ingredient 2.9 2.6 2.9 2 2.6
3 Bentazone Tech (100% Basis) Active Ingredient 12.9 22.9 20 21.4 24.3
4 Mefenpyr-diethyl Safener 1 1 1 1 1
5 Proprietary blend of phosphate ester and Sodium Naphthalene sulfonate formaldehyde condensate Dispersing cum wetting agent 1 3 3.5 3.5 3.5 3.5
6 Sulfonated kraft lignin polymer Dispersing agent 0.5 1 1 1 1
7 Highly sulfonation and low molecular weight kraft lignin polymer Dispersing cum wetting agent 2 2.5 2.5 2.5 2.5 2.5
9 China clay Filler 1 66.2 54.4 59 57.2 56.7
10 Lactose Filler 2 5 5 5 5 5
Total 100 100 100 100 100

Table 14: Quantities of active ingredients and raw material charged to prepare the composition of Metribuzin 6%+ Fenoxaprop-p-ethyl 2.9%+ Bentazone 12.9% WP
SN Ingredients Qty gm
1 Metribuzin Tech (Purity 97%) 6.18
2 Fenoxaprop-p-ethyl Tech (Purity 98%) 2.98
3 Bentazone Tech (Purity 97%) 13.29
4 Mefenpyr-diethyl 1
5 Polymeric blend of dispersing agent and wetting agent surfactant 3
6 Sulfonated kraft lignin polymer 0.5
7 Highly sulfonation and low molecular weight kraft lignin polymer 2.5
8 China clay 65.55
9 Lactose 5.00
Total 100.00

Table 15: Stability studies (Shelf life based on accelerated storage at 54 ± 2°C)
Test parameter FAO Specification ‘0’ day RT 14 days HST at 54 ± 2°C
Metribuzin Content %w/w Min. 6% (±10%) 6.12% 6.09%
Fenoxaprop-p-ethyl Content % w/w Min. 2.9% (±10%) 3.01% 2.98%
Bentazone Content %w/w Min. 12.9% (±6%) 13.12% 13.00%
Metribuzin Suspensibility %w/w Min. 80% 90.7% 88.5%
Fenoxaprop-p-ethyl Suspensibility %w/w Min. 75% 79.99% 77.98%
Bentazone Suspensibility %w/w Min. 80% 92.2% 92.3%
Wet Sieve Test (75 µm) Max. 98% material pass through test sieve 99.7% 99.8%
pH 1 % (aqueous solution) 6 to 8 5.5 5.3
Persistent foam Max. 60 mL after 1 min. 40 ml 44 ml
Wetting out time Max. 60 sec 38 sec 33 sec

Table 16: Examples 26 to 30: Metribuzin + Fenoxaprop-p-Ethyl + Bentazone sodium (SC)
SN Ingredients RM Description Eg:26 Eg:27 Eg:28 Eg:29 Eg:30
%w/w
1 Metribuzin Tech (100% Basis) Active Ingredient 6 7.1 5.1 6.4 3.4
2 Fenoxaprop-p-Ethyl Tech (100% Basis) Active Ingredient 2.9 2.6 2.9 2 2.6
3 Bentazone sodium Tech (100% Basis) Active Ingredient 12.9 22.9 20 21.4 24.3
4 Mefenpyr-diethyl Safener 1 1 1 1 1
5 Propylene glycol Anti-freeze Agent 5 5 5 5 5
6 Polymethyl methacrylate-polyethylene oxide graft copolymer Dispersing Agent 3 3 3 3 3
7 A copolymer condensate of ethylene and propylene oxide Wetting Agent 1 2 2 2 2 2
8 Sodium alkyl naphthalene sulfonate blend Wetting Agent 2 0.5 0.5 0.5 0.5 0.5
9 Polydimethylsiloxane Antifoam Emulsion Defoamer 0.5 0.5 0.5 0.5 0.5
10 Benzisothiazolin-3-one Biocide 0.1 0.1 0.1 0.1 0.1
11 Xanthan Gum (2% solution) Viscosity modifier 15 15 15 15 15
12 PPT Silica Anti-settling agent 3.5 3.5 3.5 3.5 3.5
13 D. M. Water Diluent 47.6 36.8 41.4 39.6 39.1
Total 100 100 100 100 100

Table 17: Quantities of active ingredients and raw material charged to prepare the composition of Metribuzin 6%+ Fenoxaprop-p-ethyl 2.9%+ Bentazone sodium 12.9% SC
SN Raw Materials Qty gm
1 Metribuzin Tech (Purity 97%) 6.18
2 Fenoxaprop-p-Ethyl Tech (Purity 97%) 2.98
3 Bentazone sodium Tech (Purity 95%) 13.57
4 Mefenpyr-diethyl 1
5 Propylene glycol 5
6 Polymethyl methacrylate-polyethylene oxide graft copolymer 3
7 A copolymer condensate of ethylene and propylene oxide 2
8 Sodium alkyl naphthalene sulfonate blend 0.5
9 Polydimethylsiloxane Antifoam Emulsion 0.5
10 Benzisothiazolin-3-one 0.1
11 Xanthan Gum (2% solution) 15
12 PPT Silica 3.35
13 D. M. Water 46.82
Total 100

Table 18: Stability studies (Shelf life based on accelerated storage at 54 ± 2°C)
Test parameter FAO Specification ‘0’ day RT 14 days HST at 54 ± 2°C
Metribuzin Content %w/w Min. 6% (±10%) 6.18% 6.16%
Fenoxaprop-p-Ethyl Content
%w/w Min. 2.9% (±10%) 3.06% 2.98%
Bentazone sodium Content %w/w Min. 12.9% (±6%) 13.29% 13.15%
Metribuzin Suspensibility %w/w Min. 80% 95.45% 94.40%
Fenoxaprop-p-Ethyl Suspensibility %w/w Min. 80% 91.55% 90.8%
Bentazone sodium Suspensibility
%w/w Min. 80% 97.39% 96.78%
Wet Sieve Test (75 µm) Max. 98% material pass through test sieve 99.39% 98.43%
pH 1 % (aqueous solution) 2.5 to 4 9.5 9.0
Persistent foam Max. 60 mL after 1min. 3 ml 5 ml
Specific gravity 1.09 (±0.02) 1.09 --

Table 19: Examples 31 to 35: Metribuzin + Fenoxaprop-p-Ethyl + Bentazone (SC)
SN Ingredients RM Description Eg:31 Eg:32 Eg:33 Eg:34 Eg:35
%w/w
1 Metribuzin Tech (100% Basis) Active Ingredient 6 7.1 5.1 6.4 3.4
2 Fenoxaprop-p-Ethyl Tech (100% Basis) Active Ingredient 2.9 2.6 2.9 2 2.6
3 Bentazone Tech (100% Basis) Active Ingredient 12.9 22.9 20 21.4 24.3
4 Mefenpyr-diethyl Safener 1 1 1 1 1
5 Propylene glycol Anti-freeze Agent 5 5 5 5 5
6 Polymethyl methacrylate-polyethylene oxide graft copolymer Dispersing Agent 3 3.5 3.5 3.5 3.5
7 A copolymer condensate of ethylene and propylene oxide Wetting Agent 1 2 2.5 2.5 2.5 2.5
8 Sodium alkyl naphthalene sulfonate blend Wetting Agent 2 0.5 0.5 0.5 0.5 0.5
9 Polydimethylsiloxane Antifoam Emulsion Defoamer 0.5 0.5 0.5 0.5 0.5
10 Benzisothiazolin-3-one Biocide 0.1 0.1 0.1 0.1 0.1
11 Xanthan Gum (2% solution) Viscosity modifier 15 15 15 15 15
12 D. M. Water Diluent 51.1 39.3 43.9 42.1 41.6
Total 100 100 100 100 100

Table 20: Quantities of active ingredients and raw material charged to prepare the composition of Metribuzin 6%+ Fenoxaprop-p-ethyl 2.9%+ Bentazone 12.9% SC
SN Raw Materials Qty gm
1 Metribuzin Tech (Purity 97%) 6.18
2 Fenoxaprop-p-Ethyl Tech (Purity 97%) 2.98
3 Bentazone Tech (Purity 95%) 13.57
4 Mefenpyr-diethyl 1
5 Propylene glycol 5
6 Polymethyl methacrylate-polyethylene oxide graft copolymer 3
7 A copolymer condensate of ethylene and propylene oxide 2
8 Sodium alkyl naphthalene sulfonate blend 0.5
9 Polydimethylsiloxane Antifoam Emulsion 0.5
10 Benzisothiazolin-3-one 0.1
11 Xanthan Gum (2% solution) 15
12 D. M. Water 50.17
Total 100

Table 21: Stability studies (Shelf life based on accelerated storage at 54 ± 2°C)
Test parameter FAO Specification ‘0’ day RT 14 days HST at 54 ± 2°C
Metribuzin Content %w/w Min. 6% (±10%) 6.19% 6.11%
Fenoxaprop-p-Ethyl Content
%w/w Min. 2.9% (±10%) 2.93% 2.91%
Bentazone Content %w/w Min. 12.9% (±6%) 13.05% 12.99%
Metribuzin Suspensibility %w/w Min. 80% 92.88% 92.12%
Fenoxaprop-p-Ethyl suspensibility %w/w Min. 80% 94.75% 93.89%
Bentazone Suspensibility %w/w Min. 80% 90.39% 87.78%
Wet Sieve Test (75 µm) Max. 98% material pass through test sieve 99.79% 99.67%
pH 1 % (aqueous solution) 4 to 6 5.4 5.6
Persistent foam Max. 60 mL after 1
min. 5 ml 8 ml
Specific gravity 1.09 (±0.02) 1.09 --

As evident from the foregoing tables that all the desired composition has been prepared successfully and has been tested for stability/shelf life at accelerated temperature. After 14 days of storage at 54.0 ± 2 °C, there were no significant changes in active ingredient content, suspensibility, wettability, dispersibility, pH and has passes the sieve test. Therefore, it is concluded that composition of present invention has good stability and shelf life.

Bio-efficacy of the herbicidal composition of the present invention
The abbreviations used in present application for variety of Grasses, Broad leaved Weeds (BLW/BL) and Sedges are defined below:
Grass Variety Grass Variety Grass Variety
GS1 Dactyloctenium aegyptium GS2 Echinocloa spp. GS3 Brachiaria spp.
GS4 Phalaris minor GS5 Avena fatua GS6 Poa annua

BLW Variety BLW Variety BLW Variety
BL1 Trianthama portulacastum BL2 Alternenthera sessalis BL3 Boerhaavia diffusa
BL4 Portulaca oleracea BL5 Commelina benghalensis BL6 Parthenium hysterophorus
BL7 Euphorbia hirta BL8 Setaria veridis BL9 Amaranthus viridis
BL10 Phyllanthus niruri BL11 Chenopodium album BL12 Medicago enticulate
BL13 melilotus alba BL14 Argemone mexicana BL15 Rumex denticulata

Sedges Variety Sedges Variety Sedges Variety
SD1 Cyperus rotundus SD2 Cyperus Iria SD3 Cyperus difformis

Experimental design and method for Sugarcane crop
Experimental trial was conducted to evaluate the herbicidal composition of the present invention in India against major weeds in sugarcane crop with ternary composition of present invention and comparative solo and binary compositions as per the details provided in Table 22-35.
The experiment was laid out in Randomized Block Design (RBD). The plot size was 10 m x 10 m and the spacing was 90 cm × 60 cm. All the recommended agronomic practices were followed throughout the cropping period. The different formulations were weighed according to the doses and diluted in water and applied using high volume knapsack sprayer fitted with a pressure regulator and a vertical bar with one flat fan nozzle and evaluated for % WCE (weed control efficiency) at 30 days after herbicide application (DAHA). 500 L/ha of water was used to dilute recommended doses of the formulation in the trial.
Observations from a composite sample (collected from three different spots in the experimental area) were recorded at 30 Days after herbicide application (DAHA). On the day of taking observation, weeds were collected from one square meter of each experimental plot and were cleaned. Weeds were then separated species wise and were oven dried and then weight was taken separately. Weed control efficacy for individual species was calculated using the formula:
W.C.E (%) = Weed population in control plot—weed population in treated plot X 100
Weed population in control plot

Experimental design and method for Wheat crop:
Two experimental trials to evaluate the herbicidal composition of the present invention were conducted at different trial sites in Ghaziabad (U.P.) and Karnal (Haryana), India against grassy, broad leaved weeds and sedges of wheat crop (variety DARA in Ghaziabad and HD 2968 in Karnal), which are prevalent in all wheat growing seasons with ternary composition of present invention and comparative solo and binary compositions as per the treatment details provided in Table 36-41.
The experiment was laid out in Randomized Block Design (RBD). The plot size was 10m x 10m and the spacing was 20cm × 10cm. All the recommended agronomic practices were followed throughout the cropping period. The different formulations were weighed according to the doses and diluted in water and applied using high volume knapsack sprayer fitted with a pressure regulator and a vertical bar with one flat fan nozzle at 25 days after sowing (DAS) at all locations and evaluated for % WCE (weed control efficiency) at 21 days after herbicide application (DAHA). 500 L/ha of water was used to dilute the recommended dose of formulation in all trials.
Weeds were collected from one square meter of each experimental plot and were cleaned and separated species wise. Weeds in different species were oven dried and then weight was taken separately. Weed control efficiency for individual species was calculated using the formula as provided above.
Evaluation of synergistic effect
A synergistic effect exists whenever the action of an active ingredient combination is greater than the sum of the actions of the individual components. Synergism was calculated by using Colby’s method, Weeds, vol. 15 No. 1(Jan 1967), pp. 20-2.
The synergistic action expected for a given combination of three active components can be calculated as follows:
?(E=(X+Y+Z) - ((XY+YZ+XZ))/100 +) ?( XYZ/10000)
Where:
E represents expected percentage of control for the combination of the three active ingredients at defined doses (for example equal to x, y and z respectively),
X is the percentage of control observed by the compound (I) at a defined dose (equal to x),
Y is the percentage of control observed by the compound (II) at a defined dose (equal to y),
Z is the percentage of control observed by the compound (III) at a defined dose (equal to z).
If observed control of the combination > Expected control, the combination is synergistic (Colby ratio > 1)
If observed control of the combination < Expected control, the combination is antagonistic (Colby ratio < 1)
If observed control of the combination = Expected control, the combination is additive (Colby ratio =1)

Evaluation of Sugarcane/Wheat Yield: Canes from each experimental plot were harvested and weight of canes was taken. Afterwards weight was converted to yield into ton per hectare (t/ha). Similarly, for wheat crop plants from each experimental plot were harvested and grains were separated and weight of grains was taken. Thereafter weight was converted to yield into kg per hectare. Efficacy of herbicide compositions of present invention was evaluated by calculating the % increase in yield of cane and wheat grain against control.

Phytotoxicity Observations: Synergistic ternary herbicidal compositions of the present invention were found to be non-phytotoxic on sugarcane and wheat crop.

Table 22: Treatment Details of Ternary herbicidal composition Metribuzin + Halosulfuron-methyl + Ametryn
Treatments No. (TN) Treatments Details

T1 Metribuzin 10%+Halosulfuron-methyl 2%+ Ametryn 20% WP
T2 Metribuzin 13.2%+Halosulfuron-methyl 1.8%+ Ametryn 16.8% WP
T3 Metribuzin 14.8% +Halosulfuron-methyl 1.4%+ Ametryn 13% WP
T4 Halosulfuron Methyl 12% + Metribuzin 55% WG (Ready mix)
T5 Metribuzin 70 % WP + Ametryn 80 % WDG (Tank Mix)
T6 Halosulfuron-methyl 75 % WG + Ametryn 80 % WDG (Tank Mix)
T7 Ametryn 80% WDG
T8 Metribuzin 70 % WP
T9 Halosulfuron Methyl 75% WG
T10 Untreated control (average count of 1 msq area)

Table 23: Effect of treatments on weed control efficiency against Grasses on Sugarcane crop
*TN Dose GS1 GS2 GS3
g.a.i / ha gm or ml /ha O E CR O E CR O E CR
T1 300+60+600 3000 98 72 1.36 97 68 1.42 97 64 1.51
T2 396+54+504 3000 99 72 1.37 96 68 1.41 98 64 1.53
T3 555+53+488 3750 98 72 1.36 97 68 1.42 95 64 1.48
T4 54+247.5 450 65 65 1 60 60 1 55 55 1
T5 1005+ 2000 1500 + 2500 71 72 0.98 67 68 0.98 88 64 0.96
T6 67.5 + 2000 90 + 2500 18 20 0.9 16 20 0.8 16 20 0.8
T7 2000 2500 20 - - 20 - - 20 - -
T8 1005 1500 65 - - 60 - - 55 - -
T9 67.9 90 0 - - 0 - - 0 - -
T10 NA NA 26 - - 18 - - 12 - -
*For details Refer Table 22;O=Observed WCE (%);E=Expected WCE (%) Calculated using Colby Formula;CR=Colby ratio

Table 24: Effect of treatments on weed control efficiency against Broad leaved Weeds on Sugarcane crop
*TN Dose BL1 BL2 BL3
g.a.i / ha gm or ml /ha O E CR O E CR O E CR
T1 300+60+600 3000 95 81 1.17 96 87.85 1.09 95 77.32 1.22
T2 396+54+504 3000 95 81 1.17 94 87.85 1.07 95 77.32 1.22
T3 555+53+488 3750 94 81 1.16 94 87.85 1.07 94 77.32 1.21
T4 54+247.5 450 52 52.5 0.99 59.50 59.50 1 46 46 1
T5 1005+ 2000 1500 + 2500 75 80 0.93 78 86.50 0.90 60 74.80 0.80
T6 67.5 + 2000 90 + 2500 60 62 0.96 70 73 0.95 58 62 0.93
T7 2000 2500 60 - - 70 - - 58 - -
T8 1005 1500 50 - - 55 - - 40 - -
T9 67.9 90 5 - - 10 - - 10 - -
T10 NA NA 10 - - 12 - - 22 - -
*For details Refer Table 22

Table 25: Effect of treatments on weed control efficiency against Broad leaved Weeds on Sugarcane crop
*TN Dose BL4 BL5 BL6
g.a.i / ha gm or ml /ha O E CR O E CR O E CR
T1 300+60+600 3000 93 87.2 1.06 90 63.04 1.42 90 80.53 1.11
T2 396+54+504 3000 95 87.2 1.08 75 63.04 1.18 92 80.53 1.14
T3 555+53+488 3750 94 87.2 1.07 75 63.04 1.18 92 80.53 1.14
T4 54+247.5 450 60 60 1 38 38.40 0.98 50 52.50 0.95
T5 1005+ 2000 1500 + 2500 75 87.2 0.86 50 58 0.86 80 79.50 1.00
T6 67.5 + 2000 90 + 2500 68 68 1 40 47.20 0.84 59 61.05 0.96
T7 2000 2500 68 - - 40 - - 59 - -
T8 1005 1500 60 - - 30 - - 50 - -
T9 67.9 90 0 - - 12 - - 5 - -
T10 NA NA 9 - - 10 - - 12 - -
*For details Refer Table 22

Table 26: Effect of treatments on weed control efficiency against Broad leaved Weeds on Sugarcane crop
*TN Dose BL7 BL8 BL9 BL10
g.a.i / ha gm or ml /ha O E CR O E CR O E CR O E CR
T1 300+60+600 3000 86 68.65 1.25 85 82 1.03 95 93.25 1.01 90 82 1.09
T2 396+54+504 3000 86 68.65 1.25 87 82 1.06 97 93.25 1.04 90 82 1.09
T3 555+53+488 3750 85 68.65 1.23 85 82 1.03 95 93.25 1.01 90 82 1.09
T4 54+247.5 450 43 43 1 55 55 1 70 73 0.95 55 55 1
T5 1005+ 2000 1500 + 2500 60 67 0.89 70 82 0.85 90 92.50 0.97 80 82 0.97
T6 67.5 + 2000 90 + 2500 48 47.75 1 60 60 1 75 77.50 0.96 60 60 1
T7 2000 2500 45 - - 60 - - 75 - - 60 - -
T8 1005 1500 40 - - 55 - - 70 - - 55 - -
T9 67.9 90 5 - - 0 - - 10 - - 0 - -
T10 NA NA 10 - - 8 - 14 - - 8 - -
*For details Refer Table 22

Table 27: Effect of treatments on weed control efficiency against Sedges on Sugarcane crop
*TN Dose SD1 SD2 SD3
g.a.i / ha gm or ml /ha O E CR O E CR O E CR
T1 300+60+600 3000 96 92.35 1.03 99 91.9 1.07 99 91.9 1.07
T2 396+54+504 3000 95 92.35 1.02 95 91.9 1.03 95 91.9 1.03
T3 555+53+488 3750 95 92.35 1.02 95 91.9 1.03 95 91.9 1.03
T4 54+247.5 450 80 91.50 0.87 80 91 0.87 80 91 0.87
T5 1005+ 2000 1500 + 2500 10 23.50 0.42 10 19 0.52 10 19 0.52
T6 67.5 + 2000 90 + 2500 90 91 0.98 90 91 0.98 90 91 0.98
T7 2000 2500 10 - - 10 - - 10 - -
T8 1005 1500 15 - - 10 - - 10 - -
T9 67.9 90 90 - - 90 - - 90 - -
T10 NA NA 25 - - 18 - - 15 -
*For details Refer Table 22

Table 28: Effect of treatments on Sugarcane yield at harvest
*TN Dose Cane Yield % increase against control
g.a.i / ha gm - ml /ha t/ha
T1 300+60+600 3000 95.2 39.6
T2 396+54+504 3000 93.13 36.6
T3 555+53+488 3750 91.32 33.9
T4 54+247.5 450 85.7 25.7
T5 1005+ 2000 1500 + 2500 83.23 22.0
T6 67.5 + 2000 90 + 2500 82.56 21.1
T7 2000 2500 78.9 15.7
T8 1005 1500 79.7 16.9
T9 67.9 90 74.34 9.0
T10 NA NA 68.2 -
*For details Refer Table 22

Table 29: Treatment Details of Ternary herbicidal composition Metribuzin +Halosulfuron-methyl + Bentazone/Bentazone sodium
Treatments No. (TN) Treatments Details

T1 Metribuzin 10%+Halosulfuron-methyl 2%+ Bentazone 19.2% WP
T2 Metribuzin 10%+Halosulfuron-methyl 2%+ Bentazone sodium 19.2% WP
T3 Metribuzin 16%+Halosulfuron-methyl 1.4%+ Bentazone 11.2% WP
T4 Metribuzin 16%+Halosulfuron-methyl 1.4%+ Bentazone sodium 11.2% WP
T5 Metribuzin 24%+Halosulfuron-methyl 1.8%+ Bentazone 11.2% WP
T6 Metribuzin 24%+Halosulfuron-methyl 1.8%+ Bentazone sodium 11.2% WP
T7 Halosulfuron Methyl 12% + Metribuzin 55% WG (Ready mix)
T8 Halosulfuron Methyl 75% WG + Bentazone 48 % SL
T9 Metribuzin 70 % WP + Bentazone 48 % SL
T10 Metribuzin 70 % WP
T11 Halosulfuron Methyl 75% WG
T12 Bentazone 48 % SL
T13 Untreated control (average count of 1 msq area)

Table 30: Effect of treatments on weed control efficiency against Grasses on Sugarcane crop
*TN Dose GS1 GS2 GS3
g.a.i / ha gm or ml /ha O E CR O E CR O E CR
T1 300 + 60 + 576 3000 90 78 1.15 91 60 1.51 90 50 1.8
T2 300 + 60 + 576 3000 90.2 78 1.16 92 60 1.53 90 50 1.8
T3 480 + 42 + 336 3000 92 78 1.17 93 60 1.55 92 50 1.84
T4 480 + 42 + 336 3000 92 78 1.17 93 60 1.55 92 50 1.84
T5 720 + 54 + 336 3000 96 78 1.23 94 60 1.56 96 50 1.92
T6 720 + 54 + 336 3000 96 78 1.23 74 60 1.23 96 50 1.92
T7 54 + 247.5 450 70 78 0.89 60 60 1 50 50 1
T8 67.5 + 960 90 + 2000 0 0 - 0 0 - 0 0 -
T9 1005 + 960 1500 + 2000 70 78 0.89 60 60 1 50 50 1
T10 1005 1500 78 - - 60 - - 50 - -
T11 67.9 90 0 - - 0 - - 0 - -
T12 960 2000 0 - - 0 - - 0 - -
T13 NA NA 15 - - 18 - - 22 - -
*For details Refer Table 29

Table 31: Effect of treatments on weed control efficiency against Broad leaved Weeds on Sugarcane crop
*TN Dose BL1 BL2 BL3
g.a.i / ha gm or ml /ha O E CR O E CR O E CR
T1 300 + 60 + 576 3000 95 88.8 1.06 96 88.8 1.08 90 88.24 1.01
T2 300 + 60 + 576 3000 95 88.8 1.06 96 88.8 1.08 90 88.24 1.01
T3 480 + 42 + 336 3000 92 88.8 1.03 92 88.8 1.03 90 88.24 1.01
T4 480 + 42 + 336 3000 92 88.8 1.03 92 88.8 1.03 90 88.24 1.01
T5 720 + 54 + 336 3000 91 88.8 1.02 92 88.8 1.03 90 88.24 1.01
T6 720 + 54 + 336 3000 92 88.8 1.03 93 88.8 1.04 90 88.24 1.01
T7 54+247.5 450 65 68 0.95 75 72 1.04 68 72 0.94
T8 67.5 + 960 90 + 2000 65 72 0.90 60 72 0.83 65 66.40 0.97
T9 1005 + 960 1500 + 2000 70 86 0.81 85 84 1.01 80 85.30 0.93
T10 1005 1500 60 - - 60 - - 65 - -
T11 67.9 90 20 - - 30 - - 20 - -
T12 960 2000 65 - - 60 - - 58 - -
T13 NA NA 17 - - 12 - - 12 - -
*For details Refer Table 29

Table 32: Effect of treatments on weed control efficiency against Broad leaved Weeds on Sugarcane crop
*TN Dose BL4 BL5
g.a.i / ha gm or ml /ha O E CR O E CR
T1 300 + 60 + 576 3000 96 92.16 1.04 80 75.7 1.05
T2 300 + 60 + 576 3000 96 92.16 1.04 80 75.7 1.05
T3 480 + 42 + 336 3000 96 92.16 1.04 80 75.7 1.05
T4 480 + 42 + 336 3000 95 92.16 1.03 80 75.7 1.05
T5 720 + 54 + 336 3000 98 92.16 1.06 90 75.7 1.18
T6 720 + 54 + 336 3000 98 92.16 1.06 90 75.7 1.18
T7 54+247.5 450 90 77.60 1.15 40 46 0.86
T8 67.5 + 960 90 + 2000 90 75.50 1.19 55 59.50 0.92
T9 1005 + 960 1500 + 2000 90 88.80 1.01 70 73 0.95
T10 1005 1500 68 - - 40 - -
T11 67.9 90 30 - - 10 - -
T12 960 2000 65 - - 55 - -
T13 NA NA 20 - - 14 - -
*For details Refer Table 29

Table 33: Effect of treatments on weed control efficiency against Broad leaved Weeds on Sugarcane crop
*TN Dose BL6 BL9
g.a.i / ha gm- ml /ha O E CR O E CR
T1 300 + 60 + 576 3000 95 89.2 1.06 95 89.2 1.06
T2 300 + 60 + 576 3000 95 89.2 1.06 95 89.2 1.06
T3 480 + 42 + 336 3000 95 89.2 1.06 96 89.2 1.07
T4 480 + 42 + 336 3000 96 89.2 1.07 96 89.2 1.07
T5 720 + 54 + 336 3000 96 89.2 1.07 98 89.2 1.09
T6 720 + 54 + 336 3000 96 89.2 1.07 98 89.2 1.09
T7 54+247.5 450 70 73 0.95 75 73 1.02
T8 67.5 + 960 90 + 2000 60 64 0.93 60 64 0.93
T9 1005 + 960 1500 + 2000 85 88 0.96 80 88 0.90
T10 1005 1500 70 - - 70 - -
T11 67.9 90 10 - - 10 - -
T12 960 2000 60 - - 60 - -
T13 NA NA 18 - 11 - -
*For details Refer Table 29
Table 34: Effect of treatments on weed control efficiency against Sedges on Sugarcane crop
*TN Dose SD1 SD2 SD3
g.a.i / ha gm- ml /ha O E CR O E CR O E CR
T1 300 + 60 + 576 3000 95 91 1.04 98 95.75 1.02 96 95.5 1.05
T2 300 + 60 + 576 3000 95 91 1.04 98 95.75 1.02 98 95.5 1.02
T3 480 + 42 + 336 3000 95 91 1.04 99 95.75 1.03 98 95.5 1.02
T4 480 + 42 + 336 3000 96 91 1.05 98 95.75 1.02 98 95.5 1.02
T5 720 + 54 + 336 3000 96 91 1.05 98 95.75 1.02 97 95.5 1.01
T6 720 + 54 + 336 3000 96 91 1.05 98 95.75 1.02 98 95.5 1.02
T7 54+247.5 450 80 82 0.97 89 91.50 0.97 90 91 0.98
T8 67.5 + 960 90 + 2000 80 90 0.88 89 95 0.93 90 95 0.94
T9 1005 + 960 1500 + 2000 53 55 0.96 57 57.50 0.99 52 55 0.94
T10 1005 1500 10 - - 15 - - 10 - -
T11 67.9 90 80 - - 90 - - 90 - -
T12 960 2000 50 - - 50 - - 50 - -
T13 NA NA 22 - - 12 - - 15 - -
*For details Refer Table 29

Table 35: Effect of treatments on Cane yield at harvest
*TN Dose Cane yield % increase against control
g.a.i / ha gm - ml /ha t/ha
T1 300 + 60 + 576 3000 95.2 36.4
T2 300 + 60 + 576 3000 96.3 38.0
T3 480 + 42 + 336 3000 94.2 35.0
T4 480 + 42 + 336 3000 94.4 35.2
T5 720 + 54 + 336 3000 91.2 30.7
T6 720 + 54 + 336 3000 90.4 29.5
T7 54+247.5 450 85.6 22.6
T8 67.5 + 960 90 + 2000 80.8 15.8
T9 1005 + 960 1500 + 2000 78.8 12.9
T10 1005 1500 78.3 12.2
T11 67.9 90 75.2 7.7
T12 960 2000 72.7 4.2
T13 NA NA 69.8 -
*For details Refer Table 29

Table 36: Treatment Details of Ternary herbicidal composition Metribuzin +Fenoxaprop-p-Ethyl + Bentazone /Bentazone sodium
Treatments No. (TN) Treatments Details

T1 Metribuzin 6%+Fenoxaprop-p-Ethyl 2.9%+ Bentazone 12.9% SC
T2 Metribuzin 6%+Fenoxaprop-p-Ethyl 2.9%+ Bentazone 12.9% WP
T3 Metribuzin 6%+Fenoxaprop-p-Ethyl 2.9%+ Bentazone sodium 12.9% SC
T4 Metribuzin 6%+Fenoxaprop-p-Ethyl 2.9%+ Bentazone sodium 12.9% WP
T5 Metribuzin 5.1%+Fenoxaprop-p-Ethyl2.9%+ Bentazone 20% SC
T6 Metribuzin 5.1%+Fenoxaprop-p-Ethyl2.9%+ Bentazone 20% WP
T7 Metribuzin 5.1%+Fenoxaprop-p-Ethyl2.9%+ Bentazone sodium 20% SC
T8 Metribuzin 5.1%+Fenoxaprop-p-Ethyl2.9%+ Bentazone sodium 20% WP
T9 Metribuzin 7.1%+Fenoxaprop-p-Ethyl 2.6%+ Bentazone 22.9% SC
T10 Metribuzin 7.1%+Fenoxaprop-p-Ethyl 2.6%+ Bentazone 22.9% WP
T11 Metribuzin 7.1%+Fenoxaprop-p-Ethyl 2.6%+ Bentazone sodium 22.9% SC
T12 Metribuzin 7.1%+Fenoxaprop-p-Ethyl 2.6%+ Bentazone sodium 22.9% WP
T13 Fenoxaprop-p-ethyl 7.77% + Metribuzin 13.6% EC (Ready mix)
T14 Fenoxaprop-p-ethyl 10% EC + Bentazone 48% SL (Tank Mix)
T15 Metribuzin 70% WP + Bentazone 48% SL (Tank Mix)
T16 Fenoxaprop-p-ethyl 10% EC
T17 Metribuzin 70 % WP
T18 Bentazone 48% SL
T19 Untreated control (average count of 1 msq area)

Table 37: Effect of treatments on weed control efficiency against Grasses on Wheat crop
*TN Dose GS4 GS5 GS6
g.a.i / ha gm or ml /ha O E CR O E CR O E CR
T1 180+87+387 3000 95.6 81.67 1.17 98.2 87.75 1.11 90 64 1.40
T2 180+87+387 3000 91.7 81.67 1.12 96 87.75 1.09 89 64 1.39
T3 180+87+387 3000 95 81.67 1.16 97 87.75 1.10 90 64 1.40
T4 180+87+387 3000 92 81.67 1.12 96 87.75 1.09 90 64 1.40
T5 153+87+600 3000 88.3 81.67 1.08 95 87.75 1.08 92 64 1.43
T6 153+87+600 3000 85 81.67 1.04 92 87.75 1.04 92 64 1.43
T7 153+87+600 3000 89.2 81.67 1.09 95 87.75 1.08 91 64 1.42
T8 153+87+600 3000 86.2 81.67 1.05 91 87.75 1.03 92 64 1.43
T9 213+78+687 3000 94.3 81.67 1.15 94 87.75 1.07 90 64 1.40
T10 213+78+687 3000 90 81.67 1.10 91 87.75 1.03 90 64 1.40
T11 213+78+687 3000 92.6 81.67 1.13 95.5 87.75 1.08 90 64 1.40
T12 213+78+687 3000 90 81.67 1.10 91.4 87.75 1.04 90 64 1.40
T13 100 + 175 1250 81 81.67 0.99 70 87.75 0.79 66 64 1.03
T14 120 + 960 1200 + 2000 44 53 0.83 63 65 0.96 40 40 1

T15 210 + 960 300 + 2000 59 61 0.96 65 65 1 34 40 0.85
T16 120 1200 53 - - 65 - - 40 - -
T17 210 300 61 - - 65 - - 40 - -
T18 960 2000 0 - - 0 - - 0 - -
T19 NA NA 385 - - 22 - - 28 - -
*For details Refer Table 36

Table 38: Effect of treatments on weed control efficiency against Broad leaved Weeds on Wheat crop
*TN Dose BL11 BL12 BL13
g.a.i / ha gm or ml /ha O E CR O E CR O E CR
T1 180+87+387 3000 91 82 1.10 90 82 1.09 90 82 1.09
T2 180+87+387 3000 90 82 1.09 95 82 1.15 95 82 1.15
T3 180+87+387 3000 92 82 1.12 93 82 1.13 93 82 1.13
T4 180+87+387 3000 90 82 1.09 95 82 1.15 95 82 1.15
T5 153+87+600 3000 92 82 1.12 95 82 1.15 95 82 1.15
T6 153+87+600 3000 90 82 1.09 96 82 1.17 96 82 1.17
T7 153+87+600 3000 90 82 1.09 96 82 1.17 96 82 1.17
T8 153+87+600 3000 90 82 1.09 96 82 1.17 96 82 1.17
T9 213+78+687 3000 92 82 1.12 96 82 1.17 96 82 1.17
T10 213+78+687 3000 92 82 1.12 93 82 1.13 93 82 1.13
T11 213+78+687 3000 92 82 1.12 92 82 1.12 92 82 1.12
T12 213+78+687 3000 91 82 1.10 94 82 1.14 94 82 1.14
T13 100 + 175 1250 69.5 70 0.99 70 70 1 70 70 1
T14 120 + 960 1200 + 2000 40 40 1 40 40 1 40 40 1
T15 210 + 960 300 + 2000 80 82 0.97 80 82 0.97 80 82 0.97
T16 120 1200 0 - - 0 - - 0 - -
T17 210 300 70 - - 70 - - 70 - -
T18 960 2000 40 - - 40 - - 40 - -
T19 NA NA 30 - - 18 - - 15 - -
*For details Refer Table 36

Table 39: Effect of treatments on weed control efficiency against Broad leaved Weeds on Wheat crop
*TN Dose BL14 BL15
g.a.i / ha gm or ml /ha O E CR O E CR
T1 180+87+387 3000 90 77.5 1.16 90 84 1.07
T2 180+87+387 3000 90 77.5 1.16 90 84 1.07
T3 180+87+387 3000 90 77.5 1.16 90 84 1.07
T4 180+87+387 3000 90 77.5 1.16 90 84 1.07
T5 153+87+600 3000 90 77.5 1.16 90 84 1.07
T6 153+87+600 3000 89 77.5 1.14 89 84 1.05
T7 153+87+600 3000 90 77.5 1.16 90 84 1.07
T8 153+87+600 3000 93 77.5 1.2 93 84 1.10
T9 213+78+687 3000 94 77.5 1.21 94 84 1.11
T10 213+78+687 3000 92 77.5 1.18 92 84 1.09
T11 213+78+687 3000 92 77.5 1.18 92 84 1.09
T12 213+78+687 3000 92 77.5 1.18 92 84 1.09
T13 100 + 175 1250 55 55 1 65 60 1.08
T14 120 + 960 1200 + 2000 50 50 1 60 60 1
T15 210 + 960 300 + 2000 80 77.50 1.03 82 84 0.97
T16 120 1200 0 - - 0 - -
T17 210 300 55 - - 60 - -
T18 960 2000 50 - - 60 - -
T19 NA NA 12 - - 10 - -
*For details Refer Table 36

Table 40: Effect of treatments on weed control efficiency against Sedges on Wheat crop
*TN Dose SD1
g.a.i / ha gm or ml /ha O E CR
T1 180+87+387 3000 90 84 1.07
T2 180+87+387 3000 90 84 1.07
T3 180+87+387 3000 90 84 1.07
T4 180+87+387 3000 90 84 1.07
T5 153+87+600 3000 90 84 1.07
T6 153+87+600 3000 89 84 1.05
T7 153+87+600 3000 90 84 1.07
T8 153+87+600 3000 93 84 1.10
T9 213+78+687 3000 94 84 1.11
T10 213+78+687 3000 94 84 1.11
T11 213+78+687 3000 90 84 1.07
T12 213+78+687 3000 92 84 1.09
T13 100 + 175 1250 20 20 1
T14 120 + 960 1200 + 2000 80 80 1
T15 210 + 960 300 + 2000 83 84 0.98
T16 120 1200 0 - -
T17 210 300 20 - -
T18 960 2000 80 - -
T19 NA NA 8 - -
*For details Refer Table 36

Table 41: Effect of treatments on grain yield of wheat crop at harvest
*TN Dose Grain Yield % increase against control
g.a.i / ha gm - ml /ha Kg /ha
T1 180+87+387 3000 5010 96.5
T2 180+87+387 3000 5125 101.0
T3 180+87+387 3000 4990 95.7
T4 180+87+387 3000 5005 96.3
T5 153+87+600 3000 5160 102.4
T6 153+87+600 3000 5200 103.9
T7 153+87+600 3000 5230 105.1
T8 153+87+600 3000 4980 95.3
T9 213+78+687 3000 5210 104.3
T10 213+78+687 3000 5225 104.9
T11 213+78+687 3000 5210 104.3
T12 213+78+687 3000 5200 103.9
T13 100 + 175 1250 4200 64.7
T14 120 + 960 1200 + 2000 3200 25.5
T15 210 + 960 300 + 2000 3500 37.3
T16 120 1200 3100 21.6
T17 210 300 3200 25.5
T18 960 2000 2650 3.9
T19 NA NA 2550 -
*For details Refer Table 36

It is evident from the above tables 23-27, 30-34 and 37-40 that the ternary herbicidal composition of the present invention gave good control on tested weeds/undesired vegetation on sugarcane and wheat crops wherein all the prepared ternary composition found synergistic as compared to the reference products (solo or binary composition).
It has also been found that use of ternary composition of present invention not only gave better efficiency by using low a.i., content compared to binary and solo composition but also broaden the spectrum of composition as the binary compositions are not providing sufficient weed control in given duration.
It has also been found that the ternary composition of present invention provides a readymade solution to control the grasses, broad leaved weeds and sedges in one go. It has been observed that Metribuzin is effective to control mostly grasses and broad leaved weeds Halosulfuron-methyl is effective to control only for sedges and Ametryn is effective to control mostly grasses and broad leaved weeds whereas synergistic combination of present invention Metribuzin + Halosulfuron-methyl + Ametryn gives excellent control on all the tested weeds for duration of 30 days that too in single application. In the same line of results we noted that Bentazone /Bentazone sodium is effective on broad leaved weeds and sedges whereas fenoxaprop solo is effective on grasses but the synergistic combination of present invention Metribuzin + Fenoxaprop-p-Ethyl + Bentazone/Bentazone sodium is effective on grasses, broad leaved weeds and sedges for duration of 21 days that too in single application.
Further as evident from table 28, 35 and 41 that higher yield of cane and wheat grain is observed by using the ternary composition of present invention compared to binary composition. It is evident from table 28, 35 and 41 that % increase in cane yield and wheat grain yield against control is much higher.
From the foregoing it will be observed that numerous modifications and variations can be effectuated without departing from the true spirit and scope of the novel concepts of the present invention. It is to be understood that no limitations with respect to the specific embodiments illustrated is intended or should be inferred. It should be understood that all such modifications and improvements have been deleted herein for the sake of conciseness and readability but are properly within the scope of the following claims. ,CLAIMS:We claim:
1. A synergistic ternary herbicidal compositions comprising:
a. Metribuzin;
b. at least one compound selected from Halosulfuron-methyl or Fenoxaprop-p-ethyl;
c. at least one compound selected from Ametryn or Bentazone/Bentazone sodium and
d. agriculturally acceptable additives.
2. The synergistic ternary herbicidal compositions as claimed in claim 1, comprising:
a. Metribuzin in the range of 3.4 to 24% w/w;
b. at least one compound selected from Halosulfuron-methyl in the range of 1.4 to 2.6% w/w or Fenoxaprop-p-ethyl in the range of 2.0 to 2.9% w/w;
c. at least one compound selected from Ametryn in the range of 13 to 24% w/w or Bentazone/Bentazone sodium in the range of 11.2 to 24.3% and
d. agriculturally acceptable additives.
3. The synergistic ternary herbicidal compositions as claimed in claim 1, wherein the composition is formulated as Capsule suspension (CS), Dispersible concentrate (DC), Dustable powder (DP), Emulsifiable granule (EG), Emulsion water-in-oil (EO), Emulsifiable powder (EP), Granules (GR), Oil-dispersion (OD), Oil miscible flowable concentrate (OF), Oil miscible liquid (OL), Oil dispersible powder 5 (OP), Suspension concentrate (SC), Suspension concentrate for direct application (SD), Suspo-emulsion (SE), Water soluble granule (SG), Soluble concentrate (SL), Spreading oil (SO), Water soluble powder (SP), Water soluble tablet (ST), Ultra-low volume (ULV) suspension, Tablet (TB), Ultra-low volume (ULV) liquid, Water dispersible granules (WG), Wettable powder (WP), Water dispersible tablet (WT), a mixed formulation of CS and SC (ZC) or A mixed formulation of CS and SE (ZE), preferably WP and SC.

4. The synergistic ternary herbicidal compositions as claimed in claim 1, wherein the agriculturally acceptable additives is selected from the group comprising of dispersing agent, wetting agent, dispersing cum wetting agent, safener, defoamer, biocide/preservatives, viscosity modifier, anti-settling agent, filler and diluent.

5. The synergistic ternary herbicidal compositions as claimed in claim 4, wherein

a. the dispersing agent is selected from the group comprising naphthalene sulfonate formaldehyde condensate, sulfonated kraft lignin polymer, polymethyl methacrylate-polyethylene oxide graft copolymer, amine salt of phosphate tristyryl phenol ethoxylated, acrylic copolymer, graft copolymer, salt of naphthalene sulphonate, phosphate ester, salt of polycarboxylate, alcohol block copolymer, ethoxylated polyarylphenol phosphate ester, tristyrylphenol ethoxylate phosphate ester, or a combination thereof and present in an amount in the range from 0.1-5% w/w;

b. the wetting agent is selected from the group comprising sodium isopropyl naphthalene sulfonate, sodium dioctyl sulphosuccinate, a copolymer condensate of ethylene and propylene oxide, sodium alkyl naphthalene sulfonate blend, ethoxylated polyarylphenol phosphate ester, non-ionic ethoxylate, castor oil ethoxylate or a combination thereof and present in an amount in the range from 0.1-5% w/w;.

c. the dispersing cum wetting agent is selected from the group comprising proprietary blend of phosphate ester and sodium naphthalene sulfonate formaldehyde condensate, highly sulfonation and low molecular weight kraft lignin polymer, sodium salt of aromatic ring surfactant, ammonium salt of aromatic ring surfactant, sodium salt of naphthalene sulphonic acid condensation, proprietary blend of anionic surfactant, sodium methyl oleoyl taurate, tristyrylphenol ethoxylate phosphate ester or a combination thereof and present in an amount in the range from 2-7% w/w;

d. the safener is mefenpyr-diethyl present in an amount in the range from 0.01 to 2% w/w;

e. the defoamer is polydimethylsiloxane antifoam emulsion present in an amount in the range from 0.01 to 1% w/w;

f. the biocide/preservative is selected from the group comprising 20% aqueous dipropyleneglycol solution of 1,2- benzisothiazolin-3-one, formaldehyde, isothiazolinone or a combination thereof and present in an amount in the range from 0.01 to 1% w/w;

g. the viscosity modifier is selected from the group comprising xanthan gum (2% solution), guar gum and present in an amount in the range from 5-15% w/w;

h. the anti-settling agent is selected from the group comprising precipitated silica, organic bentonite, polyolefin particles and fumed silica and present in an amount in the range from 1.5 to 3.5% w/w;

i. the filler is selected from the group comprising, silica, sodium bicarbonate, china clay, lactose, bentonite clay, kaolin, diatomaceous earth or a combination thereof and present in an amount quantity sufficient; and

j. the diluent is demineralised water and present in an amount quantity sufficient.