DESC:FIELD OF THE INVENTION
[0001] The present disclosure pertains to technical field of agrochemicals. More specifically, the present disclosure pertains to a herbicidal synergistic composition comprising mixture of three herbicides, formulation thereof and to a method of controlling undesired vegetation in crops of useful plants.

BACKGROUND OF THE INVENTION
[0002] The background description includes information that may be useful in understanding the present invention. It is not an admission that any of the information provided herein is prior art or relevant to the presently claimed invention, or that any publication specifically or implicitly referenced is prior art.
[0003] Protection of crops from weeds and other vegetation which inhibit crop growth is a constantly recurring problem in agriculture. To address this problem, researchers are trying to produce an extensive variety of active agents and active agent formulations effective in the control of such undesirable plant growth. Chemical herbicides of many types have been disclosed in the art and a large number are in commercial use. In crop protection, it is desirable in principle to increase specificity and reliability of action of herbicidally active agents. In particular, it is desirable for a crop protection product to control undesirable plants effectively and, at the same time, to be tolerated by useful plants in question.
[0004] Pretilachlor, pyrazosulfuron-ethyl and chlorimuron are compounds known to be herbicidally active and to be of use in the control of undesirable vegetation, for example in the protection of a range of crops. The herbicides pretilachlor, pyrazosulfuron-ethyl and chlorimuron are independently known in the art for their herbicidal potency. They are disclosed in ‘The Pesticide Manual’ 15th Edition, published 2009 by the British Crop Protection Council, and are also commercially available.
[0005] Although pretilachlor, pyrazosulfuron-ethyl and chlorimuron are herbicidally active, in many cases they do not provide sufficient control of relevant harmful plants and their activities at low application rates are not always satisfactory. The recommended level of herbicide that may be applied per unit of area is under pressure from governmental, as well as for economic and environmental reasons.
[0006] Further, certain species of undesirable broadleaf vegetation and grassy weeds are becoming more and more resistant to a number of most widely used herbicides. Thus, on one hand ever more stringent conditions are being placed on the type and use rate of herbicides, while on the other hand approved herbicides are becoming less and less effective over time in certain species of undesirable plants.
[0007] Furthermore, it is very expensive and time consuming to seek and obtain registration of a new herbicidal compound, including its proposed use rate. Approval data required must not only include evidence of efficacy at the application rates proposed but also safety of herbicide when applied at the recommended level.
[0008] Accordingly, demonstration of synergism by combination of existing herbicidal agents, permits use of individual agents of synergistic combination at lower rates than when used alone, and in many instances ameliorates increasing resistance to herbicidal effectiveness.
[0009] Thus, there is a great need in the art for improved herbicidal composition and a method for controlling undesirable vegetation without adversely affecting desirable plants and which reduces dosage of herbicidal agents necessary to obtain acceptable weed control.
[0010] The present invention satisfies the existing needs, as well as others, and generally overcomes the deficiencies found in the prior art.

OBJECTS OF THE INVENTION
[0011] It is an object of the present disclosure to provide a synergistically acting herbicide mixture for controlling undesired vegetation in crops of useful plants.
[0012] It is another object of the present disclosure to provide an improved herbicide composition and a method for controlling undesirable vegetation without substantially affecting desirable vegetation.
[0013] It is another object of the present disclosure to provide an improved herbicide composition that is safe while being highly effective in controlling undesirable vegetation.
[0014] It is another object of the present disclosure to provide a herbicide composition that exhibits a synergistic herbicidal activity against a broad spectrum of economically important weeds.
[0015] It is yet another object of the present disclosure to provide a process for preparation of formulation comprising the above herbicide composition.

SUMMARY OF THE INVENTION
[0016] The present disclosure provides a synergistic herbicidal composition for selective control of undesirable vegetation in crops of agriculturally useful plants. The present disclosure is based upon a surprising finding that pretilachlor, pyrazosulfuron-ethyl and chlorimuron display a synergistic herbicidal effect in the control of undesirable vegetation when applied in combination, for example in a composition comprising all three compounds. The synergistic effects allow a reduction in application rate of individual active ingredients, a faster onset of herbicidal action, a longer-lasting action, better control of undesirable vegetation with only one or a few applications, and a broadening of possible application period.
[0017] The herbicide composition of the present disclosure includes a herbicidally effective amount of the active ingredients pretilachlor, pyrazosulfuron-ethyl and chlorimuron, and may include further constituents, for example customary auxiliary additives like inert formulation auxiliaries and/or agrochemical active compounds.
[0018] In various aspects, the active ingredient chlorimuron can be selected from chlorimuron and its agriculturally acceptable derivatives.
[0019] In at least one aspect, the active ingredient chlorimuron is chlorimuron-ethyl.
[0020] In an aspect the present disclosure provides a herbicide composition comprising a herbicidally effective amount of the active ingredients pretilachlor, pyrazosulfuron-ethyl and chlorimuron-ethyl, and auxiliary additives.
[0021] According to aspects of the present disclosure, the herbicide combination can exist as mixed formulations of pretilachlor, pyrazosulfuron-ethyl and chlorimuron-ethyl, which can then be used in a conventional way diluted with water, or be prepared as tank mixes by jointly diluting separately formulated or partially separately formulated active ingredients with water or with aqueous solutions.
[0022] In various aspects, the herbicide combination described herein can be formulated in a number of ways for suitable application. Examples of suitable formulations include water-dispersible granules (WDG or WG), water-soluble granules (SG), wettable powder (WP), water-dispersible powder (WDP), water-soluble powder (SP), granules (GR), encapsulated granules (CG), fine granules (FG), macrogranules (GG), microgranules (MG), suspension concentrate (SC), water-soluble concentrate (SL), emulsifiable concentrate (EC), emulsion (EW), micro-emulsion (ME), oil-based suspension concentrate (OD), flowable suspension (FS), suspoemulsion (SE) and microencapsulated suspension (CS).
[0023] The herbicide composition according to the present disclosure is suitable for selectively controlling undesirable vegetation in cereal crops, preferably rice, and more preferably transplanted rice. Further, the herbicide composition according to the present disclosure can exhibit a synergistic herbicidal activity against a broad spectrum of economically important weeds, including broadleaf, sedge and grass weeds.
[0024] The broadleaf weeds that can be controlled by the herbicide composition of the present invention include without any limitation Eclipta alba, Ludwigia spp ,Monochoria vaginalis, Alternanthera sessilis, Commelina sp., and Amaranthus viridis or the like.
[0025] The sedges can be controlled by the herbicide composition of the present disclosure include without limitation Cyperus iria, C. Diformis, C.rotundus or the like.
[0026] The grasses can be controlled by the herbicide composition of the present disclosure include without limitation Echinochloa crus-galli, Echinochloa colona, Leptochloa chinensis, Ischaemum rugosum, Digitaria spp, Panicum spp or the like.
[0027] The herbicide composition according to the present disclosure is suitable for all application methods conventionally used in agriculture, for example pre-emergence application and early post-emergence application.
[0028] The present disclosure further provides a process for preparing the herbicide composition described herein. The herbicide composition can be prepared by mixing the respective active compounds and, if appropriate, one or more formulation auxiliaries.
[0029] Various objects, features, aspects and advantages of the inventive subject matter will become more apparent from the following detailed description of preferred embodiments.

DETAILED DESCRIPTION OF THE INVENTION
[0030] The following is a detailed description of embodiments of the present disclosure. The embodiments are in such detail as to clearly communicate the disclosure. However, the amount of detail offered is not intended to limit the anticipated variations of embodiments; on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the present disclosure as defined by the appended claims.
[0031] Unless the context requires otherwise, throughout the specification which follow, the word “comprise” and variations thereof, such as, “comprises” and “comprising” are to be construed in an open, inclusive sense that is as “including, but not limited to.”
[0032] Reference throughout this specification to “one embodiment” or “an embodiment” means that a particular feature, structure or characteristic described in connection with the embodiment is included in at least one embodiment. Thus, the appearances of the phrases “in one embodiment” or “in an embodiment” in various places throughout this specification are not necessarily all referring to the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
[0033] As used in this specification and the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the content clearly dictates otherwise. It should also be noted that the term “or” is generally employed in its sense including “and/or” unless the content clearly dictates otherwise.
[0034] In some embodiments, the numbers expressing quantities of ingredients, properties such as concentration, process conditions, and so forth, used to describe and claim certain embodiments of the invention are to be understood as being modified in some instances by the term “about.” Accordingly, in some embodiments, the numerical parameters set forth in the written description are approximations that can vary depending upon the desired properties sought to be obtained by a particular embodiment. In some embodiments, the numerical parameters should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of some embodiments of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as practicable.
[0035] The recitation of ranges of values herein is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range. Unless otherwise indicated herein, each individual value is incorporated into the specification as if it were individually recited herein.
[0036] All methods described herein can be performed in suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g. “such as”) provided with respect to certain embodiments herein is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention otherwise claimed. No language in the specification should be construed as indicating any non-claimed element essential to the practice of the invention.
[0037] The headings and abstract of the invention provided herein are for convenience only and do not interpret the scope or meaning of the embodiments.
[0038] The following discussion provides many example embodiments of the inventive subject matter. Although each embodiment represents a single combination of inventive elements, the inventive subject matter is considered to include all possible combinations of the disclosed elements. Thus, if one embodiment comprises elements A, B, and C, and a second embodiment comprises elements B and D, then the inventive subject matter is also considered to include other remaining combinations of A, B, C, or D, even if not explicitly disclosed.
[0039] Various terms are used herein. To the extent a term used in a claim is not defined below, it should be given the broadest definition persons in the pertinent art have given that term as reflected in printed publications and issued patents at the time of filing.
[0040] The term “herbicide” as used herein, refers to a compound that controls growth of undesirable vegetation.
[0041] The phrase “herbicidally effective amount” as used herein, refers to quantity of such a compound or combination of such compounds that is capable of producing a controlling effect on growth of undesirable vegetation.
[0042] As used herein, the term "locus" includes not only areas where weeds may already be growing, but also areas where weeds have yet to emerge, and also areas under cultivation.
[0043] The term “plant” refers to all physical parts of a plant, including shoots, leaves, needles, stalks, stems, fruit bodies, fruits, seeds, roots, tubers and rhizomes.
[0044] As used herein, the phrase “auxiliary additives” include inert formulation auxiliaries. In certain embodiments the “auxiliary additives” can include adjuvants.
[0045] As used herein, the phrase "formulation auxiliaries" means auxiliaries which are known and accepted in the art for formation of formulations for agricultural or horticultural use.
[0046] As used herein, the phrase "formulation auxiliaries" means and can be used interchangeably with agrochemically acceptable excipients.
[0047] As used herein, the term "pre-emergence" refers to application of the herbicide composition to a habitat, a weed, or soil, prior to emergence of weeds from a soil surface. The term "early post-emergence," refers to application of the herbicide composition to weeds that have just emerged from a soil surface.
[0048] The present disclosure provides a herbicide composition comprising combination of pretilachlor, pyrazosulfuron-ethyl and chlorimuron. It has surprisingly been found that pretilachlor, pyrazosulfuron-ethyl and chlorimuron display a synergistic herbicidal effect in the control of undesirable vegetation when applied in combination, for example in a composition comprising all three compounds.
[0049] In an embodiment the present disclosure provides a herbicide composition comprising a herbicidally effective amount of the active ingredients pretilachlor, pyrazosulfuron-ethyl and chlorimuron, and auxiliary additives.
[0050] In various embodiments, the active ingredient chlorimuron can be selected from chlorimuron and its agriculturally acceptable derivatives.
[0051] In at least one embodiment, the active ingredient chlorimuron is chlorimuron-ethyl.
[0052] In one embodiment the present disclosure provides a herbicide composition comprising a herbicidally effective amount of the active ingredients pretilachlor, pyrazosulfuron-ethyl and chlorimuron-ethyl, and one or more auxiliary additives.
[0053] The active ingredients pretilachlor, pyrazosulfuron-ethyl and chlorimuron may be present in the composition of the present disclosure in a wide range of amounts. In preferred embodiments, the total amount of pretilachlor, pyrazosulfuron-ethyl and chlorimuron in the composition can range from about 0.1% to about 95% by weight of the composition.
[0054] In certain embodiments, pretilachlor can be present in the composition in amount by weight from about 0.01% to about 40%, preferably from about 0.05% to about 35%, more preferably from 0.1% to about 30%.
[0055] In certain embodiments, pyrazosulfuron-ethyl can be present in the composition in amount by weight from about 0.01% to about 40%, preferably from about 0.05% to about 35% of pyrazosulfuron-ethyl, more preferably from about 0.1% to about 30%.
[0056] In certain embodiments, chlorimuron-ethyl or its agriculturally acceptable derivatives can be present in the composition in amount by weight from about 0.01% to about 30%, preferably from 0.05% to about 25%, more preferably from about 0.07% to about 20%.
[0057] In some embodiments, the composition comprises, by weight, from about 0.01% to about 40% of pretilachlor, from about 0.01% to about 40% of pyrazosulfuron-ethyl and from about 0.01% to about 30% of chlorimuron-ethyl or its agriculturally acceptable derivatives.
[0058] In some preferred embodiments, the composition comprises, by weight, from about 0.05% to about 35% of pretilachlor, from about 0.05% to about 35% of pyrazosulfuron-ethyl and from about 0.05% to about 25% of chlorimuron-ethyl or its agriculturally acceptable derivatives.
[0059] In some more preferred embodiments, the composition comprises, by weight, from about 0.1% to about 30% of pretilachlor, from about 0.1% to about 30% of pyrazosulfuron-ethyl and from about 0.07% to about 20% of chlorimuron-ethyl or its agriculturally acceptable derivatives.
[0060] In various embodiments, the herbicide composition of the present disclosure can be formulated by mixing pretilachlor, pyrazosulfuron-ethyl and chlorimuron with one or more formulation auxiliaries. Suitable auxiliary additives will depend upon such factors as the type of formulation and the manner of the end use of the formulation, and will be known to a person skilled in the art. In some preferred embodiments, the one or more auxiliary additives are selected from without limitation inert carriers, solvents, anti-foaming agents, dispersing agents, wetting agents, stabilizing agents, anti-caking agents, buffering agents, surfactants, emulsifiers, pH stabilizer, anti-freezing agents, binding agents, antioxidants, colorants, and thickeners.
[0061] As indicated above, the herbicide composition may comprise one or more inert carriers. Suitable inert carrier(s) for use in the composition include, but not limited to, natural ground minerals, such as kaolin or china clay, alumina, talc, chalk, quartz, attapulgite, montmorillonite, and diatomaceous earth, or synthetic ground minerals, such as highly dispersed silicic acid, aluminium oxide, silicates, and calcium phosphates and calcium hydrogen phosphates, or combinations thereof. Suitable inert carrier(s) for granules include, for example, crushed and fractionated natural minerals, such as calcite, marble, pumice, sepiolite, bentonite, river sand, zeolites, starch, sand, talc, quartz and dolomite, or synthetic granules of inorganic and organic ground materials, as well as granules of organic material, such as sawdust, coconut husks, corn cobs, and tobacco stalks, or combinations thereof. The inert carrier may be used in an amount of from about 0.01% to about 99%, preferably from about 0.1% to about 95% by weight of the composition.
[0062] In at least one embodiment, the dispersing agent can be selected from lignosulphonates, sodium lignosulfonate, phenyl naphthalene sulphonates, ethoxylated alkyl phenols, ethoxylated fatty acids, alkoxylated linear alcohols, polyaromatic sulfonates, sodium alkyl aryl sulfonates, maleic anhydride copolymers, phosphate esters, condensation products of aryl/alkyl sulphonic acids and formaldehyde, addition products of ethylene oxide and fatty acid esters, sulfonates of condensed naphthalene, lignin derivatives, naphthalene formaldehyde condensates, polycarboxylates, sodium alkyl benzene sulfonates, salts of sulfonated naphthalene, ammonium salts of sulfonated naphthalene, salts of polyacrylic acids, salts of phenol sulfonic acids or combinations thereof. Dispersing agent is present in an amount of from about 0.05% to about 25%, preferably from about 0.3% to about 18% by weight of the composition.
[0063] In at least one embodiment, the wetting agent can be selected from alkyl phenol ethoxylate, fatty oil ethoxylate, phenyl naphthalene sulphonates, alkyl naphthalene sulfonates, sodium salt of alkyl naphthalene sulfonate, sodium salt of sulfonated alkyl carboxylate, polyoxyalkylated ethyl phenols, polyoxyethoxylated fatty alcohols, polyoxyethoxylated fatty amines, lignin derivatives, alkane sulfonates, alkylbenzene sulfonates, salts of polycarboxylic acids, salts of esters of sulfosuccinic acid, alkylnaphthalenesulfonates, alkylbenzenesulfonates, alkylpolyglycol ether sulfonates, alkyl ether phosphates, alkyl ether sulfates and alkyl sulfosuccinic monoesters, or combinations thereof. The wetting agent may be used in an amount of from about 0.01% to about 20%, preferably from about 0.01% to about 15% by weight of the composition.
[0064] In one embodiment, the stabilizing agent can be selected from modified hydrophobic silica, colloidal silica, precipitated silica, hydrophobic silica powder and mixtures thereof. Preferably, the stabilizing agent is dimethyldichlorosilane-treated fumed silica. In another embodiment, the stabilizing agent can be selected from epoxidized soybean oil, gamma butyrolactone, butylated hydroxyl toluene and its derivatives, epichlorhydrin, quinone derivatives, hydrazine hydrates and its derivatives, general class UV stabilizers, glycols and its derivatives or combinations thereof. The stabilizing agent may be used in an amount of from about 0.01% to about 10% by weight, preferably from about 0.01% to about 5% by weight based on a total weight of the composition.
[0065] In at least one embodiment, the anti-caking agent can be selected from kaolin clay, precipitate silica, colloidal silica, fumed silica, talc, gypsum, silicates, calcium carbonate, magnesium carbonate, magnesium sulfate, or combinations thereof. The anti-caking agent may be used in an amount of from about 0% to about 10%, preferably from about 0% to about 5% by weight of the composition.
[0066] In at least one embodiment, the binding agent can be selected from polyvinyl pyrrolidone (PVP), polyvinyl alcohol, sodium bentonite, ethyl cellulose, microcrystalline cellulose, carboxymethyl cellulose, lactose, lignin or starch and the mixture thereof. The binding agent is present in an amount of from about 0.01% to about 10%, preferably from about 0.01% to about 5% by weight of the composition.
[0067] In at least one embodiment, the buffering agent can be selected from H+ bentonite, calcium bentonite, sodium bentonite, H+ hectorite, calcium hectorite, sodium hectorite or combinations thereof. The buffering agent is present in an amount of from about 0% to about 10%, preferably from about 0% to about 5% by weight of the composition.
[0068] Suitable anti-foaming agents for use in the composition include all substances which can normally be used for this purpose in agrochemical compositions. Particularly preferred anti-foaming agents are mixtures of polydimethylsiloxanes and perfluroalkylphosphonic acids, such as the silicone anti-foaming agents available from GE or Compton. The anti-foaming agent may be used in an amount of from about 0% to about 6%, preferably from about 0% to about 3% by weight of the composition.
[0069] Suitable solvents for use in the composition may be selected from all customary organic solvents which dissolve one or more of the active ingredients employed. Suitable organic solvents for the compounds pretilachlor, pyrazosulfuron-ethyl and chlorimuron are known in the art. Preferred solvent include, but not limited to, deionized (DI) water, water immiscible solvent, vegetable oils, methylated vegetable oil and paraffin oil. Water immiscible solvent can be selected from but not limiting to aromatic hydrocarbon, solvent naphtha (heavy, medium, light), turpentine oil, Pine oil, Pseudocumene (1,2,4-trimethylbenzene) and blends thereof; (b) high HLB emulsifier: ethoxylated branched C11-14, C13-rich alcohols or combinations thereof. Solvents may present in the composition in an amount ranging from about 0.01 to about 20%, preferably from about 0.1% to about 10% by weight of the composition.
[0070] Suitable pH stabilizer can be selected from without limitation trisodium citrate, trisodium phosphate, tripotassium phosphate, triethanol amine, triethyl amine, ammonioum hydroxide, magnesium carbonate, magnesium sulphate, sodium bentonite, china clay, attapulgite, and diatomaceous earth or combination thereof. The pH stabilizer is used to adjust the pH ranging from about 8.0 – 10.0. The pH stabilizer may present in the composition in an amount ranging from about 0.01 to about 70%, preferably from about 0. 1% to about 50% by weight of the composition
[0071] Suitable antioxidants are all substances which can normally be used for this purpose in agrochemical compositions, as is known in the art. Preferred antioxidant is butylated hydroxytoluene. Antioxidant may present in the composition in an amount ranging from about 0 to about 10%, preferably from about 0% to about 5% by weight of the composition.
[0072] Suitable thickeners for use in the composition include all substances which can normally be used for this purpose in agrochemical compositions. Examples include xanthan gum, polyvinyl alcohol, cellulose and its derivatives, hydrated clay minerals, magnesium aluminium silicates or combinations thereof. Thickener may present in the composition in an amount ranging from about 0 to about 10%, preferably from about 0% to about 5% by weight of the composition.
[0073] Suitable anti-freezing agents include organic solvents which are completely miscible with water, such as ethylene glycol, propylene glycol, other glycols, glycerine, urea or combinations thereof. Anti-freezing agent may present in the composition in an amount ranging from about 0 to about 15%, preferably from about 0% to about 10% by weight of the composition.
[0074] Suitable surfactants or emulsifiers for use in the composition include all substances which can normally be used for this purpose in agrochemical compositions. Examples include substances which are non-ionic, cationic and/or anionic in nature. Suitable surfactants or emulsifiers can be selected from but not limited to, ethoxylated fatty alcohol (Atlox ™ 4991 also known as Polyoxyethylene alkyl ether), salts of polyacrylic acids, salts of lignosulphonic acid, salts of phenylsulphonic or naphthalenesulphonic acids, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols, especially alkylphenols, sulphosuccinic ester salts, taurine derivatives, especially alkyl taurates, and phosphoric esters of polyethoxylated phenols or alcohols. Surfactant may present in the composition in an amount ranging from about 0.01 to about 15%, preferably from about 0.01% to about 10% by weight of the composition.
[0075] The presence of at least one surfactant or emulsifier is generally required when the active ingredient(s) and/or the auxiliary additives are insoluble in water and the vehicle for the final application of the composition is water.
[0076] According to embodiments of the present disclosure, the disclosed herbicide composition can additionally include one or more further agrochemical active compounds, such as insecticides, nematicides, fungicides, safeners, growth factor enhancers and fertilizers, in addition to the components pretilachlor, pyrazosulfuron-ethyl and chlorimuron.
[0077] According to embodiments of the present disclosure, the composition of the present disclosure can be provided as a formulation.
[0078] In certain embodiments the composition of the present disclosure can used in a conventional way diluted with water. In certain embodiment, the present disclosure provides a tank mix comprising separately formulated or partially separately formulated pretilachlor, pyrazosulfuron-ethyl and chlorimuron-ethyl.
[0079] In various embodiments, the present disclosure provides formulations comprising the herbicide composition of the present invention.
[0080] In an embodiment, the present disclosure provides a formulation comprising a herbicidally effective amount of the active ingredients pretilachlor, pyrazosulfuron-ethyl and chlorimuron-ethyl, and one or more auxiliary additives, wherein the ratio of pretilachlor : pyrazosulfuron-ethyl : chlorimuron is ranges from about 1 : 0.001 : 0.0001 to about 10 : 8: 4, preferably from about 1 : 0.01 : 0.001 to about 5 : 4 : 1.8.
[0081] Formulations can be in liquid or solid form. In preferred embodiments, the disclosed formulations comprising the herbicide composition can be without limitation water-dispersible granule (WDG or WG), a water-soluble granule (SG), a wettable powder (WP), a water-dispersible powder (WDP), a water-soluble powder (SP), a granule (GR), an encapsulated granule (CG), a fine granule (FG), a macrogranule (GG), a microgranule (MG), a suspension concentrate (SC), a water-soluble concentrate (SL), an emulsifiable concentrate (EC), an emulsion (EW), a micro-emulsion (ME), an oil-based suspension concentrate (OD), a flowable suspension (FS), a suspoemulsion (SE), or a microencapsulated suspension (CS).
[0082] The present disclosure further provides a process for preparing the formulation comprising the herbicide composition described herein. The formulation can be prepared by mixing and/or grinding the respective active compounds and, if appropriate, one or more auxiliary additives.
[0083] The synergistic effects of the combination of pretilachlor, pyrazosulfuron-ethyl and chlorimuron can provide one or more of a number of advantages over the use of each active ingredient alone. In particular, the rates of application of each active ingredient can be markedly reduced, when the three compounds are used in combination, while maintaining a high level of herbicidal efficacy. More especially, the use of the combination of pretilachlor, pyrazosulfuron-ethyl and chlorimuron has the potential to control weed species at a low application rate, in particular at a rate of application at which the individual active ingredients alone are ineffective. A treatment using the combination of pretilachlor, pyrazosulfuron-ethyl and chlorimuron can exhibit a considerably broader weed spectrum than the compounds when used alone. The use of a composition comprising the three aforementioned active ingredients also has a speed of action which is faster than that which would have been predicted from the speed of each ingredient used individually.
[0084] The herbicide composition of the present disclosure is useful for both pre-emergence and early post-emergence control of undesirable vegetation. As employed herein, the term “undesirable vegetation” denotes non-crop plant species that otherwise tend to grow in areas where crops are planted, and includes both volunteer crops and weeds. The term "control of undesirable vegetation" refers to interference with normal growth and development of undesired vegetation. Examples of control activity include, but not limited to, inhibition of root growth, inhibition of shoot growth, inhibition of shoot emergence, inhibition of seed production, or reduction of weed bio mass. The undesirable vegetation whose control is of greatest interest in the practice of present invention are weeds, and primarily those weeds associated with common crops such as rice, preferably transplanted rice. The control of undesirable vegetation in such crops may be achieved by applying to the undesirable vegetation or to locus of the vegetation the combination of pretilachlor, pyrazosulfuron-ethyl and chlorimuron in suitable amounts.
[0085] In various embodiments, the present disclosure provides a method of controlling undesirable vegetation in crops of useful plants, which comprises allowing a herbicidally active amount of a composition according to the present disclosure to act on the crop plant or its environment.
[0086] In certain embodiment, the method of controlling undesirable vegetation in crops of useful plants comprises treating the undesirable vegetation in crops of useful plants with the composition or tank mix or formulation of the present disclosure, by applying the same at a rate which corresponds to a total amount of 0.05 to 6 kg of active ingredient per hectare.
[0087] In various embodiments, the herbicide composition according to the present disclosure is particularly advantageous in the protection of cereals, more preferably rice crops.
[0088] In various embodiments, the herbicide composition according to the present disclosure can exhibit a synergistic herbicidal activity against a broad spectrum of economically important weeds, including broadleaf, sedge and grass weeds.
[0089] The disclosed herbicide composition comprising combination of pretilachlor, pyrazosulfuron-ethyl and chlorimuron-ethyl can be applied in a variety of ways known to those skilled in the art, at various concentrations. The herbicide composition of the present disclosure is useful in controlling growth of undesirable vegetation by pre-emergence and/or early post-emergence application to undesirable vegetation and/or locus thereof where control is desired. The herbicide composition may be applied to undesirable vegetation and/or locus thereof by broadcasting with sand.
[0090] In various embodiments, effective herbicidal effects can be achieved with both pre-emergence application and early post-emergence application of the herbicide composition of the present disclosure. Useful methods of application include broadcasting.The application rates of the herbicide composition to soil can vary over a wide range. The optimal application rates will depend on the crop to be protected, the stage of growth of the crop and of the weed, and the manner in which application is made.. The total application rate of pretilachlor, pyrazosulfuron-ethyl and chlorimuron can vary within a wide range, for example from 1 to 2000g per hectare (g/ha). Preferably, the application rate ranges from 2 to 1000 g/ha.
[0091] According to embodiments, the herbicide composition disclosed herein may be applied in a single treatment or in several treatments (sequential application), for example one or more pre-emergence applications, followed by one or more early post-emergence applications, While the foregoing description discloses various embodiments of the disclosure, other and further embodiments of the invention may be devised without departing from the basic scope of the disclosure. The invention is not limited to the described embodiments, versions or examples, which are included to enable a person having ordinary skill in the art to make and use the invention when combined with information and knowledge available to the person having ordinary skill in the art.

EXAMPLES
[0092] The present disclosure is further explained in the form of following examples. However, it is to be understood that the foregoing examples are merely illustrative and are not to be taken as limitations upon the scope of the invention. Various changes and modifications to the disclosed embodiments will be apparent to those skilled in the art. Such changes and modifications may be made without departing from the scope of the invention.

Example 1:
Aqueous Tank Mix
[0093] An aqueous tank mix was prepared by mixing Pretilachlor 50% EC, Pyrazosulfuron-ethyl 10% WP, Chlorimuron-ethyl 25% WP, and water at room temperature. The tank mix composition comprising the herbicide combination was tested for its biological activity and the results are shown in Tables 1 & 2 below:

Table-1: Field Test Results of the Combination of Pretilachlor, Pyrazosulfuron-ethyl and Chlorimuron-ethyl applied (as pre-emergent) at 2 DAP1 for weed control in transplanted rice

Treatment Dosage Mean no. of weeds/0.25sq.mt area (33 DAA3)
g a.i./ha2 Formulation
(g/mL/kg/ha) Grasses Broadleaf weeds Sedges Total
Pretilachlor 50% EC + Pyrazosulfuron-ethyl 10%WP +Chlorimuron-ethyl 25%WP 750 + 20 + 6 1500 + 200 + 24 0.00 0.00 0.00 0.00
Pretilachlor 50% EC + Pyrazosulfuron-ethyl 10%WP +Chlorimuron-ethyl 25%WP 712.5 + 19 + 5.7 1425 + 190 + 22.8 0.00 0.50 0.50 1.00
Pretilachlor 50% EC + Pyrazosulfuron-ethyl 10%WP +Chlorimuron-ethyl 25%WP 625 + 18 + 5.4 1350 + 180 + 21.6 2.50 2.17 1.50 6.17
Pretilachlor 50% EC 750 1500 3.33 3.50 1.67 8.50
Pyrazosulfuron-ethyl 10% WP 20 200 4.50 5.50 2.67 12.67
Chlorimuron-ethyl 25% WP 6 24 6.67 0.83 2.33 9.83
Pretilachlor 6% + Pyrazosulfuron-ethyl 0.15% GR (Standard) 600 + 15 10 2.67 2.50 1.33 6.50
Untreated check - - 18.33 11.50 7.67 37.50
DAP1 = Days after planting
2Application rate is stated in units of grams active ingredient per hectare
DAA3 = Days after application

Table-2: Field Test Results of the Combination of Pretilachlor, Pyrazosulfuron-ethyl and Chlorimuron-ethyl applied (as pre-emergent) at 2 DAP1 for weed control in transplanted rice (% Weed control relative to untreated check)

Treatment Dosage % control over untreated check (33 DAA3)
g a.i./ha2 Formulation
(g/mL/kg/ha) Grasses Broadleaf weeds Sedges % Mean control
Pretilachlor 50% EC + Pyrazosulfuron-ethyl 10%WP +Chlorimuron-ethyl 25%WP 750 + 20 + 6 1500 + 200 + 24 100.00 100.00 94.00 98.00
Pretilachlor 50% EC + Pyrazosulfuron-ethyl 10%WP +Chlorimuron-ethyl 25%WP 712.5 + 19 + 5.7 1425 + 190 + 22.8 100.00 95.65 93.48 96.37
Pretilachlor 50% EC + Pyrazosulfuron-ethyl 10%WP +Chlorimuron-ethyl 25%WP 625 + 18 + 5.4 1350 + 180 + 21.6 86.36 81.16 80.43 82.65
Pretilachlor 50% EC 750 1500 81.82 69.57 78.26 76.55
Pyrazosulfuron-ethyl 10% WP 20 200 75.45 52.17 65.22 64.28
Chlorimuron-ethyl 25% WP 6 24 63.64 92.75 69.57 75.32
Pretilachlor 6% + Pyrazosulfuron-ethyl 0.15% GR (Standard) 600 + 15 10 85.45 78.26 82.61 82.10
Untreated check - - 0.00 0.00 0.00 -
DAP1 = Days after planting
2Application rate is stated in units of grams active ingredient per hectare
DAA3 = Days after application

[0094] From the test results shown above, it is evident that there is an unexpected and surprising result, that is synergistic effect of the combination of pretilachlor, pyrazosulfuron-ethyl and chlorimuron-ethyl in the control of weeds in rice fields. As can be seen from Tables 1 and 2, the combined administration of pretilachlor, pyrazosulfuron-ethyl and chlorimuron-ethyl resulted in significant reduction in weeds population as compared to single administration of the individual herbicides. As can be seen from Tables 1 and 2, the present herbicide combination applied in a single treatment to the transplanted rice crop kills substantially all of the weeds, thereby avoiding a need for successive treatments. It is also evident that the combination preparation in accordance with the present invention exhibits a superior herbicidal effect as compared to other known herbicidal products available in the market.

Examples 2-4
Granular (GR) Formulations
[0095] Granular (GR) formulations were prepared as per compositions provided in Table 3 and the process provided below:

1. Compositions:
Table 3: A. Compositions for GR Formulations:
Ingredients Category Example-2
% w/w Example-3
% w/w Example-4
% w/w
Chlorimuron ethyl Active ingredient 0.10 0.5 0.3
Pyrazosulfuron ethyl Active ingredient 0.30 1.0 1.5
Pretilachlor Active ingredient 9.0 7.5 6.0
Solvent naphtha Water immiscible solvent 3.0 2.5 2.3
Atlox ™ 4991 Emulsifier 0.5 0.5 1.0
Sodium lignosulfonate Dispersing agent 8.0 6.0 9.0
Polyvinyl pyrrolidone Binding agent 0.5 0.5 0.5
Trisodium phosphate pH stabilizer 0.6 1.2 2.2
Sodium bentonite pH stabilizer 20.0 10.0 2.0
Polydimethylsiloxane Antifoaming agent 0.5 0.4 0.30
China clay Inert Carrier Q.S Q.S Q.S
Total 100.00 100.00 100.00

2. Process:
[0096] GR formulations were prepared as per the following process steps.
Step 1: Preparation of emulsion part:
[0097] In a clean and dry mixing vessel fitted with homogenizer, solvent naptha, Atlox ™ 4991(ethoxylated fatty alcohol), poly dimethyl siloxane and pretilachlor were weighed and added. Components were mixed for 30 mins in homogenizer. To this water was added and mixing was continued for 1 hour under high speed homogenizer of about 5000 – 6000 rpm to obtain emulsion.
Step 2: Preparation of milled powder part:
[0098] In a clean and dry ribbon blender weighed quantity of sodium bentonite, china clay, sodium lignosulfonate, polyvinyl pyrrolidone, trisodium phosphate, chlorimuron-ethyl and pyrazosulfuron ethyl were added and mixed well for 1 hr to provide a pre-mixed powder. This pre-mixed powder was passed through air jet mill for particle size reduction, to obtain d(90) less than 15 microns. Post mixing the milled powder was added to a ribbon blender and blended for 2 hours to obtain homogenous powder.
Step 3: Preparation of GR formulation:
[0099] A dough maker was charged with emulsion part into and previously prepared milled powder part, to which demineralized water was added to form a smooth dough. The dough was extruded through a basket extruder and the granules obtained were dried in a fluid bed drier (FBD) to obtain granular formulations (GR).

Examples 5-6
Water dispersible granules (WG) Formulations
[00100] Water dispersible granules (WG) formulations were prepared as per compositions provided in Table 4 and the process provided below:

Table 4: B. Compositions for WG Formulations:
Ingredients Category Example-5
% w/w Example-6
% w/w
Chlorimuron ethyl tech Active ingredient 1.0 5.0
Pyrazosulfuron ethyl tech Active ingredient 3.0 10.0
Pretilachlor tech Active ingredient 18.0 15.0
Solvent naphtha Water immiscible solvent 4.5 3.5
Atlox ™ 4991 Emulsifier 5.0 3.0
Poly dimethylsiloxane Antifoaming agent 0.5 0.5
Sodium lignosulfonate Dispersing agent 10.0 8.0
Polyvinyl pyrrolidone Binding agent 0.8 0.7
Sodium salt of alkyl naphthalene sulfonate Wetting agent 2.0 1.5
Trisodium phosphate pH Stabilizer 1.1 0.8
Sodium bentonite pH Stabilizer 12.0 14.0
China clay Inert Carrier Q.S Q.S
Total 100.00 100.00

2. Process:
[00101] WG formulations were prepared as per the following process steps.
[00102] Step 1: Preparation of emulsion part:
[00103] In a clean and dry mixing vessel fitted with homogenizer, solvent naptha, Atlox ™ 4991(ethoxylated fatty alcohol), poly dimethyl siloxane and pretilachlor were weighed and added. Components were mixed for 30 mins in homogenizer. To this water was added and mixing was continued for 1 hour under high speed homogenizer of about 5000 – 6000 rpm to obtain emulsion.
Step 2: Preparation of milled powder part:
[00104] In a clean and dry ribbon blender weighed quantity of sodium lignosulphonate, polyvinyl pyrrolidone, trisodium phosphate, sodium salt of alkyl naphthalene sulfonate, china clay and sodium bentonite added and mixed well for 1 hr to provide a pre-mixed powder. This pre-mixed powder was passed through air jet mill for particle size reduction, to obtain d(90) less than 15 microns. Post mixing the milled powder was added to a ribbon blender and blended for 2 hours to obtain homogenous powder.
Step 3: Preparation of WG formulation:
[00105] A dough maker was charged with emulsion part into and previously prepared milled powder part, to which demineralized water was added to form a smooth dough. The dough was extruded through a basket extruder and the granules obtained were dried in a fluid bed drier (FBD) to obtain water dispersible granules (WG).

Example 7
Accelerated Storage test (Stability Study)
[00106] The GR formulation obtained as per Example 2 was subjected to Accelerated Storage test. According to the FAO/WHO manual, the “accelerated storage test” is considered as an indicative of product stability. That is accelerated storage test data provides an indication that the product is stable for at least two years at ambient temperature. Further, the FAO/WHO manual indicates storage at 54°C ± 2°C for 14 days as the default test conditions.
[00107] The “ambient sample” is the sample at the room temperature which is before subjecting to the accelerated storage tests at 54±2°C for 14 days.
[00108] The “accelerated storage sample” is the sample after subjecting to the accelerated storage test.
[00109] Table 5 shows the physical and chemical properties of the GR formulation of Example 2 before and after the accelerated storage test

Table 5: Stability Data
S. No. Tests Product Specifications Ambient Sample
(Before) Accelerated Storage Sample Tested @ 54±2°C For 14 Days
(After)
1 Description Off white to light brown color free flowing granules Complies Complies
2 Active content
(i) Chlorimuron-ethyl content, % w/w 0.095 - 0.110 0.10 0.099
(ii) Pyrazosulfuron-ethyl content, % w/w 0.285 – 0.33 0.30 0.3
(iii) Pretilachlor content, % w/w 8.55 – 9.90 9.0 8.98
3 pH of 1% aq. suspension 8.0 - 10.0 9.20 9.32
4 Moisture content, %w/w Max 1.0 0.20 0.20
5 Dustiness, material passing through 75 micron test sieve, % w/w Max 30 mg nil nil
6 Attrition resistance,%w/w Max 99.0 99.60 99.62
7 Sieving Analysis:-

Material passing through IS 1200 micron sieve (14BSS), % w/w

Material retained on 420 micron (36 BSS) sieve, % w/w

Min 97

Min 95

98.97


99.18

98.95


99.20

[00110] From the above data it can be seen that the content of chlorimuron-ethyl, pyrazosulfuron-ethyl and pretilachlor is found to be 0.10% w/w, 0.30% w/w, 9.0% w/w respectively before subjecting the ambient sample to the accelerated storage test. After subjecting the ambient sample to the accelerated storage test (that is storing at 54±2°C for 14 days in the HDPE containers) the content of chlorimuron-ethyl, pyrazosulfuron-ethyl and pretilachlor is found to be almost same, that is 0.099%w/w, 0.30%w/w, 8.98%w/w respectively. It indicates that the content of chlorimuron-ethyl, pyrazosulfuron-ethyl and pretilachlor is degraded only by 1.0%, 0% and 0.22% respectively and falls within the product specification range and hence the content of the active ingredients in the formulation is stableThe pH of the ambient sample of the GR before subjecting it to the accelerated storage test was found to be 9.20. However, even after subjecting the ambient sample to the accelerated storage test the pH was found to be almost same, that is 9.32. It indicates that the GR was adhering to the pH range of 8.0 - 10.0 which indicates that the formulation is stable.
[00111] Moisture content test showed low moisture content of 0.20% indicating dried granules.
[00112] Dustiness test showed no dust generation (nil) indicating no dust formation during, handling, transportation and storage.
[00113] Attrition resistance showed high attrition resistance of 99.60% w/wand 99.62% w/w of granules indicating no breakage of granules during transport.
[00114] Sieving Analysis test showed passing of 98.97 % w/w and 98.95% w/w of granules through 1200 micron sieve and 99.18% w/w and 99.20% w/w of granules through 420 micron sieve indicating the presence of homogeneous granules without any fines and odd size granules.

Example 8
Field Trial Data Showing Synergistic Activity
[00115] Effect of the GR formulation prepared as per Example 2 were studies against major weeds in transplanted rice field.
i) Effect of GR formulation of Example 2 against major weeds in Kharif rice field in Mandya, Karnatak, in 2021
Date of transplanting: 04/09/2021
Date of application: 06/09/2021(2 days after planting)
Method of application: Soil application by broadcasting with sand
Dates of observation: 06/10/2021
Table 6: The results in terms of reduction in mean no of weeds.
Treatment Dosage Mean no.of weeds /0.25sq.mt area(30 days after spraying)
g a.i./ha Formulation (g/ml/ha) Grasses BLW Sedges Total
Pretilachlor 9%+ Pyrazosulfuron-ethyl 0.3% + Chlorimuron ethyl 0.1%GR 470 5000 0.00 0.00 0.00 0.00
Pretilachlor 9%+ Pyrazosulfuron-ethyl 0.3% + Chlorimuron ethyl 0.1%GR 423 4500 0.00 0.50 0.33 0.83
Pretilachlor 9%+ Pyrazosulfuron-ethyl 0.3% + Chlorimuron ethyl 0.1%GR 376 4000 1.83 2.33 1.17 5.33
Pretilachlor 50% EC+Pyrazosulfuron Ethyl 10% WP+Chlorimuron ethyl 25% WP
(Tank mix) 500+20+6 1000+200+24 1.33 2.00 1.00 4.33
Pretilachlor 50% EC 500 1000 4.33 3.50 2.17 10.00
Pyrazosulfuron Ethyl 10% WP 20 200 5.83 3.00 2.33 11.17
Chlorimuron ethyl 25% WP 6 24 7.67 1.17 4.33 13.17
Pretilachlor 6%+Pyrazosulfuron Ethyl 0.15% GR (Standard check) 615 10 000 1.67 2.00 1.17 4.83
UTC - - 19.00 11.50 8.17 38.67

ii) Effect of GR formulation of Example 2 against major weeds in Kharif rice field in Mandya, Karnatak, in 2021
Date of transplanting: 04/09/2021
Date of application: 06/09/2021 (2 days after planting)
Method of application: Soil application by broadcasting with sand
Dates of observation: 06/10/2021
Table 7: The result in terms of percent reduction over the untreated check (UTC)
Treatment Dosage % Control over UTC
( 30 days after spraying)
g a.i./ha Formulation (g/ml/ha) Grasses BLW Sedges % Mean
Pretilachlor 9%+ Pyrazosulfuron-ethyl 0.3% + Chlorimuron ethyl 0.1%GR 470 5000 100.00 100.00 100.00 100.00
Pretilachlor 9%+ Pyrazosulfuron-ethyl 0.3% + Chlorimuron ethyl 0.1%GR 423 4500 100.00 95.65 95.92 97.19
Pretilachlor 9%+ Pyrazosulfuron-ethyl 0.3% + Chlorimuron ethyl 0.1%GR 376 4000 90.35 79.71 85.71 85.26
Pretilachlor 50% EC+Pyrazosulfuron Ethyl 10% WP+Chlorimuron ethyl 25% WP (Tank mix) 500+20+6 1000+200+24 92.98 82.61 87.76 87.78
Pretilachlor 50% EC 500 1000 77.19 69.57 73.47 73.41
Pyrazosulfuron Ethyl 10% WP 20 200 69.30 73.91 71.43 71.54
Chlorimuron ethyl 25% WP 6 24 59.65 89.86 46.94 65.48
Pretilachlor 6%+Pyrazosulfuron Ethyl 0.15% GR (Standard check) 615 10 000 91.23 82.61 85.71 86.51
UTC - - - - - -

iii) Effect of GR formulation of Example 2 against major weeds in Kharif rice field in Ponnuru, Andra Pradesh, in 2021

Date of transplanting: 02/09/2021
Date of application: 03/09/2021 (1 day after planting)
Method of application: Soil application by broadcasting with sand
Dates of observation: 09/10/2021
Table 8: The result in terms of reduction in mean no of weeds
Treatment Dosage Mean no. of weeds /0.25sq.mt area(36 days after spraying)
g a.i./ha Formulation (g/ml/ha) Grasses BLW Sedges Total
Pretilachlor 9%+ Pyrazosulfuron-ethyl 0.3% + Chlorimuron ethyl 0.1%GR 470 5000 0.33 0.00 0.67 1.00
Pretilachlor 9%+ Pyrazosulfuron-ethyl 0.3% + Chlorimuron ethyl 0.1%GR 423 4500 0.33 0.00 1.00 1.33
Pretilachlor 9%+ Pyrazosulfuron-ethyl 0.3% + Chlorimuron ethyl 0.1%GR 376 4000 0.67 0.33 0.33 1.33
Pretilachlor 50% EC+Pyrazosulfuron Ethyl 10% WP+Chlorimuron ethyl 25% WP (Tank mix) 500+20+6 1000+200+24 0.33 0.33 0.67 1.33
Pretilachlor 50% EC 500 1000 0.33 0.67 2.00 3.00
Pyrazosulfuron Ethyl 10% WP 20 200 2.00 1.00 0.00 3.00
Chlorimuron ethyl 25% WP 6 24 0.67 0.33 1.33 2.33
Pretilachlor 6%+Pyrazosulfuron Ethyl 0.15% GR (Standard check) 615 10 000 1.00 0.67 1.00 2.67
UTC - - 5.00 2.33 6.00 13.33

iv) Effect of GR formulation of Example 2 against major weeds in Kharif rice field in Ponnuru, Andra Pradesh, in 2021
Date of transplanting: 02/09/2021
Date of application: 03/09/2021 (1 day after planting)
Method of application: Soil application by broadcasting with sand
Dates of observation: 09/10/2021
Table 9: The result in terms of percent reduction over the untreated check (UTC).
Treatment Dosage % Control over UTC
( 36 days after spraying)
g a.i./ha Formulation (g/ml/ha) Grasses BLW Sedges % Mean
Pretilachlor 9%+ Pyrazosulfuron-ethyl 0.3% + Chlorimuron ethyl 0.1%GR 470 5000 93.33 100.00 88.89 94.07
Pretilachlor 9%+ Pyrazosulfuron-ethyl 0.3% + Chlorimuron ethyl 0.1%GR 423 4500 93.33 100.00 83.33 92.22
Pretilachlor 9%+ Pyrazosulfuron-ethyl 0.3% + Chlorimuron ethyl 0.1%GR 376 4000 86.67 85.69 94.44 88.93
Pretilachlor 50% EC+Pyrazosulfuron Ethyl 10% WP+Chlorimuron ethyl 25% WP (Tank mix) 500+20+6 1000+200+24 93.33 85.69 88.89 89.31
Pretilachlor 50% EC 500 1000 93.33 71.39 66.67 77.13
Pyrazosulfuron Ethyl 10% WP 20 200 60.00 57.08 100.00 72.36
Chlorimuron ethyl 25% WP 6 24 86.67 85.69 77.78 83.38
Pretilachlor 6%+Pyrazosulfuron Ethyl 0.15% GR (Standard check) 615 10 000 80.00 71.39 83.33 78.24
UTC - - - - - -

v) Effect of GR formulation of Example 2 against major weeds in Kharif rice field in Dhamtari,Chhatisgarh, in 2021
Date of transplanting: 02/08/2021
Date of application: 03/08/2021 (1 day after planting)
Method of application: Soil application by broadcasting with sand
Dates of observation: 03/09/2021
Table 10: The result in terms of reduction in mean no of weeds.
Treatment Dosage Mean no.of weeds /0.25sq.mt area(30 days after spraying)
g a.i./ha Formulation (g/ml/ha) Grasses BLW Sedges Total
Pretilachlor 9%+ Pyrazosulfuron-ethyl 0.3% + Chlorimuron ethyl 0.1%GR 470 5000 1.00 0.33 0.67 2.00
Pretilachlor 9%+ Pyrazosulfuron-ethyl 0.3% + Chlorimuron ethyl 0.1%GR 423 4500 2.33 2.33 1.67 6.33
Pretilachlor 9%+ Pyrazosulfuron-ethyl 0.3% + Chlorimuron ethyl 0.1%GR 376 4000 2.00 5.67 2.00 9.67
Pretilachlor 50% EC +Pyrazosulfuron Ethyl 10% WP +Chlorimuron ethyl 25% WP (Tank mix) 500+20+6 1000+200+24 3.67 5.00 3.33 12.00
Pretilachlor 50% EC 500 1000 2.67 8.33 11.00 22.00
Pyrazosulfuron Ethyl 10% WP 20 200 2.33 11.00 3.00 16.33
Chlorimuron ethyl 25% WP 6 24 4.00 4.67 12.33 21.00
Pretilachlor 6%+Pyrazosulfuron Ethyl 0.15% GR (Standard check) 615 10 000 3.67 8.67 3.67 16.00
Pretilachlor 9%+ Pyrazosulfuron-ethyl 0.3% + Chlorimuron ethyl 0.1%GR - - 25.67 37.33 81.67 144.67

vi) Effect of GR formulation of Example 2 against major weeds in Kharif rice field in Dhamtari,Chhatisgarh, in 2021

Date of transplanting: 02/08/2021
Date of application: 03/08/2021 (1 day after planting)
Method of application: Soil application by broadcasting with sand
Dates of observation: 03/09/2021
Table 11: The result in terms of percent reduction over the untreated check (UTC).
Treatment Dosage % Control over UTC
(30 days after spraying)
g a.i./ha Formulation (g/ml/ha) Grasses BLW Sedges % Mean
Pretilachlor 9%+ Pyrazosulfuron-ethyl 0.3% + Chlorimuron ethyl 0.1%GR 470 5000 96.10 99.11 99.18 98.13
Pretilachlor 9%+ Pyrazosulfuron-ethyl 0.3% + Chlorimuron ethyl 0.1%GR 423 4500 90.91 93.75 97.96 94.20
Pretilachlor 9%+ Pyrazosulfuron-ethyl 0.3% + Chlorimuron ethyl 0.1%GR 376 4000 92.21 84.82 97.55 91.52
Pretilachlor 50% EC +Pyrazosulfuron Ethyl 10% WP +Chlorimuron ethyl 25% WP (Tank mix) 500+20+6 1000+200+24 80.52 86.61 95.92 87.68
Pretilachlor 50% EC 500 1000 89.61 77.68 86.53 84.60
Pyrazosulfuron Ethyl 10% WP 20 200 90.91 70.54 96.33 85.92
Chlorimuron ethyl 25% WP 6 24 84.42 87.50 84.90 85.60
Pretilachlor 6%+Pyrazosulfuron Ethyl 0.15% GR (Standard check) 615 10 000 85.71 76.79 95.51 86.00
UTC - - - - - -

[00116] The above data shows the following advantageous effect of the composition of the present disclosure:
[00117] GR formulation compirising pretilachlor 9%, pyrazosulfuron-ethyl 0.3%, chlorimuron ethyl 0.1% when applied at the rate of 5kg/ha was found to be highly effective against all types of major weeds in rice in comparison with standard check and untreated check. The efficacy rate was very high (>92%). The data proves that the composition showed very good synergistic activity. There was effective control of key grasses, sedges and BLW with a longer duration of control (>36 days).
[00118] The foregoing examples are merely illustrative and are not to be taken as limitations upon the scope of the invention. Various changes and modifications to the disclosed examples will be apparent to those skilled in the art. Such changes and modifications may be made without departing from the scope of the invention.

,CLAIMS:1. A herbicide composition comprising a herbicidally effective amount of the active ingredients pretilachlor, pyrazosulfuron-ethyl and chlorimuron-ethyl, and one or more auxiliary additives.

2. The herbicide composition as claimed in claim 1, wherein the pretilachlor is present in the composition in an amount by weight ranging from about 0.01% to about 40%, preferably from about 0.05% to about 35%, more preferably from 0.1% to about 30%.

3. The herbicide composition as claimed in claim 1, wherein the pyrazosulfuron-ethyl is present in the composition in an amount by weight ranging from about 0.01% to about 40%, preferably from about 0.05% to about 35% of pyrazosulfuron-ethyl, more preferably from about 0.1% to about 30%.

4. The herbicide composition as claimed in claim 1, wherein the chlorimuron-ethyl is present in the composition in an amount by weight ranging from about 0.01% to about 30%, preferably from 0.05% to about 25%, more preferably from about 0.07% to about 20%.

5. The herbicide composition as claimed in claim 1, wherein the one or more auxiliary additives are selected from inert carriers, solvents, anti-foaming agents, dispersing agents, wetting agents, stabilizing agents, anti-caking agents, buffering agents, surfactants, emulsifiers, pH stabilizer, anti-freezing agents, binding agents, antioxidants, colorants, and thickeners.

6. The herbicide composition as claimed in claim 5, wherein the inert carrier(s) is selected from kaolin or china clay, alumina, talc, chalk, quartz, attapulgite, montmorillonite, diatomaceous earth, highly dispersed silicic acid, aluminium oxide, silicates, calcium phosphates, calcium hydrogen phosphates, calcite, marble, pumice, sepiolite, bentonite, river sand, zeolites, starch, sand, talc, quartz, dolomite, sawdust, coconut husks, corn cobs, tobacco stalks, or combinations thereof.

7. The herbicide composition as claimed in claim 6, wherein the inert carrier(s) is present in an amount from about 0.01% to about 99%, preferably from about 0.1% to about 95% by weight of the composition.

8. The herbicide composition as claimed in claim 5, wherein the dispersing agent is selected from lignosulphonates, sodium lignosulfonate, phenyl naphthalene sulphonates, ethoxylated alkyl phenols, ethoxylated fatty acids, alkoxylated linear alcohols, polyaromatic sulfonates, sodium alkyl aryl sulfonates, maleic anhydride copolymers, phosphate esters, condensation products of aryl/alkyl sulphonic acids and formaldehyde, addition products of ethylene oxide and fatty acid esters, sulfonates of condensed naphthalene, lignin derivatives, naphthalene formaldehyde condensates, polycarboxylates, sodium alkyl benzene sulfonates, salts of sulfonated naphthalene, ammonium salts of sulfonated naphthalene, salts of polyacrylic acids, salts of phenol sulfonic acids or combinations thereof.

9. The herbicide composition as claimed in claim 8, wherein the dispersing agent is present in an amount from about 0.05% to about 25%, preferably from about 0.3% to about 18% by weight of the composition.

10. The herbicide composition as claimed in claim 5, wherein the wetting agent is selected from alkyl phenol ethoxylate, fatty oil ethoxylate, phenyl naphthalene sulphonates, alkyl naphthalene sulfonates, sodium salt of alkyl naphthalene sulfonate, sodium salt of sulfonated alkyl carboxylate, polyoxyalkylated ethyl phenols, polyoxyethoxylated fatty alcohols, polyoxyethoxylated fatty amines, lignin derivatives, alkane sulfonates, alkylbenzene sulfonates, salts of polycarboxylic acids, salts of esters of sulfosuccinic acid, alkylnaphthalenesulfonates, alkylbenzenesulfonates, alkylpolyglycol ether sulfonates, alkyl ether phosphates, alkyl ether sulfates and alkyl sulfosuccinic monoesters, or combinations thereof.

11. The herbicide composition as claimed in claim 10, wherein the wetting agent is present in an amount from about 0.01% to about 20%, preferably from about 0.01% to about 15% by weight of the composition.

12. The herbicide composition as claimed in claim 5, wherein the binding agent is selected from polyvinyl pyrrolidone (PVP), polyvinyl alcohol, sodium bentonite, ethyl cellulose, microcrystalline cellulose, carboxymethyl cellulose, lactose, lignin or starch and the mixture thereof.

13. The herbicide composition as claimed in claim 12, wherein the binding agent is present in an amount from about 0.01% to about 10%, preferably from about 0.01% to about 5% by weight of the composition.

14. The herbicide composition as claimed in claim 5, wherein the anti-foaming agent is a mixtures of polydimethylsiloxanes and perfluroalkylphosphonic acids.

15. The herbicide composition as claimed in claim 14, wherein the anti-foaming agent is present in an amount from about 0% to about 6%, preferably from about 0% to about 3% by weight of the composition.

16. The herbicide composition as claimed in claim 5, wherein the solvent is selected from deionized (DI) water, water immiscible solvent, vegetable oils, methylated vegetable oil and paraffin oil , aromatic hydrocarbon, solvent naphtha (heavy, medium, light), turpentine oil, Pine oil, Pseudocumene (1,2,4-trimethylbenzene) and blends thereof, high HLB emulsifier, ethoxylated branched C11-14, C13-rich alcohols, or combinations thereof.

17. The herbicide composition as claimed in claim 16, wherein the solvent is present in an amount ranging from about 0.01 to about 20%, preferably from about 0.1% to about 10% by weight of the composition.

18. The herbicide composition as claimed in claim 5, wherein the pH stabilizer is selected from trisodium citrate, trisodium phosphate, tripotassium phosphate, triethanol amine, triethyl amine, ammonioum hydroxide, magnesium carbonate, magnesium sulphate, sodium bentonite, china clay, attapulgite, and diatomaceous earth or combination thereof.

19. The herbicide composition as claimed in claim 18, wherein the pH stabilizer is is present in an amount ranging from about 0.01 to about 70%, preferably from about 0. 1% to about 50% by weight of the composition.

20. The herbicide composition as claimed in claim 5, wherein the surfactants or emulsifiers can be selected from ethoxylated fatty alcohols, salts of polyacrylic acids, salts of lignosulphonic acid, salts of phenylsulphonic or naphthalenesulphonic acids, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols, especially alkylphenols, sulphosuccinic ester salts, taurine derivatives, especially alkyl taurates, and phosphoric esters of polyethoxylated phenols or alcohols.

21. The herbicide composition as claimed in claim 20, wherein the surfactant or emulsifier is present in an amount ranging from about 0.01 to about 15%, preferably from about 0.01% to about 10% by weight of the composition.

22. The herbicide composition as claimed in claim 5, wherein the composition further comprises one or more agrochemical active compound selected from insecticides, nematicides, fungicides, safeners, growth factor enhancers and fertilizers.

23. The herbicide composition as claimed in any one of the preceding claims wherein the composition is provided in the form of a tank mix or a formulation.

24. A tank mix comprising separately formulated or partially separately formulated pretilachlor, pyrazosulfuron-ethyl and chlorimuron-ethyl.

25. A formulation comprising a herbicidally effective amount of the active ingredients pretilachlor, pyrazosulfuron-ethyl and chlorimuron-ethyl, and one or more auxiliary additives.

26. The formulation as claimed in claim 25,wherein the formulation is selected from water-dispersible granule (WDG or WG), a water-soluble granule (SG), a wettable powder (WP), a water-dispersible powder (WDP), a water-soluble powder (SP), a granule (GR), an encapsulated granule (CG), a fine granule (FG), a macrogranule (GG), a microgranule (MG), a suspension concentrate (SC), a water-soluble concentrate (SL), an emulsifiable concentrate (EC), an emulsion (EW), a micro-emulsion (ME), an oil-based suspension concentrate (OD), a flowable suspension (FS), a suspoemulsion (SE), or a microencapsulated suspension (CS).

27. A method of controlling undesirable vegetation in crops of useful plants, which comprises allowing a herbicidally active amount of active constituent of composition as claimed in any one of claims 1 to 26 to act on the crop plant or its environment.
28. A method of controlling undesirable vegetation in crops of useful plants, which comprises treating the undesirable vegetation in crops of useful plants by applying the composition as claimed in any one of the claims 1 to 27 or the tank mix as claimed in claim 24, or the formulation as claimed in claims 25 to 26 at a rate which corresponds to a total amount of 0.05 to 6 kg of active ingredient per hectare.