WO2022023911A1

WO2022023911A1 - Synergistic ternary herbicidal composition

Info

Publication number: WO2022023911A1
Application number: PCT/IB2021/056687
Authority: WO
Inventors: Mallikarjunappa Siddappa; Kendappa GOWDRA NANJAPPA; Rupak PAUL; Vijay Kumar Reddy; Shivappa AGADI
Original assignee: Rallis India Limited
Priority date: 2020-07-25
Filing date: 2021-07-24
Publication date: 2022-02-03

Abstract

The present disclosure provides a synergistic herbicide composition comprising combination of bispyribac-sodium, metsulfuron-methyl and pyrazosulfuron-ethyl. The ternary herbicide composition is suitable for selectively controlling undesirable vegetation in crops of agriculturally useful plants and exhibits a synergistic herbicidal activity against a broad spectrum of economically important weeds, including broadleaf, sedge and grass weeds.

Description

SYNERGISTIC TERNARY HERBICIDAL COMPOSITION

FIELD OF THE INVENTION

[0001] The present disclosure pertains to technical field of agrochemical composition. More specifically, the present disclosure pertains to a novel composition comprising mixture of three herbicides 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 inhibits 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] Bispyribac-sodium, metsulfuron-methyl and pyrazosulfuron-ethyl are compounds known to be herbicidally active and to be of use in the control of undesirable vegetation such as broadleaf weeds and grassy weeds, in the protection of a range of crops. The herbicides bispyribac-sodium, metsulfuron-methyl and pyrazosulfuron-ethyl are independently known in the art for their herbicidal potency. They are disclosed in ‘The Pesticide Manual’ 15^th Edition, published 2009 by the British Crop Protection Council, and are also commercially available.

[0005] Although bispyribac-sodium, metsulfuron-methyl and pyrazosulfuron-ethyl 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.

SUMMARY OF THE INVENTION

[0015] 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 bispyribac-sodium, metsulfuron-methyl and pyrazosulfuron-ethyl 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.

[0016] The herbicide composition of the present disclosure includes a herbicidally effective amount of active ingredients bispyribac-sodium, metsulfuron-methyl and pyrazosulfuron- ethyl, and may include further constituents, for example formulation auxiliaries and/or agrochemical active compounds.

[0017] 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), 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), oilbased suspension concentrate (OD), flowable suspension (FS), suspoemulsion (SE), dispersion concentrate (DC), or a microencapsulated suspension (CS).

[0018] The herbicide composition according to the present disclosure is suitable for selectively controlling undesirable vegetation in crops of useful plants such as 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. [0019] The herbicide composition according to the present disclosure is suitable for all application methods conventionally used in agriculture, for example post-emergence application.

[0020] 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

[0021] 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.

[0022] 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.”

[0023] 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 com in any suitable manner in one or more embodiments.

[0024] 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 di ctates otherwise.

[0025] 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.

[0026] 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.

[0027] 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.

[0028] The headings and abstract of the invention provided herein are for convenience only and do not interpret the scope or meaning of the embodiments.

[0029] 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.

[0030] 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.

[0031] The term “herbicide” as used herein, refers to a compound that controls growth of undesirable vegetation.

[0032] 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.

[0033] 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 to areas under cultivation.

[0034] 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.

[0035] 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.

[0036] As used herein, the term "post-emergence," refers to application of the herbicide composition to weeds that have already emerged from a soil surface.

[0037] The present disclosure provides a herbicide composition comprising combination of bispyribac-sodium, metsulfuron-methyl and pyrazosulfuron-ethyl. It has surprisingly been found that bispyribac-sodium, metsulfuron-methyl and pyrazosulfuron-ethyl display a synergistic herbicidal effect in the control of undesirable vegetation when applied in combination, for example in a composition comprising all three compounds.

[0038] The synergistic effects of the combination of bispyribac-sodium, metsulfuron- methyl and pyrazosulfuron-ethyl 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 bispyribac-sodium, metsulfuron-methyl and pyrazosulfuron-ethyl 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 bisp yribac- sodium, metsulfuron-methyl and pyrazosulfuron-ethyl 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.

[0039] The herbicide composition of the present disclosure is useful for 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. 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 bispyribac-sodium, metsulfuron-methyl and pyrazosulfuron-ethyl in suitable amounts.

[0040] In various embodiments, the herbicide composition according to the present disclosure is particularly advantageous in the protection of rice crop.

[0041] 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.

[0042] In various embodiments, effective herbicidal effects can be achieved with postemergence application of the herbicide composition of the present disclosure. Useful methods of application include broadcast or localized spraying, drip irrigation or other forms of irrigation, and any of these methods followed by soil tilling. 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, i.e., whether by spraying, irrigation, or other means. The total application rate of bispyribac-sodium, metsulfuron-methyl and pyrazosulfuron-ethyl can vary within a wide range, for example from 1 to 500g per hectare (g/ha). Preferably, the application rate ranges from 2 to 400 g/ha, more preferably from 3 to 300 g/ha, still more preferably from 5 to 200 g/ha.

[0043] 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 post-emergence applications or one or more early post-emergence applications, and/or followed by one or more applications at medium or late post-emergence.

[0044] In the composition of present disclosure, the bispyribac-sodium: metsulfuron- methyl: pyrazosulfuron-ethyl weight ratio at which the herbicidal effect is synergistic lies within the range of from about 1:0.1: 1 to about 40:10:40.

[0045] The active ingredients bispyribac-sodium, metsulfuron-methyl and pyrazosulfuron- ethyl may be present in the composition of the present disclosure in a wide range of amounts. In preferred embodiments, the total amount of bispyribac-sodium, metsulfuron-methyl and pyrazosulfuron-ethyl in the composition can range from 5% to 95% by weight of the composition. In some preferred embodiments, the composition comprises, by weight, from 1% to 40% of bispyribac-sodium, from 0.1% to 10% of metsulfuron-methyl and from 1% to 40% of pyrazosulfuron-ethyl.

[0046] In various embodiments, the herbicide composition of the present disclosure can be formulated in conventional manner, for example by mixing bispyribac-sodium, metsulfuron- methyl and pyrazosulfuron-ethyl with one or more formulation auxiliaries. Suitable auxiliaries 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 formulation auxiliaries are selected from inert carriers, dispersing agents, wetting agents, stabilizing agents, anti-caking agents, buffering agents, surfactants, solvents, anti-foaming agents, anti-freezing agents, antioxidants, colorants, and thickeners.

[0047] According to embodiments of the present disclosure, the herbicide composition comprising the combination of bispyribac-sodium, metsulfuron-methyl and pyrazosulfuron- ethyl can be formulated in liquid or solid form. In preferred embodiments, the disclosed herbicide composition is formulated as a water-dispersible granule (WDG), 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), dispersion concentrate (DC), or a microencapsulated suspension (CS).

[0048] In some preferred embodiments, the herbicide composition comprising the combination of bisp yribac- sodium, metsulfuron-methyl and pyrazosulfuron-ethyl is formulated as a wettable powder (WP). The wettable powder may be dispersed in water at a suitable proportion to provide an aqueous composition that can be applied at a suitable spray rate.

[0049] 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. Suitable inert carrier(s) for granules include, for example, crushed and fractionated natural minerals, such as calcite, marble, pumice, sepiolite, 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. The inert carrier may preferably be used in an amount of from about 5% to about 80% by weight based on a total weight of the composition.

[0050] In at least one embodiment, the dispersing agent can be selected from lignosulphonates, 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 and mixtures thereof. Preferably, dispersing agent is present in an amount of from about 1% to about 15% by weight based on a total weight of the composition.

[0051] 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 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, and mixtures thereof. The wetting agent may preferably be used in an amount of from about 1% to about 8% by weight based on a total weight of the composition.

[0052] 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 and mixtures thereof. The stabilizing agent may preferably be used in an amount of from about 0.1% to about 6% by weight based on a total weight of the composition.

[0053] 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, and mixtures thereof. The anti-caking agent may preferably be used in an amount of from about 0.1% to about 6% by weight based on a total weight of the composition.

[0054] In at least one embodiment, the buffering agent can be selected from H+ bentonite, calcium bentonite, sodium bentonite, H+ hectorite, calcium hectorite, sodium hectorite and mixtures thereof. Preferably, buffering agent is present in an amount of from about 0.1% to about 5% by weight based on a total weight of the composition. [0055] 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.

[0056] 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 bispyribac-sodium, metsulfuron-methyl and pyrazosulfuron-ethyl are known in the art.

[0057] 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 hydroxy toluene.

[0058] 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 and mixtures thereof.

[0059] Suitable anti-freezing agents include organic solvents which are completely miscible with water, such as ethylene glycol, propylene glycol, other glycols, glycerine or urea.

[0060] Suitable surfactants 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 include, but not limited to, salts of polyacrylic acids, salts of ligno sulphonic 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 poly ethoxylated phenols or alcohols.

[0061] The presence of at least one surfactant is generally required when the active ingredient(s) and/or the formulation auxiliaries are insoluble in water and the vehicle for the final application of the composition is water.

[0062] 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 bispyribac-sodium, metsulfuron-methyl and pyrazo sulfuron-ethyl .

[0063] The disclosed herbicide composition comprising combination of bispyribac-sodium, metsulfuron-methyl and pyrazosulfuron-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 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 conventional methods, including coating, spraying, sprinkling, dipping, soaking, injection, irrigation, and the like.

[0064] 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.

[0065] 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.

EXAMPLES

I. Preparation of Wettable Powder (WP)

[0066] Wettable powder formulations were prepared according to the ingredients and concentrations illustrated in the following examples:

Example 1: Bispyribac Sodium 25% +Metsulfuron methyl 4% + Pyrazosuluron ethyl 20% WP Table 1: Composition for WP Formulation 1

[0067] Preparation method: Bispyribac sodium 25.0 parts, metsulfuron methyl 4.0 parts and pyrazosulfuron ethyl 20.0 parts were mixed with 10.0 parts of dispersing agent comprising alkylnaphthalene sulfonate formaldehyde condensate, 4.0 parts of wetting agent comprising alkylnaphthalene sulfonate, 3.0 parts of stabilizer comprising fumed silica modified with dimethyldichlorosilane, 3.0 parts of anti-caking agent comprising precipitated silica, 2.0 parts buffering agent comprising sodium bentonite and 29.0 parts of inert carrier comprising China clay. The resulting mixture was pre-blended for 60 minutes and passed through air-jet mill for particle size reduction (Dv90 <12p). After milling, the mixture was blended for another 120 minutes in a post blender to get homogeneous wettable powder (WP).

Example 2: Bispyribac Sodium 10% +Metsulfuron methyl 6% + Pyrazosulfuron ethyl 30% WP

Table 2: Composition for WP Formulation 2

[0068] Bispyribac sodium 10.0 parts, metsulfuron methyl 6.0 parts and pyrazosulfuron ethyl 30.0 parts were mixed with 8.0 parts of dispersing agent comprising alkylnaphthalene sulfonate formaldehyde condensate, 3.0 parts of wetting agent comprising alkylnaphthalene sulfonate, 2.0 parts of stabilizer comprising fumed silica modified with dimethyldichlorosilane, 4.0 parts of anti-caking agent comprising precipitated silica, 1.0 parts buffering agent comprising Sodium bentonite and 36.0 parts of inert carrier comprising China clay. The resulting mixture was pre -blended for 60 minutes and passed through air-jet mill for particle size reduction (Dv90 <12p). After milling, the mixture was blended for another 120 minutes in a post blender to get homogeneous wettable powder (WP).

Example 3: Bispyribac Sodium 35% +Metsulfuron methyl 3% + Pyrazosulfuron ethyl 15%

WP

Table 3: Composition for WP Formulation 3

[0069] Bispyribac sodium 35.0 parts, metsulfuron methyl 3.0 parts and pyrazosulfuron ethyl 15.0 parts were mixed with 11.0 parts of dispersing agent comprising Alkylnaphthalene sulfonate formaldehyde condensate, 6.0 parts of wetting agent comprising alkylnaphthalene sulfonate, 4.0 parts of stabilizer comprising fumed silica modified with dimethyldichlorosilane, 1.0 parts of anti-caking agent comprising precipitated silica, 2.5.0 parts buffering agent comprising Sodium bentonite and 22.5 parts of inert carrier comprising China clay. The resulting mixture was pre -blended for 60 minutes and passed through air-jet mill for particle size reduction (Dv90 <12p). After milling, the mixture was blended for another 120 minutes in a post blender to get homogeneous wettable powder (WP).

II. Preparation of Water Dispersible Granule (WDG)

[0070] Water dispersible granule formulations were prepared according to the ingredients and concentrations mentioned in the following examples:

Examples 4-5: Bispyribac Sodium + Metsulfuron Methyl + Pyrazosulfuron Ethyl WDG Formulations

Table 4: Compositions for WDG Formulatio ns

[0071] In a clean pre-mixer vessel, all the ingredients as per Table 4 were weighed, charged and blended uniformly, the blending was continued for 60 mins. The blended material was passed through airjet mill for particle size reduction. Air jetting was continued for another 120 mins to get homogeneity of the material. The homogenous material after air jetting was added to a dough maker and required quantity of dematerialized water was added to make extrudable dough. The dough was extruded through an extruder and extrudates were dried to obtain water dispersible granules (WDG).

III. Preparation of Granules (GR) [0072] Granules were prepared according to the ingredients and concentrations mentioned in the following examples:

Examples 6-8: Bispyribac Sodium + Metsulfuron Methyl + Pyrazosulfuron Ethyl Granules

Table 5: Compositions for Granules

[0073] In a clean pre-mixer vessel, all the above mentioned ingredients were weighed, charged and blended, the blending was continued for 60 mins. The blended material was passed through airjet mill for particle size reduction. The air jetted powder was air jetted for another 120 mins to get homogeneity of the material. The homogenous material was added to a dough maker and required quantity of dematerialized water was added to make extrudable dough. The dough was extruded through an extruder and extrudates were dried to obtain granules (GR). IV. Preparation of Emulsifiable Concentrate (EC)

[0074] EC formulations were prepared according to the ingredients and concentrations mentioned in the following examples:

Examples 9-11: Bispyribac Sodium + Metsulfuron Methyl + Pyrazosulfuron Ethyl EC formulations

Table 6: Compositions for EC Formulations

[0075] In a dry and clean mixing vessel, solvent C9, cyclohexanone, triethanol amine, calcium dodecylbenzene sulfonate and ethopropoxylated polyarylphenol in quantities as per Table 6 were added and mixed well. To the mixture obtained, bispyribac sodium, metsulfuron methyl and pyrazosulfuron ethyl in the quantities as per the above Table 6 were added and mixing was further continued to mix until a transparent homogeneous solution form was obtained.

V. Preparation of Water-soluble concentrate (SL)

[0076] SL formulations were prepared according to the ingredients and concentrations mentioned in the following examples:

Examples 12-13: Bispyribac Sodium + Metsulfuron Methyl + Pyrazosulfuron Ethyl SL formulations

Table 7: Compositions for SL Formulations

[0077] In a dry and clean mixing vessel, N-methyl-2-pyrrolidone, dimethyl sulfoxide, triethanol amine, ethopropoxylated polyarylphenol in quantities as per Table 7 were charges and mixed well. Polyvinyl alcohol in the quantity as per above Table 7 was added to the mixture and mixed well. Bispyribac sodium, metsulfuron methyl and pyrazosulfuron ethyl were added as per the quantities based on Table 7, mixing was continued until a clear and transparent homogeneous water-soluble concentrate (SL) formulation was obtained. VI. Preparation of Suspension Concentrate (SC)

[0078] SC formulations were prepared according to the ingredients and concentrations mentioned in the following examples:

Examples 14-16: Bispyribac Sodium + Metsulfuron Methyl + Pyrazosulfuron Ethyl SC formulations

Table 8: Compositions for SC Formulations

[0079] In a clean pre-mixer vessel, DM water, propylene glycol, polyoxyethylene alkyl ether, acrylic copolymer, poly dimethylsiloxane, l,2-benzisothiazolin-3-one in the quantities based on Table 8 were added and mixed for 15 mins. To the mixture, alkylnaphthalene sulfonate formaldehyde condensate, trisodium citrate, bispyribac sodium, metsulfuron methyl, pyrazosulfuron ethyl were charged in the quantities as per Table 8 and mixing was continued for 30 mins. The pre mixed slurry was passed through jacketed dyno mill for particle size reduction. The milled slurry was collected into post mixing vessel and xanthan gum was added in a quantity as per Table 8. Mixing was continued until a homogeneous suspension (SC) was obtained. VII. Preparation of Suspo-emulsion (SE)

[0080] SE formulations were prepared according to the ingredients and concentrations mentioned in the following examples:

Examples 17-18: Bispyribac Sodium + Metsulfuron Methyl + Pyrazosulfuron Ethyl SE formulations

Table 9: Compositions for SE Formulations

[0081] Suspo-emulsion formulations were prepared as follows:

Part A (SC part): [0082] In a clean pre-mixer vessel, DM water, propylene glycol, acrylic copolymer, polydimethylsiloxane, l,2-benzisothiazolin-3-one, alkylnaphthalene sulfonate formaldehyde condensate, trisodium citrate in the quantities as per the Table 9 were added and mixed, the mixing was continued for 15 mins. To the mixture, bispyribac sodium, prazosulfuron ethyl were added in a quantity based on Table 9 and mixing was continued for another 30 mins to obtain a pre-mix slurry. The pre mixed slurry was passed through jacketed dyno mill for particle size reduction. The milled slurry was collected into post mixing vessel and mixing was continued until formation of a homogeneous suspension (SC).

Part B (EW part):

[0083] In a dry and clean mixing vessel, solvent C9, cyclohexanone, polyoxyethylene alkyl ether, ethoxylated fatty alcohol in quantity based on Table 9 were charged and mixed well for 10 minutes. To the mixture, metsulfuron methyl in a quantity as per Table 9 was charged and mixing was continued until dissolved. Polyvinyl pyrrolidone and DM water in quantity as per Table 9 were added and mixing was continued to stir for 30 mins to obtain the pre-mix solution. The pre-mixed solution was passed through highspeed homogenizer to achieve desirable emulsion particle size, the emulsion was obtained into post mixing vessel and mixing was continued until a homogeneous EW was obtained.

Mixing of Parts A and B to obtain Suspo-emulsion (SE):

[0084] In a mixing vessel weighed quantity of Bispyribac sodium + Pyrazosulfuron ethyl SC (Part A) was added. To Part A, weighed quantity of Metsulfuron methyl EW (Part B) was added and mixed. Mixing was continued for 1 hr. To the mixture, xanthan gum in a quantity as per Table 9 was added and mixing was continued until a homogeneous suspo-emulsion (SE) was obtained.

VIII. Preparation of Oil-based suspension concentrate (OD)

[0085] Oil-based suspension concentrate (OD) formulations were prepared according to the ingredients and concentrations mentioned in the following examples:

Examples 19-21: Bispyribac Sodium + Metsulfuron Methyl + Pyrazosulfuron Ethyl OD formulations

Table 10: Compositions for OD Formulations

[0086] In a clean pre-mixer vessel, weighed quantity of methylated soyabean oil, calcium dodecylbenzene sulfonate, tridecylalcohol ethoxylate, polyethylene glycol polymer, EO-PO block copolymer, poly dimethylsiloxane, trisodium citrate were added and mixed. Mixing was continued for 15 mins. To the mixture, weighed quantity of bispyribac sodium, metsulfuron methyl, pyrazosulfuron ethyl were added and mixing was continued for 30 mins to obtain the pre-mix slurry. The pre mixed slurry was passed through jacketed bead mill for particle size reduction, and the milled slurry was collected into post mixing vessel, to which weighed quantity of organic derivative of hectorite clay was added and mixing was continued until the formation of a homogeneous suspension (OD).

IX: Field Tests

[0087] Field test studies were carried out as per the following Example. Example 22: Field Tests

[0088] The formulation of Example 1 was tested for its biological activity and the results are shown in Tables 11 & 12 below: Table 11: Field Test Results of the Combination of Bispyribac-sodium, Metsulfuron- methyl and Pyrazosulfuron-ethyl applied at 15 DAP¹ for weed control in transplanted rice

DAP = Days after planting

2

Application rate is stated in units of grams active ingredient per hectare a

DAA = Days after application

Table 12: Field Test Results of the Combination of Bispyribac-sodium, Metsulfuron- methyl and Pyrazosulfuron-ethyl applied at 15 DAP¹ for weed control in transplanted rice (% Weed control relative to untreated check)

DAP = Days after planting

2

Application rate is stated in units of grams active ingredient per hectare a

DAA = Days after application [0089] From the test results shown above, it is evident that there is an unexpected and surprising result i.e., synergistic effect of the combination of bispyribac-sodium, metsulfuron- methyl and pyrazosulfuron-ethyl in the control of weeds in rice fields. As can be seen from Tables 11 and 12, the combined administration of bispyribac-sodium, metsulfuron-methyl and pyrazosulfuron-ethyl resulted in significant reduction in weeds population as compared to single administration of the individual herbicides. 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.

[0090] 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

26 We Claim:

1. A ternary herbicide composition comprising bispynbac-sodium, metsulfuron-methyl and pyrazosulfuron-ethyl.

2. The ternary herbicide composition as claimed in claim 1, wherein the composition comprising bisp yribac- sodium in an amount of from 1% to 40% w/w, metsulfuron-methyl in an amount of from 0.1% to 10% w/w, and pyrazosulfuron-ethyl in an amount of from 1% to 40% w/w.

3. The ternary herbicide composition as claimed in claim 1, wherein the weight ratio of bispyribac-sodium to metsulfuron-methyl to pyrazosulfuron-ethyl is in the range of from 1:0.1: 1 to 40:10:40.

4. The ternary herbicide composition as claimed in claim 1, wherein the composition comprising bispyribac-sodium, metsulfuron-methyl and pyrazosulfuron-ethyl in an amount of from 5% to 95% by weight of the composition.

5. The ternary herbicide composition as claimed in claim 1, further comprising one or more formulation auxiliaries.

6. The ternary herbicide composition as claimed in claim 5, wherein the one or more formulation auxiliaries are selected from the group consisting of an inert carrier, a dispersing agent, a wetting agent, a stabilizing agent, an anti-caking agent, a buffering agent, a surfactant, a solvent, an anti-foaming agent, an anti-freezing agent, an antioxidant, a colorant, and a thickener.

7. The ternary herbicide composition as claimed in claim 1, wherein the composition is formulated as a water-dispersible granule (WDG), 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).

8. The ternary herbicide composition as claimed in claim 1, further comprising one or more further agrochemical active compounds selected from the group consisting of insecticides, nematicides, fungicides, safeners, growth factor enhancers and fertilizers.

9. A herbicide composition, comprising: 1-40% w/w of bispyribac-sodium;

0.1-10% w/w of metsulfuron-methyl;

1-40% w/w of pyrazosulfuron-ethyl;

1-15% w/w of a dispersing agent;

1-8% w/w of a wetting agent; 0.1-6% w/w of a stabilizing agent;

0.1-6% w/w of an anti-caking agent;

0.1-5% w/w of a buffering agent; and

5-80% w/w of an inert carrier.

10. The herbicide composition as claimed in claim 9, which is a wettable powder (WP) formulation.