Abstract: The present invention relates to a binary herbicidal composition comprising 4-amino-6-tert-butyl-3-(methylthio)-1,2,4-triazin-5(4H)-one (metribuzin) and ethyl 5-{[(4,6-dimethoxypyrimidin-2-yl)carbamoyl]sulfamoyl}-1-methyl-1H-pyrazole-4-carboxylate (pyrazosulfuron-ethyl) and a stabilizing agent for control of weeds, Ipomoea purpurea and Cyperus rotundus. The present invention further relates to a WP and WDG herbicidal formulation comprising the metribuzin, pyrazosulfuron-ethyl and a stabilizing agent and process for preparing the same.
DESC:FIELD OF THE INVENTION
[0001] The present invention relates to a general field of herbicides. Specifically, the present invention relates to a binary herbicidal composition and formulation comprising 4-amino-6-tert-butyl-3-(methylthio)-1,2,4-triazin-5(4H)-one commonly known as metribuzin; and ethyl 5-{[(4,6-dimethoxypyrimidin-2-yl)carbamoyl]sulfamoyl}-1-methyl-1H-pyrazole-4-carboxylate commonly known as pyrazosulfuron-ethyl. More specifically the present invention relates to a binary herbicidal composition and a formulation comprising metribuzin, pyrazosulfuron-ethyl and a stabilizing agent for control of weeds for example Ipomoea purpurea and Cyperus rotundus. The present invention further relates to a method for preparing a binary herbicidal formulation comprising metribuzin, pyrazosulfuron-ethyl and a stabilizing agent.
BACKGROUND OF THE INVENTION
[0002] 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] The protection of crops from weeds and other vegetation that inhibit crop growth is a significant challenge in the field agriculture. To help combat this challenge, researchers in the field of synthetic chemistry have produced an extensive array of chemicals and those experts in the art of formulation have formulated variety of formulations including such active chemical ingredients to be effective in the control of such unwanted growth of weeds. Chemical herbicides of many types have been disclosed in the literature and large numbers of herbicides are in commercial use.
[0004] The search for compounds which in combination exhibit excellent herbicidal activity towards target weeds and low toxicity towards non-target plants is a continuing one because of factors such as the desire for products with better activity and selectivity, lesser or no undesirable phytotoxicity to the healthy crop and environmental impact, counter weed resistance to the herbicides in use and can be produced by economical production method.
[0005] In some cases, herbicidal active ingredients have been shown to be more effective in combination than when applied individually, and this is referred to as "synergism." As described in the Herbicide Handbook of the Weed Science Society of America, Eighth Edition, 2002, p. 462, "’synergism’ is an interaction of two or more factors such that the effect when combined is greater than the predicted effect based on the response to each factor applied separately."
[0006] Therefore, to achieve one or more of the aforementioned advantages, combinations of active ingredients are considered promising. However, to arrive at the synergistic combination is challenging as the two ingredients must not inhibit or diminish the effects of each other, should be compatible with each other and able to provide one or more of the advantageous effects, most importantly for effectively control the weeds growing amongst desired crops.
[0007] Hence, there still remains a need to arrive at a herbicidal combination of active ingredients that are compatible, can overcome deficiencies known in the art such as requirement of higher concentrations and repeated application of single active ingredient leading to resistance to weeds, phytotoxicity to crop, adverse environmental impact, high cost of production and inadequate weed control and achieve one or more advantages including effective control of the target weeds, such as Ipomoea purpurea and Cyperus rotundus, a low toxicity towards non- target plants, exhibit a greater activity, better bio-efficacy, better selectivity, lower undesirable environmental impact, devoid of phytotoxicity to the locus of application, lower production and market cost and higher effectiveness against weeds’ resistance to known herbicides.
SUMMARY OF THE INVENTION
[0008] The present invention relates to herbicidal composition. Specifically, the present invention relates to a binary herbicidal composition comprising 4-amino-6-tert-butyl-3-(methylthio)-1,2,4-triazin-5(4H)-one commonly known as metribuzin; and ethyl 5-{[(4,6-dimethoxypyrimidin-2-yl)carbamoyl]sulfamoyl}-1-methyl-1H-pyrazole-4-carboxylate commonly known as pyrazosulfuron-ethyl and a stabilizing agent for control of weeds for example Ipomoea purpurea and Cyperus rotundus.
[0009] Accordingly, in one aspect, the present invention provides a binary herbicidal composition comprising active ingredients metribuzin, pyrazosulfuron-ethyl, a stabilizing agent and agriculturally acceptable excipient(s) for control of weeds like Ipomoea purpurea and Cyperus rotundus.
[0010] In certain aspect of the present disclosure, the agriculturally acceptable excipients can be selected from but not limiting to the group consisting of wetting agent(s), dispersing agent(s), antifoaming agent(s) and inert carrier(s).
[0011] In one more aspect, the present disclosure provides a binary herbicidal composition comprising of:
a) about 50% to about 90% metribuzin by weight of the composition;
b) about 0.1% to about 10% pyrazosulfuron-ethyl by weight of the composition;
c) about 0.01 to about 5.0% stabilizing agent by weight of the composition; and
d) about 0.1% to about 49.89% by weight of agriculturally acceptable excipient(s).
[0012] Accordingly, in another aspect, the present invention provides a binary herbicidal formulation comprising active ingredients metribuzin, pyrazosulfuron-ethyl, a stabilizing agent and agriculturally acceptable excipient(s) for control of weeds like Ipomoea purpurea and Cyperus rotundus.
[0013] In one aspect, the present disclosure provides a binary herbicidal formulation comprising of:
a) about 50% to about 90% metribuzin by weight of the formulation;
b) about 0.1% to about 10% pyrazosulfuron-ethyl by weight of the formulation;
c) about 0.01 to about 5.0% stabilizing agent by weight of the formulation; and
d) about 0.1% to about 49.89% by weight of agriculturally acceptable excipient(s).
[0014] The present invention in further aspects provides a method for preparing formulation such as the wettable powder (WP) and water dispersible granule (WDG) comprising metribuzin, pyrazosulfuron-ethyl and a stabilizing agent.
[0015] In another aspect, the present disclosure provides a method of preparation of an herbicidal wettable powder (WP) formulation comprising the steps of:
a) mixing active ingredients, stabilizing agent and agriculturally acceptable excipient(s) for about 1 hour to about 4 hours to obtain a pre-blended mixture;
b) grinding the pre-blended mixture through a mill to obtain a milled powder; and
c) homogenising the milled powder for about 1 hour to about 4 hours, to obtain a homogeneous wettable powder (WP) formulation.
[0016] In another aspect, the present disclosure provides a method of preparation of an herbicidal wettable powder (WP) formulation comprising the steps of:
a) mixing metribuzin about 50% to about 90% w/w, pyrazosulfuron-ethyl about 0.1% to about 10% w/w, stabilizing agent about 0.01% to about 5.0% w/w, and agriculturally acceptable excipient(s) about 0.1% to about 49.89% w/w of the formulation for about 1 hour to about 4 hours, preferably for about 2 hours to obtain a pre-blended mixture;
b) grinding the pre-blended mixture through a mill to obtain a milled powder; and
c) homogenising the milled powder for about 1 hour to about 4 hours, preferably for about 2 hours to obtain a homogeneous wettable powder (WP) formulation.
[0017] In yet another aspect, the present disclosure provides a method of preparation of an herbicidal water dispersible granule (WDG) formulation comprising the steps of:
a) mixing active ingredients, stabilizing agent and agriculturally acceptable excipient(s) for about 1 hour to about 4 hours to obtain a pre-blended mixture;
b) grinding the pre-blended mixture through a mill to obtain a milled powder;
c) homogenising the milled powder for about 1 hour to about 4 hours to obtain a homogeneous powder;
d) spraying de-mineralized water on the homogeneous powder and mixing to prepare a uniform dough; and
e) extruding the uniform dough through an extruder to obtain extruded granules and drying the extruded granules in a fluid bed dryer to obtain the water dispersible granule (WDG) formulation.
[0018] In another aspect, the present disclosure provides a method of preparation of an herbicidal WDG formulation comprising the steps of:
a) mixing metribuzin about 50% to about 90% w/w, pyrazosulfuron-ethyl about 0.1% to about 10% w/w, a stabilizing agent about 0.01% to about 5.0% w/w of the formulation, and agriculturally acceptable excipient(s) about 0.1% to about 49.89% w/w of the formulation for about 1 hour to about 4 hours, preferably for about 2 hours to obtain a pre-blended mixture;
b) grinding the pre-blended mixture through a mill to obtain a milled powder;
c) homogenising the milled powder for about 1 hour to about 4 hours, preferably for about 2 hours to obtain a homogeneous powder;
d) spraying de-mineralized water on the homogeneous powder and mixing to prepare a uniform dough; and
e) extruding the uniform dough through an extruder to obtain extruded granules and drying the extruded granules in a fluid bed dryer to obtain the water dispersible granule (WDG) formulation.
[0019] In an embodiment, the present invention relates to a method for controlling weeds using the herbicidal WP or WDG formulation comprising combination of metribuzin, pyrazosulfuron-ethyl, a stabilizing agent and one or more agriculturally acceptable excipient.
[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
[0021] The following is a detailed description of embodiments of the 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] All publications herein are incorporated by reference to the same extent as if each individual publication or patent application were specifically and individually indicated to be incorporated by reference. Where a definition or use of a term in an incorporated reference is inconsistent or contrary to the definition of that term provided herein, the definition of that term provided herein applies and the definition of that term in the reference does not apply.
[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 combined in any suitable manner in one or more embodiments.
[0024] In some embodiments, the numbers expressing quantities of ingredients, properties such as concentration, reaction 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 and attached claims 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. The numerical values presented in some embodiments of the invention may contain certain errors necessarily resulting from the standard deviation found in their respective testing measurements.
[0025] As used in the description herein and throughout the claims that follow, the meaning of “a,” “an,” and “the” includes plural reference unless the context clearly dictates otherwise. Also, as used in the description herein, the meaning of “in” includes “in” and “on” unless the context clearly dictates otherwise.
[0026] 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.”
[0027] 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. All methods described herein can be performed in any 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] Groupings of alternative elements or embodiments of the invention disclosed herein are not to be construed as limitations. Each group member can be referred to and claimed individually or in any combination with other members of the group or other elements found herein. One or more members of a group can be included in, or deleted from, a group for reasons of convenience and/or patentability. When any such inclusion or deletion occurs, the specification is herein deemed to contain the group as modified thus fulfilling the written
[0029] The description that follows, and the embodiments described therein, is provided by way of illustration of an example, or examples, of particular embodiments of the principles and aspects of the present disclosure. These examples are provided for the purposes of explanation, and not of limitation, of those principles and of the disclosure.
[0030] It should also be appreciated that the present disclosure can be implemented in numerous ways, including as a system, a method or a device. In this specification, these implementations, or any other form that the invention may take, may be referred to as processes. In general, the order of the steps of the disclosed processes may be altered within the scope of the invention.
[0031] The headings and abstract of the invention provided herein are for convenience only and do not interpret the scope or meaning of the embodiments.
[0032] 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.
[0033] Various terms as used herein are shown below. 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.
[0034] The term, “WP formulation” as used herein refers to wettable powder formulation. The WP formulation consists of the finely milled powder.
[0035] The term, “WDG formulation” as used herein refers to water dispersible granule formulation. The WDG formulation consists of granules to be applied after disintegration and dispersion in water.
[0036] The term, “agriculturally acceptable excipient” as used herein refers to any agriculturally acceptable inactive substance or mixture or adjuvant added to a formulation of an herbicidal active ingredient. Examples of agriculturally acceptable excipient include, but not limited to wetting agent(s), dispersing agent(s), antifoaming agent(s), pH modifying agent(s), inert carrier(s), surfactant(s), antifreeze agent(s), clay(s), solvent(s), water, salt(s), polymer(s), emulsifying agent(s), suspension and density balancing agent(s), anti-crystalline agent (s), rheology modifier(s), spreading agent (s), anti-caking agent(s), antioxidant (s), biocide (s), capsule forming agent (s), quenching agent (s) and super spreader(s).
[0037] The term, “weed” as used herein refers to unwanted plant harmful to plant of interest.
[0038] The term, “herbicidally effective amount”, as used herein refers to the quantity of herbicidal active agent, applied in an amount which will provide the required control of weed on commercial crops. The particular amount is dependent upon many factors including, for example, type of formulations, the crop, weed sought to be controlled and environmental conditions.
[0039] The term, “control” or “controlling”, as used herein refers to preventing, reducing, killing, inhibiting the growth of, inhibiting the reproduction of, and/or eliminating at least one weed i.e. an undesirable plant in a crop growing environment.
[0040] The compound metribuzin is also known as 4-amino-6-tert-butyl-3-(methylthio)-1,2,4-triazin-5(4H)-one and belongs to a class of triazinone herbicides that inhibit photosynthesis in susceptible plants by binding to a protein of the photosystem II complex.
[0041] The compound pyrazosulfuron-ethyl is also known as ethyl 5-{[(4,6-dimethoxypyrimidin-2-yl)carbamoyl]sulfamoyl}-1-methyl-1H-pyrazole-4-carboxylate and belongs to a class of pyrazole herbicides and pyrimidinylsulfonylurea herbicides that inhibit the catalysis of the enzyme, acetolactate synthase (ALS) in susceptible plants.
[0042] In one embodiment, the present disclosure provides a binary herbicidal composition comprising active ingredients metribuzin, pyrazosulfuron-ethyl, a stabilizing agent and agriculturally acceptable excipient(s) for control of weeds like Ipomoea purpurea and Cyperus rotundus.
[0043] In one embodiment, the present disclosure provides a binary herbicidal composition comprising:
a) about 50% to about 90% metribuzin by weight of the composition;
b) about 0.1% to about 10% pyrazosulfuron-ethyl by weight of the composition;
c) about 0.01 to about 5.0% stabilizing agent by weight of the composition; and
d) about 0.1% to about 49.89% by weight of agriculturally acceptable excipient(s).
[0044] In embodiment, the agriculturally acceptable excipient(s) can be selected without limitation from the group comprising about 0.1% to 8% wetting agent w/w, about 0.1% to 20.0% dispersing agent w/w, about 0.01% to 5.0% antifoaming agent w/w and about 0.1% to 49.68% one or more inert carrier w/w or mixture thereof.
[0045] In one embodiment, a binary herbicidal composition comprises,
a) about 50% to about 90% metribuzin by weight of the composition;
b) about 0.1% to about 10% pyrazosulfuron-ethyl by weight of the composition;
c) about 0.01% to about 5.0% stabilizing agent by weight of the composition;
d) about 0.1% to about 8 % wetting agent by weight of the composition;
e) about 0.1% to about 20.0% dispersing agent by weight of the composition;
f) about 0.01% to about 5.0% antifoaming agent by weight of the composition; and
g) about 0.1% to about 49.68% one or more inert carrier by weight of the composition.
[0046] In another embodiment, the present disclosure provides formulation comprising the composition in accordance with the present disclosure. The formulation may be a solid, semi-solid or liquid formulation.
[0047] In certain embodiments, the present disclosure provides a formulation comprising the binary herbicidal composition in accordance with the present disclosure comprising metribuzin, pyrazosulfuron-ethyl stabilizing agent and agriculturally acceptable excipient(s) for control of weeds like Ipomoea purpurea and Cyperus rotundus.
[0048] In one embodiment, the present disclosure provides a binary herbicidal formulation comprising:
a) about 50% to about 90% metribuzin by weight of the formulation;
b) about 0.1% to about 10% pyrazosulfuron-ethyl by weight of the formulation;
c) about 0.01 to about 5.0% stabilizing agent by weight of the formulation; and
d) about 0.1% to about 49.89% by weight of agriculturally acceptable excipient(s).
[0049] In embodiment, the agriculturally acceptable excipient(s) excipients can be selected without limitation from the group comprising 0.1% to 8% wetting agent w/w, 0.1% to 20.0% dispersing agent w/w and 0.01% to 5.0% antifoaming agent w/w and 0.1% to 49.68% one or more inert carrier w/w or mixture thereof.
[0050] In an embodiment, the formulation can be selected from the group consisting of capsule suspension (CS), controlled release granules (CR), dispersible concentrate (DC), emulsifiable concentrate (EC), emulsion, water in oil (EO), emulsion, oil in water (EW), granule (GR), soil applied granules (SAG), jambo balls, bags, bags in water soluble pouch, micro-emulsion (ME), oil dispersion (OD), oil miscible flowable concentrate (oil miscible suspension) (OF), oil miscible liquid (OL), suspension concentrate (SC), suspo-emulsion (SE), soluble concentrate (SL), water soluble granule (SG), water soluble powder (SP), water dispersible granule (WDG or WG), wettable powder (WP), a water-dispersible powder (WDP), encapsulated granule (CG), a fine granule (FG), a macrogranule (GG), a microgranule (MG), a flowable suspension (FS), dustable powder (DP), a gel, a water-dispersible tablet (WT), a mixed formulation of CS and SC (ZC), a mixed formulation of CS and SE (ZE), and a mixed formulation of CS and EW (ZW).
[0051] In one embodiment, the formulation of the present invention is wettable powder (WP) formulation
[0052] In another embodiment, the formulation of the present invention is water dispersible granule (WDG) formulation.
[0053] In one embodiment, the present invention provides a wettable powder (WP) formulation comprising metribuzin, pyrazosulfuron-ethyl, stabilizing agent and agriculturally acceptable excipient(s).
[0054] In another embodiment, the present disclosure provides water dispersible granule (WDG) formulation comprising metribuzin, pyrazosulfuron ethyl, stabilizing agent and agriculturally acceptable excipient(s).
[0055] In an embodiment, the herbicidal WP or WDG formulation comprises,
a) about 50% to about 90% w/w metribuzin;
b) about 0.1% to about 10% w/w pyrazosulfuron-ethyl;
c) about 0.01% to about 5.0% w/w stabilizing agent ;
d) about 0.1% to about 8 % w/w wetting agent;
e) about 0.1 % to about 20.0% w/w dispersing agent;
f) about 0.01% to about 5.0% w/w antifoaming agent; and
g) about 0.1% to about 49.68% w/w one or more inert carrier.
[0056] In one embodiment, the wettable powder (WP) formulation comprises:
a) about 75% metribuzin by weight of the formulation;
b) about 4% pyrazosulfuron-ethyl by weight of the formulation;
c) about 0.6% citric acid monohydrate by weight of the formulation;
d) about 3.5% sodium cetyl oleyl sulphate by weight of the formulation;
e) about 4.0% alkyl naphthalene sulfonate formaldehyde condensate by weight of the formulation;
f) about 8.0% sodium lignosulfonate by weight of the formulation;
g) about 0.7% poly dimethylsiloxane by weight of the formulation;
h) about 2.0% ammonium sulphate by weight of the formulation;
i) about 2.0% precipitated silica by weight of the formulation; and
j) about 0.2% china clay by weight of the formulation.
[0057] In one embodiment, the water dispersible granule (WDG)comprises:
a) about 70% metribuzin by weight of the formulation;
b) about 2% pyrazosulfuron-ethyl by weight of the formulation;
c) about 0.5% citric acid monohydrate by weight of the formulation;
d) about 5.6% sodium salt of alkyl naphthalene sulfonate by weight of the formulation;
e) about 8.5% styrene (meth)acrylic copolymer, sodium salt by weight of the formulation;
f) about 1.0% poly dimethylsiloxane by weight of the formulation;
g) about 2.0% ammonium sulphate by weight of the formulation;
h) about 2.0% precipitated silica by weight of the formulation; and
i) about 8.4% china clay by weight of the formulation.
[0058] In an embodiment, the stabilizing agent is selected without limitation from the group comprising of citric acid monohydrate, citric acid anhydrous, ortho phosphoric acid, oxalic acid, hydrochloric acid, acetic acid, sodium silicate, potassium silicate, magnesium silicate, sodium pyrophosphate, sodium, acetate, sodium oxalate, sodium carbonate, magnesium carbonate, sodium bicarbonate, sodium bentonite, attapulgite, diatomaceous earth sodium zeolite, trisodium phosphate, trisodium citrate, magnesium carbonate, magnesium sulphate, ammonium sulphate, monoethanol amine, triethanol amine, triethylamine, dibasic esters selected from dimethyl succinate, dimethyl glutarate or dimethyl adipate or the mixture thereof.
[0059] In an embodiment, the wetting agent is selected from but not limited to sodium cetyl oleyl sulphate, sodium salt of alkyl naphthalene sulfonate, sodium salt of isopropyl naphthalene sulfonate, sodium dioctyl sulfosuccinate, sodium lauryl sulfate and sodium dodecyl benzene sulfonate, alkyl diphenyl sulfonates, alpha olefin sulfonate, phenyl naphthalene sulfonates, sodium salt of sulfonated alkyl carboxylate, dioctyl sulfosuccinate sodium salt and sodium isopropyl naphthalene sulfonate, polyoxyalkylated ethyl phenols, polyoxyethoxylated fatty alcohols, polyoxyethoxylated fatty amines, alkane sulfonates, alpha olefin sulfonates, alkylbenzene sulfonates, salts of polycarboxylic acids, salts of esters of sulfosuccinic acid, octyl phenol ether sulphatedisodium laureth sulfosuccinate, diisodecyl sodium sulfosuccinate, or the mixture thereof.
[0060] In an embodiment, the dispersing agent is selected from but not limited to alkyl naphthalene sulfonate formaldehyde condensate, sodium lignosulfonate, styrene (meth)acrylic copolymer sodium salt, isopropyl naphthalene sulfonate formaldehyde condensate, polyesters, polyamides, poly-carbonates, acrylic polymers and copolymers, styrene copolymers, butadiene copolymers, polyolefins copolymers, sodium alkyl aryl sulfonates, maleic anhydride copolymers, condensation products of aryl/alkyl sulphonic acids and formaldehyde, addition products of ethylene oxide and fatty acid esters, sodium alkyl benzene sulfonates, polystyrenated acrylated co- polymer, salts of polyacrylic acids, or mixtures thereof.
[0061] In an embodiment, the anti-foaming agent is selected without limitation from perfluroalkylphosphonic acids, polydimethyl siloxane or mixtures thereof.
[0062] In an embodiment, the inert carrier can be selected from but not limited to natural ground minerals, such as kaolin 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, crushed and fractionated natural minerals, such as calcite, marble, pumice, sepiolite, bentonite, river sand, zeolites, sand and dolomite, or synthetic granules of inorganic and organic ground materials, urea, potassium dihydrogen phosphate, superphosphate, diatomite, white carbon, precipitated calcium carbonate, sawdust, and starch, ammonium sulphate, precipitated silica, china clay or mixture thereof.
[0063] In certain embodiments, the present disclosure provides a method of preparation of a formulation comprising the constituents of the composition of the present disclosure.
[0064] In one embodiment, the present disclosure provides a method of preparation of an herbicidal wettable powder (WP) formulation comprising the steps of:
a) mixing active ingredients, stabilizing agent and agriculturally acceptable excipient(s) for about 1 hour to about 4 hours to obtain a pre-blended mixture;
b) grinding the pre-blended mixture through a mill to obtain a milled powder; and
c) homogenising the milled powder for about 1 hour to about 4 hours, to obtain a homogeneous wettable powder (WP) formulation.
[0065] In some specific embodiment, the present disclosure provides a method of preparation of an herbicidal wettable powder (WP) formulation comprising the steps of:
a) mixing metribuzin about 50% to about 90% w/w, pyrazosulfuron-ethyl about 0.1% to about 10% w/w, stabilizing agent about 0.01% to about 5.0% w/w, and agriculturally acceptable excipient(s) about 0.1% to 49.89% w/w of the of the formulation for about 1 hour to about 4 hours to obtain a pre-blended mixture;
b) grinding the pre-blended mixture through a mill to obtain a milled powder; and
c) homogenising the milled powder for about 1 hour to about 4 hours, preferably for about 2 hours to obtain a homogeneous wettable powder (WP) formulation.
[0066] In another embodiment, the present disclosure provides a method of preparation of an herbicidal water dispersible granule (WDG) formulation comprising the steps of:
a) mixing active ingredients, stabilizing agent and agriculturally acceptable excipient(s) for about 1 hour to about 4 hours to obtain a pre-blended mixture;
b) grinding the pre-blended mixture through a mill to obtain a milled powder;
c) homogenising the milled powder for about 1 hour to about 4 hours to obtain a homogeneous powder;
d) spraying de-mineralized water on the homogeneous powder and mixing to prepare a uniform dough; and
e) extruding the uniform dough through an extruder to obtain extruded granules and drying the extruded granules in a fluid bed dryer to obtain the water dispersible granule (WDG) formulation.
[0067] In a specific embodiment, the present disclosure provides a method of preparation of an herbicidal WDG formulation comprising the steps of:
a) mixing metribuzin about 50% to about 90% w/w, pyrazosulfuron-ethyl about 0.1% to about 10% w/w, stabilizing agent about 0.01% to about 5.0% w/w of the composition, and agriculturally acceptable excipient(s) about 0.1% to about 49.89% w/w of the formulation for about 1 hour to about 4 hours to obtain a pre-blended mixture;
b) grinding the pre-blended mixture through a mill to obtain a milled powder;
c) homogenising the milled powder for about 1 hour to about 4 hours to obtain a homogeneous powder;
d) spraying de-mineralized water on the homogeneous powder and mixing to prepare a uniform dough; and
e) extruding the uniform dough through an extruder to obtain extruded granules and drying the extruded granules in a fluid bed dryer to obtain the water dispersible granule (WDG) formulation.
[0068] Mixing of the ingredients in the method of the present disclosure is carried out in a blender of suitable size and configuration.
[0069] The grinding of the pre-blended mixture in the method of the present disclosure is in an air-jet mill to obtain air jet milled powder.
[0070] In one embodiment, the grinding can be carried out for about 2 hours to obtain a pre-blended mixture or a homogeneous powder.
[0071] In the method of the present disclosure making of the uniform dough is carried out in suitable dough maker.
[0072] In the method of the present disclosure the uniform dough is extruded through a basket type extruder.
[0073] In certain embodiment, in the methods of the present disclosure, the pH of the composition or formulation is maintained between the range 5.0 – 9.0, preferably 6.0 – 8.0 by adding a stabilizing agent.
[0074] It was observed that the pH between said range of 5.0 – 9.0 helps to maintain the composition and formulation comprising the same stable. It was surprisingly found that pH range between 5.0 - 9.0 unexpectedly helps in particularly to maintain the stability of the active ingredient pyrazosulfuron-ethyl, which otherwise was found to degrade at pH below 5.0 and above pH 9.0.
[0075] The formulation of the present disclosure having a pH in the range between 5.0 – 9.0 was found to more stable, which leads to the increased bioefficacy.
[0076] The binary herbicidal composition comprising the combination of metribuzin, pyrazosulfuron-ethyl and stabilizing agent and WP and WDG formulations comprising the same surprisingly show synergistic herbicidal activity at much lesser amounts of metribuzin and pyrazosulfuron-ethyl as compared to the amounts when said ingredients used alone.
[0077] The herbicidal WP or WDG formulation in accordance with the present disclosure can be applied at the target site in a suitable manner for example by foliar spray on weeds.
[0078] In an embodiment, the binary herbicidal composition comprising combination of metribuzin, pyrazosulfuron-ethyl, stabilizing agent and WP or WDG formulation comprising the same in accordance with the present disclosure can be used for controlling, i.e. preventing or destroying, and suppressing weeds associated with crops in agriculture.
[0079] In an embodiment, binary herbicidal composition comprising a combination of metribuzin, pyrazosulfuron-ethyl and stabilizing agent and WP and WDG formulation comprising the same are useful for controlling weeds in crops, preferably sugarcane crop.
[0080] In another embodiment, the present invention provides a method for controlling weed that is unwanted plant growth among the crop of interest, which comprises applying the WP or WDG formulation formulated from the binary herbicidal composition comprising combination of metribuzin, pyrazosulfuron-ethyl and stabilizing agent to plants, plant parts, plant seeds or areas where plants grow, preferably for selective control of weeds in crops. The herbicidal formulation of the present disclosure can be applied to the weeds, especially to the surface of weeds that are harmful to crop growth or easily affected by the weeds.
[0081] In an embodiment, the herbicidal WP or WDG formulation can be used for controlling, i.e. preventing, destroying, or suppressing Ipomoea purpurea and Cyperus rotundus weeds.
[0082] While the foregoing describes various embodiments of the disclosure, other and further embodiments of the disclosure may be devised without departing from the basic scope thereof. 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
[0083] The present disclosure is further explained in the form of following examples. However, it is to be understood that the following examples are merely illustrative and are not to be taken as limiting to 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 disclosure of the present application.
Example 1
Preparation of WP formulation comprising Metribuzin, Pyrazosulfuron Ethyl and stabilizing agent.
[0084] The following Table 1 shows the composition for a binary herbicidal composition in accordance with exemplary embodiments.
Table 1. Composition for binary herbicidal composition.
S. No. Ingredient Class of ingredient Example-1
%w/w
1 Active Ingredient Metribuzin 75
2 Active Ingredient Pyrazosulfuron-ethyl 4
3 Stabilizing agent Citric acid monohydrate 0.6
4 Wetting agent Sodium cetyl oleyl sulphate 3.5
5 Dispersing agent Alkyl naphthalene sulfonate formaldehyde condensate 4.0
6 Dispersing agent Sodium lignosulfonate 8.0
7 Antifoaming agent Poly dimethylsiloxane 0.7
8 Inert carrier Ammonium sulphate 2.0
9 Inert carrier Precipitated silica 2.0
10 Inert carrier China clay Q.S.
Total 100%
[0085] The binary herbicidal compositions as per above Table 1 were formulated into wet table powder (WP) formulation following the below method:
a) All the ingredients were added to a clean pre-blender and mixed for 2 hours to get a pre-blended mixture.
b) The pre-blended mixture obtained in the above step was subjected to grinding through air-jet mill to obtain desirable particle size milled powder.
c) The milled powder in the post blender was mixed for 2 hours to obtain the homogeneous wettable powder (WP).
Examples 2-3
Preparation of WDG formulation comprising Metribuzin, Pyrazosulfuron Ethyl and stabilizing agent.
[0086] The following Table 2 shows the composition for a binary herbicidal composition in accordance with exemplary embodiments.
Table 2: Compositions for binary herbicidal composition
S. No. Class of ingredient Ingredient Example-2 Example-3
%w/w %w/w
1 Active Ingredient Metribuzin 70 60
2 Active Ingredient Pyrazosulfuron-ethyl 2 4
3 Stabilizing agent Citric acid monohydrate 0.5 0.7
4 Wetting agent sodium salt of alkyl naphthalene sulfonate 5.6 4.0
5 Dispersing agent Styrene (meth)acrylic copolymer, Sodium salt 8.5 8.0
6 Antifoaming agent Poly dimethylsiloxane 1.0 0.8
7 Inert carrier Ammonium sulphate 2.0 2.0
8 Inert carrier Precipitated silica 2.0 1.5
9 Inert carrier China clay Q.S. Q.S.
Total 100% 100%
[0087] The binary herbicidal compositions as per above Table 2 were formulated into water dispersible granules (WDG) formulation following the below method:
a) All the ingredients were added to a clean pre-blender and mixed for 2 hours to get a pre-blended mixture.
b) The pre-blended mixture obtained in the above step was subjected to grinding through air-jet mill to obtain desirable particle size milled powder.
c) The milled powder in the post blender was mixed for 2 hours to ensure homogeneity of the mixture.
d) The homogenous mixture was charged in a dough maker and the demineralised water was sprayed onto it to prepare uniform dough.
e) The dough was extruded through a basket type extruder and dried in fluid bed drier to obtain WDG formulation.
Examples 4
Accelerated Storage test (Stability Study).
[0088] 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.
[0089] The “ambient sample” is the sample at the room temperature which is before subjecting to the accelerated storage test.
[0090] The “accelerated storage sample” is the sample after subjecting to the accelerated storage test.
[0091] The ambient sample of the water dispersible granules (WDG) formulation of the above Example 2 was subjected to the accelerated storage test to find out the product stability.
[0092] Table 3 shows the physical and chemical properties of the water dispersible granules (WDG) formulation of the above Example 2 before and after the accelerated storage test.
Table 3. Physical and chemical properties of the water dispersible granules (WDG) formulation of the Example 2 before and after the accelerated storage test.
S.No. TESTS RT 0 days AHS 54°C, 2 weeks Method of Analysis
1 Description Off white to cream colored granules Off white to cream colored granules
Visual
2 Active ingredient (% w/w)
(i) Pyrazosulfuron-ethyl content 2.0 1.97 (1.50%) By HPLC Method
(ii) Metribuzin content 70.0 69.04 (1.37%)
3 Suspensibility (% w/w)
(i) Pyrazosulfuron-ethyl 99.4 98.8 CIPAC MT 184
(ii) Metribuzin 99.7 98. 6
4 Wettability, Sec 20 22 CIPAC MT 53.3.2
5 Wet sieve passing through 75? test sieve (% w/w) 99.9 99.8 CIPAC MT 185
6 Degree of dispersion (% w/w) 93.8 91.8 CIPAC MT 174
7 Persistent foam after 1 min, mL 8 10 CIPAC MT 47.2
8 pH of 1% Aq. dispersion 6.3 6.5 CIPAC MT 75.3
9 Dust content, mg 8 6 CIPAC MT 171
CIPAC MT: Collaborative International Pesticides Analytical Council Miscellaneous techniques
[0093] The results in Table 3 show that various parameters of the stability studies before the after the stability studies remained almost the same after, which prove that the (WDG) formulation of the Example 2 of the present invention is stable.
[0094] The results of the persistent foam test showed low persistent foam of 10ml indicating the less froth formation indicating less wastage of the formulation.
[0095] The results of the degree of dispersion test and suspensibility test showed that the formulation dispersed uniformly and formed homogeneous suspension spontaneously.
[0096] In view of the above test results, the WDG formulation of the present invention is extrapolated to be stable for 2 years.
[0097] The advantages of the) of the WDG formulation of the present invention include no long term storage stability issues and easy to handle while maintaining the efficacy.
Example 5.
Field Tests.
[0098] The water dispersible granules (WDG) formulation of the above Example 2 was tested for its biological activity and the results are shown in Tables 4 to 5 below:
Table 4: Field test results of the effect of Formulation of Example 2 against major weeds in Sugarcane, Vuyyuru, Vijayawada, A.P in Kharif, 2022.
Treatment Dosage Mean no. of weeds/Sq.mt area
( 30 days after application)
g a.i./ha Formulation (g/ml/ha) Grasses BLW Sedges Total
Example 2 Formulation 700 + 20 1000 0.20 0.50 3.72 4.42
2,4 D sodium salt 44% + Metribuzin 35% + Pyrazosulfuron ethyl 1% WG 1320 + 1050 + 30 3000 0.57 0.87 4.67 6.10
Pyrazosulfuron ethyl 10%WP 20 200 1.30 2.80 7.80 11.90
Metribuzin 70%WP 700 1000 0.73 1.31 5.20 7.24
Untreated check - - 3.38 5.96 24.67 34.01
Observations:
[0099] The application of Example 2 formulation @ 1000g/ha recorded less number of weeds and was found to be superior to the use of each active ingredients individually and standard check. The formulation in accordance with the present invention showed synergistic activity on all the major weeds.
Table 5: Field test results of the effect of Formulation of Example 2 against major weeds in Sugarcane, Vuyyuru, Vijayawada, A.P in Kharif, 2022.
Treatment Dosage % Control over UTC
(9 days after spraying)
g a.i./ha Formulation (g/ml/ha) Grasses BLW Sedges % Mean control
Example 2 Formulation 700 + 20 1000 94.08 91.61 84.92 89.12
2,4 D sodium salt 44% + Metribuzin 35% + Pyrazosulfuron ethyl 1% WG 1320 + 1050 + 30 3000 83.25 85.45 80.75 81.96
Pyrazosulfuron ethyl 10%WP 20 200 61.53 53.02 68.38 60.97
Metribuzin 70%WP 700 1000 78.39 77.98 78.97 78.75
Untreated check - - - - - -
Observations:
[00100] The application of Example 2 formulation @ 1000g/ha recorded higher efficacy (>89%) and was found to be superior to the use of each active ingredients individually and standard check.
[00101] Accordingly, the above test results of show unexpected and surprising results proving the synergistic effect of the combination of metribuzin, pyrazosulfuron ethyl and stabilizing agent in respect of better efficacy and superior effect against major weeds including most problematic weeds viz., Ipomoea spp. and Cyperus rotundus as compared to each active ingredient individually and standard check. There was no regrowth or fresh growth was observed of problematic weeds viz., Ipomoea spp. and Cyperus rotundus. As can be seen from Tables 4 to 5, the formulation comprising composition as per Example 2 with combination of metribuzin, pyrazosulfuron ethyl and stabilizing agent exhibited synergistic effect to combat all the major weeds and was also highly safe to sugarcane
[00102] 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.
ADVANTAGES OF THE PRESENT INVENTION
[00103] The present invention provides a binary herbicidal composition comprising metribuzin, pyrazosulfuron ethyl and a stabilizing agent that shows synergistic activity with better efficacy of controlling weeds and no fresh emergence of weeds.
[00104] The present invention provides an herbicidal WP and WDG formulations comprising metribuzin, pyrazosulfuron ethyl and a stabilizing agent that shows synergistic activity with better efficacy of controlling weeds for longer duration.
[00105] The present invention provides a binary herbicidal composition comprising metribuzin, pyrazosulfuron ethyl and a stabilizing agent and WP and WDG formulation thereof that does not result in phytotoxicity on applied crop and is safe to use.
,CLAIMS:1. A binary herbicidal composition comprising:
a) 50% to 90% metribuzin by weight of the composition;
b) 0.1% to 10% pyrazosulfuron-ethyl by weight of the composition;
c) 0.01% to 5.0% stabilizing agent by weight of the composition;
d) 0.1% to 49.89% one or more agriculturally acceptable excipient(s) by weight of the composition.
2. The binary herbicidal composition as claimed in claim 1, wherein agriculturally acceptable excipient(s) are selected from the group comprising 0.1% to 8% wetting agent w/w, 0.1% to 20.0% dispersing agent w/w and 0.01% to 5.0% antifoaming agent w/w and 0.1% to 49.68% one or more inert carrier w/w.
3. A binary herbicidal formulation comprising:
a) 50% to 90% metribuzin by weight of the formulation;
b) 0.1% to 10% pyrazosulfuron-ethyl by weight of the formulation;
c) 0.01% to 5.0% stabilizing agent by weight of the formulation;
d) 0.1% to 49.89% one or more agriculturally acceptable excipient(s) by weight of the formulation.
4. The binary herbicidal formulation as claimed in claim 3, wherein agriculturally acceptable excipient(s) are selected from the group comprising 0.1% to 8% wetting agent w/w, 0.1% to 20.0% dispersing agent w/w and 0.01% to 5.0% antifoaming agent w/w and 0.1% to 49.68% one or more inert carrier w/w.
5. The binary herbicidal formulation as claimed in any one of the claims 3-4, wherein the formulation is selected from the group consisting of capsule suspension (CS), controlled release granules (CR), dispersible concentrate (DC), emulsifiable concentrate (EC), emulsion, water in oil (EO), emulsion, oil in water (EW), granule (GR), soil applied granules (SAG), jambo balls, bags, bags in water soluble pouch, micro-emulsion (ME), oil dispersion (OD), oil miscible flowable concentrate (oil miscible suspension) (OF), oil miscible liquid (OL), suspension concentrate (SC), suspo-emulsion (SE), soluble concentrate (SL), water soluble granule (SG), water soluble powder (SP), water dispersible granule (WDG or WG), wettable powder (WP), a water-dispersible powder (WDP), encapsulated granule (CG), a fine granule (FG), a macrogranule (GG), a microgranule (MG), a flowable suspension (FS), dustable powder (DP), a gel, a water-dispersible tablet (WT), a mixed formulation of CS and SC (ZC), a mixed formulation of CS and SE (ZE), and a mixed formulation of CS and EW (ZW).
6. The binary herbicidal formulation as claimed in claim 5, wherein the formulation is wettable powder (WP) formulation.
7. The binary herbicidal formulation as claimed in claim 5, wherein the formulation is water dispersible granule (WDG) formulation.
8. The binary herbicidal formulation as claimed in any one of claims 3-7, wherein the stabilizing agent is selected from the group comprising of citric acid monohydrate, citric acid anhydrous, ortho phosphoric acid, oxalic acid, hydrochloric acid, acetic acid, sodium silicate, potassium silicate, magnesium silicate, sodium pyrophosphate, sodium, acetate, sodium oxalate, sodium carbonate, magnesium carbonate, sodium bicarbonate, sodium bentonite, attapulgite, diatomaceous earth sodium zeolite, trisodium phosphate, trisodium citrate, magnesium carbonate, magnesium sulphate, ammonium sulphate, monoethanol amine, triethanol amine, triethylamine, dibasic esters selected from dimethyl succinate, dimethyl glutarate or dimethyl adipate or the mixture thereof.
9. The binary herbicidal formulation as claimed in any one of claims 3-8, wherein the wetting agent is selected from the group comprising of sodium cetyl oleyl sulphate, sodium salt of alkyl naphthalene sulfonate, sodium salt of isopropyl naphthalene sulfonate, sodium dioctyl sulfosuccinate, sodium lauryl sulfate and sodium dodecyl benzene sulfonate, alkyl diphenyl sulfonates, alpha olefin sulfonate, phenyl naphthalene sulfonates, sodium salt of sulfonated alkyl carboxylate, dioctyl sulfosuccinate sodium salt and sodium isopropyl naphthalene sulfonate, polyoxyalkylated ethyl phenols, polyoxyethoxylated fatty alcohols, polyoxyethoxylated fatty amines, alkane sulfonates, alpha olefin sulfonates, alkylbenzene sulfonates, salts of polycarboxylic acids, salts of esters of sulfosuccinic acid, octyl phenol ether sulphatedisodium laureth sulfosuccinate, diisodecyl sodium sulfosuccinate, or the mixture thereof.
10. The binary herbicidal formulation as claimed in any one of claims 3-9, wherein the dispersing agent is selected from the group comprising of alkyl naphthalene sulfonate formaldehyde condensate, sodium lignosulfonate, styrene (meth)acrylic copolymer sodium salt, isopropyl naphthalene sulfonate formaldehyde condensate, polyesters, polyamides, poly-carbonates, acrylic polymers and copolymers, styrene copolymers, butadiene copolymers, polyolefins copolymers, sodium alkyl aryl sulfonates, maleic anhydride copolymers, condensation products of aryl/alkyl sulphonic acids and formaldehyde, addition products of ethylene oxide and fatty acid esters, sodium alkyl benzene sulfonates, polystyrenated acrylated co- polymer, salts of polyacrylic acids, or mixtures thereof.
11. The binary herbicidal formulation as claimed in any one of claims 3-10, wherein the anti-foaming agent is selected from the group comprising of perfluroalkylphosphonic acids, polydimethyl siloxane or mixtures thereof.
12. The binary herbicidal formulation as claimed in any one of claims 3-11, wherein the inert carrier can be selected from but not limited to natural ground minerals, such as kaolin 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, crushed and fractionated natural minerals, such as calcite, marble, pumice, sepiolite, bentonite, river sand, zeolites, sand and dolomite, or synthetic granules of inorganic and organic ground materials, urea, potassium dihydrogen phosphate, superphosphate, diatomite, white carbon, precipitated calcium carbonate, sawdust, and starch, ammonium sulphate, precipitated silica, china clay or mixture thereof.
13. The binary herbicidal formulation as claimed in claim 6, wherein the WP formulation comprises:
a) 75% metribuzin by weight of the formulation;
b) 4% pyrazosulfuron-ethyl by weight of the formulation;
c) 0.6% citric acid monohydrate by weight of the formulation;
d) 3.5% sodium cetyl oleyl sulphate by weight of the formulation;
e) 4.0% alkyl naphthalene sulfonate formaldehyde condensate by weight of the formulation;
f) 8.0% sodium lignosulfonate by weight of the formulation;
g) 0.7% poly dimethylsiloxane by weight of the formulation;
h) 2.0% ammonium sulphate by weight of the formulation;
i) 2.0% precipitated silica by weight of the formulation; and
j) 0.2% china clay by weight of the formulation.
14. A method of preparation of an herbicidal wettable powder (WP) formulation as claimed in claim 13, the method comprises the steps of:
a) mixing metribuzin about 50% to about 90% w/w, pyrazosulfuron-ethyl about 0.1% to about 10% w/w, stabilizing agent about 0.01% to about 5.0% w/w, and agriculturally acceptable excipient(s) about 0.1% to 49.89% w/w of the formulation for about 1 hour to about 4 hours to obtain a pre-blended mixture;
b) grinding the pre-blended mixture through a mill to obtain a milled powder; and
c) homogenising the milled powder for about 1 hour to about 4 hours to obtain a homogeneous wettable powder (WP) formulation.
15. The binary herbicidal formulation as claimed in claim 7, wherein the water dispersible granule (WDG) formulation comprises:
a) 70% metribuzin by weight of the formulation;
b) 2% pyrazosulfuron-ethyl by weight of the formulation;
c) 0.5% citric acid monohydrate by weight of the formulation;
d) 5.6% sodium salt of alkyl naphthalene sulfonate by weight of the formulation;
e) 8.5% styrene (meth)acrylic copolymer, Sodium salt by weight of the formulation;
f) 1.0% poly dimethylsiloxane by weight of the formulation;
g) 2.0% ammonium sulphate by weight of the formulation;
h) 2.0% precipitated silica by weight of the formulation; and
i) 8.4% china clay by weight of the formulation.
16. A method of preparation of an herbicidal WDG formulation as claimed in claim 15, the method comprises the steps of:
a) mixing metribuzin about 50% to about 90% w/w, pyrazosulfuron-ethyl about 0.1% to about 10% w/w, stabilizing agent about 0.01% to about 5.0% w/w, and agriculturally acceptable excipient(s) about 0.1% to 49.89% w/w of the formulation for about 1 hour to about 4 hours to obtain a pre-blended mixture;
b) grinding the pre-blended mixture through a mill to obtain a milled powder;
c) homogenising the milled powder for about 1 hour to about 4 hours to obtain a homogeneous powder;
d) spraying de-mineralized water on the homogeneous powder and mixing to prepare a uniform dough; and
e) extruding the uniform dough through an extruder to obtain extruded granules and drying the extruded granules in a fluid bed dryer to obtain the water dispersible granule (WDG) formulation.
17. The method as claimed in any one of the claims 14 or 16 wherein, the pH of the formulation is maintained between the range 5.0 – 9.0, preferably 6.0 – 8.0 by adding a stabilizing agent.
| # | Name | Date |
|---|---|---|
| 1 | 202121055817-STATEMENT OF UNDERTAKING (FORM 3) [02-12-2021(online)].pdf | 2021-12-02 |
| 2 | 202121055817-PROVISIONAL SPECIFICATION [02-12-2021(online)].pdf | 2021-12-02 |
| 3 | 202121055817-FORM 1 [02-12-2021(online)].pdf | 2021-12-02 |
| 4 | 202121055817-DECLARATION OF INVENTORSHIP (FORM 5) [02-12-2021(online)].pdf | 2021-12-02 |
| 5 | 202121055817-FORM-26 [11-02-2022(online)].pdf | 2022-02-11 |
| 6 | 202121055817-Proof of Right [11-05-2022(online)].pdf | 2022-05-11 |
| 7 | 202121055817-RELEVANT DOCUMENTS [30-11-2022(online)].pdf | 2022-11-30 |
| 8 | 202121055817-FORM 13 [30-11-2022(online)].pdf | 2022-11-30 |
| 9 | 202121055817-ENDORSEMENT BY INVENTORS [02-12-2022(online)].pdf | 2022-12-02 |
| 10 | 202121055817-CORRESPONDENCE-OTHERS [02-12-2022(online)].pdf | 2022-12-02 |
| 11 | 202121055817-COMPLETE SPECIFICATION [02-12-2022(online)].pdf | 2022-12-02 |
| 12 | 202121055817-FORM 18 [05-12-2022(online)].pdf | 2022-12-05 |
| 13 | 202121055817-FER.pdf | 2024-01-19 |
| 14 | 202121055817-FER_SER_REPLY [19-07-2024(online)].pdf | 2024-07-19 |
| 15 | 202121055817-CORRESPONDENCE [19-07-2024(online)].pdf | 2024-07-19 |
| 16 | 202121055817-US(14)-HearingNotice-(HearingDate-22-07-2025).pdf | 2025-06-13 |
| 17 | 202121055817-FORM-26 [16-07-2025(online)].pdf | 2025-07-16 |
| 18 | 202121055817-Correspondence to notify the Controller [16-07-2025(online)].pdf | 2025-07-16 |
| 19 | 202121055817-Response to office action [21-07-2025(online)].pdf | 2025-07-21 |
| 20 | 202121055817-Written submissions and relevant documents [06-08-2025(online)].pdf | 2025-08-06 |
| 21 | 202121055817-Annexure [06-08-2025(online)].pdf | 2025-08-06 |
| 22 | 202121055817-US(14)-ExtendedHearingNotice-(HearingDate-26-11-2025)-1130.pdf | 2025-10-29 |
| 23 | 202121055817-Correspondence to notify the Controller [20-11-2025(online)].pdf | 2025-11-20 |
| 1 | SearchHistory(1)E_18-01-2024.pdf |