DESC:FIELD OF THE INVENTION
[0001] The present invention relates to a stable formulation of two herbicides having different modes of action for weed control in agriculture. In particular, this invention pertains to an improved stable herbicidal formulation comprising combination of flumioxazin and diclosulam for weed control in agriculture.

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] This invention pertains to a stable formulation of two herbicides: flumioxazin and diclosulam for weed control. Flumioxazin is protoporphyrinogen oxidase inhibitor, which acts by inducing massive accumulation of porphyrins and enhancing peroxidation of membrane lipids, which leads to irreversible damage of the membrane function and structure of susceptible weeds. Flumioxazin is generally used for pre-emergence control of annual broad-leaved and some annual grass weeds in soybean, peanuts and other crops. Diclosulam can be used as preemergence, pre-plant or pre-plant incorporated control of broad-leaved weeds in soybean, peanuts and other crops. Diclosulam inhibits the acetolactate synthase (ALS) enzyme. The primary site of activity is within the chloroplasts in plant meristems. Diclosulam is taken up by both roots and foliage and translocated to new growing points. Lethal amount of diclosulam accumulates in meristems, halting cell division and resulting in the death of weed plants. Flumioxazin is an N-phenylphthalimide herbicide while diclosulam belongs to triazolopyrimidine group of chemicals.
[0004] Flumioxazin 50% SC was developed by Sumitomo Chemical Company and marketed in India by Sumitomo Chemical India Ltd. (hereinafter named as SCIL). This formulation i.e. Flumioxazin 50% SC is registered in India as single active ingredient-based product providing control of some weed species. At times, this becomes a limitation of formulations based on single active ingredient and farmers need to use multiple products for controlling various kinds of weeds, which might lead to deploying labours each time for performing spray application of single herbicide-based products. This becomes a cumbersome and cost-intensive affair.
[0005] The outcome of combining two chemicals is often unpredictable due to their differing chemical, physical, and biological properties. Combining two chemicals can lead to instability, degradation, or undesired reactions, making it challenging to maintain efficacy over the product's shelf life. Issues like precipitation, phase separation, or crystallization may also arise when the two substances are mixed.
[0006] Further, it is quite possible that the combined product might exhibit reduced efficacy due to antagonistic interactions between the two chemicals. Demonstrating synergistic effects between two chemicals often requires extensive experimentation, as interactions between the two chemicals can be highly unpredictable. Determining the optimal ratio or concentration for each chemical to achieve desired efficacy without adverse effects requires extensive research and iterative testing. Designing a stable and uniform formulation may involve overcoming significant technical barriers such as ensuring homogeneity, avoiding degradation, and achieving desired release profiles.
[0007] Developing a composition of Flumioxazin and Diclosulam based on its herbicidal properties was a challenging task and keeping that in view, the present inventors invented a unique formulation of these two herbicides. The distinctive strength of these two herbicides was devised by the inventors in order to get better performance than its individual components. After significant research, the formulation proved to be novel in many aspects: a) This formulation was found to be effective against a variety of weeds, b) The product was found stable for two years, c) Both the individual molecules i.e. flumioxazin and diclosulam belong to different chemical groups and have different mode of actions, which make them ideal combination partners for use in Integrated Weed Management practices as well as resistance management strategies, d) There has not been any such formulation commercialized in India that is based on a combination of flumioxazin and diclosulam, e) This product has exhibited its bio-efficacy on soybean and other crops, and f) The farmers come across with a lot of economic losses due to many types of weed problems in their crops, which could be tackled through this formulation. In view of above, the said formulation can be considered as novel and a boon to farmers and the agricultural community.
[0008] Attempts to combine flumioxazin and diclosulam into a single composition are described in CN110024796A and JP2001233717A. However, it may be noted that the process of combining the individual active ingredients or formulating two or more herbicides in a single composition poses many challenges to the formulator. Major challenges being stability of the co-formulation, decomposition of an active ingredient, antagonism of the active ingredients, and/or phytotoxicity in the treated crops. It has also been found that solid formulations prepared with a combination of flumioxazin and diclosulam, such as water dispersible granules and wettable powder, have reduced product performance indexes, especially a low suspensibility and dispersibility after shelf storage tests. Therefore, it is necessary to study and develop a new solid formulation to solve the technical problem of the long-term storage performance indexes of products prepared from a combination of flumioxazin and diclosulam being reduced.
[0009] The present invention satisfies the existing needs, as well as others, and generally overcomes the deficiencies found in the prior art.

OBJECT OF THE INVENTION
[0010] An object of the present invention is to address the stability issues that can occur when flumioxazin and diclosulam are co-formulated as a solid granular formulation.
[0011] It is also an object of the present invention to provide a co-formulation of flumioxazin and diclosulam that has advantageously improved storage stability, without significant reduction in product performance indexes, such as suspensibility and spontaneous dispersibility after long-term storage.
[0012] Further object of the present invention is to provide an improved co-formulation of flumioxazin and diclosulam that is safe while being highly effective in controlling weeds.
[0013] Still further object of the present invention is to provide a method of preparing stable solid formulations of mixtures of flumioxazin and diclosulam.

SUMMARY OF THE INVENTION
[0014] Aspects of the present invention relate to stable solid granular formulations comprising combination of flumioxazin and diclosulam that have advantageously improved storage stability and exhibit advantageous herbicidal activity profile. The inventors have surprisingly discovered that a combination of excipients comprising sodium alkylnaphthalenesulfonate formaldehyde condensate as a first dispersing agent and sodium lignosulfonate as a second dispersing agent is capable of forming stable solid granular formulations of flumioxazin and diclosulam that can provide good dispersion and suspension properties upon extended storage of the formulations. The inventors have surprisingly found that when the particular formulation excipients described herein are employed, a more storage-stable and more effective solid granular formulations of flumioxazin and diclosulam can be achieved than could previously be achieved with formulation approaches known in the prior art.
[0015] Accordingly, one aspect of the present invention is directed to a solid granular formulation comprising flumioxazin, diclosulam, sodium alkylnaphthalenesulfonate formaldehyde condensate as a first dispersing agent and sodium lignosulfonate as a second dispersing agent. The ensuing formulation has advantageously improved storage stability, without significant reduction in product performance indexes, such as suspensibility and spontaneous dispersibility upon long-term storage and exhibits advantageous herbicidal activity profile. In some embodiments, the solid granular formulation is in the form of water dispersible granules (WDG). In some embodiments, the solid granular formulation is in the form of a wettable powder (WP). In some embodiments, the solid granular formulation is in the form of water disintegrable granules. In some embodiments, the solid granular formulation is in the form of spheronised granules. In some embodiments, the solid granular formulation is in the form of extruded granules.
[0016] The solid granular formulation according to the present invention is suitable for selectively controlling weeds in crops of useful plants such as soybeans, rice, wheat, cereals, oilseed rape, sugar beet, sugarcane, cotton, maize, corn, and vegetables in general. Further, the formulation can exhibit a synergistic herbicidal activity against a broad spectrum of economically important weeds, including broadleaf, sedge, and grass weeds. The formulation is suitable for all application methods conventionally used in agriculture, for example pre-emergence application, post-emergence application and seed dressing.
[0017] 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
[0018] The advances in weed science research, over the years, have witnessed many new weed control technologies including development of combination products having more than one active ingredient to enhance their spectrum of weed control. This progressive approach of combining two active ingredients in a specific ratio of synergy to give desired results is the outcome of many years’ extensive research and development as the combinations are evaluated thoroughly under field conditions viz., variations in climate, soil type, crops and methods of application and many other relevant situations. The application of two herbicides as pre-mix formulation produces desirable control of different weed species. This invention relates to a combination of Flumioxazin and Diclosulam developed with other ingredients e.g. adjuvants, inerts, etc. The concept of synergism (collective action encountered in combination products, wherein the combined activity of two compounds exceeds the sum of the activities of the compounds when used alone) was applied in various formulation types. The optimum efficacy was achieved in a specific solid, non-dusty granular formulation i.e. water dispersible granules, or wettable powder or water disintegrable granules or extruded granules or spheronized granules. The present invention not only protects crops from noxious weeds but also, increases yield through synergistically enhanced action and to a method of improving the health of plants by applying said compositions to the plants or the locus thereof. An important aspect of this invention is to primarily aim to protect crop from noxious weeds.
[0019] The results show the marked synergistic interaction of the compositions of the invention. After extensive tests and trials, it was found that the mortality of noxious weeds occurred due to synergistic effect of this combination is unexpectedly greater than that to be expected from the added effects of the individual components. The synergistic compositions of this invention may be employed to control a variety of noxious weeds in crops of useful plants including soybean. The formulation is prepared by incorporating suitable adjuvants, carriers and other ingredients in order to provide stability to the formulation for at least up to two years without impacting its bio-efficacy parameters.
[0020] This invention relates to a synergistic herbicidal composition comprising: (a) Flumioxazin in the range of 1% to 85%; (b) Diclosulam in the range of 1% to 90%; and (c) at least one excipient in the range of 0.05% to 80%.
[0021] In one embodiment, the synergistic herbicidal composition controls various types of weeds viz., Commelina benghalensis; Euphorbia spp., Digera arvensis, Acalypha spp.; Echinochloa spp., Trianthema spp.; Portulaca oleracea; Parthenium hysterophorus; Amaranthus viridis, Dinebra retroflexa, Alternanthera sessilis, Phylanthus sp, etc. in Soybean.
[0022] In another embodiment, the synergistic herbicidal composition controls annual broad-leaved and some annual grass weeds in soybean and other crops.
[0023] The term “herbicide” as used herein, refers to a compound that controls growth of undesirable vegetation.
[0024] 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 weeds.
[0025] 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.
[0026] 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.
[0027] As used herein, the phrase "agrochemically acceptable excipients" means excipients which are known and accepted in the art for formation of formulations for agricultural or horticultural use.
[0028] As used herein, the term "pre-emergence" refers to application of the herbicide composition to a habitat, a weed, or soil, prior to emergence of weeds from a soil surface. The term "post-emergence," refers to application of the herbicide composition to weeds that have already emerged from a soil surface.
[0029] In one aspect, the present invention is directed to improved stable solid granular formulations comprising combination of flumioxazin and diclosulam that have advantageously improved storage stability and exhibit advantageous herbicidal activity profile. Based on extensive research, and as is shown in more detail below, the inventors have discovered that an excipient combination comprising sodium alkylnaphthalenesulfonate formaldehyde condensate as a first dispersing agent and sodium lignosulfonate as a second dispersing agent can be used to address the stability issues that occur when flumioxazin and diclosulam are co-formulated as a solid preparation (water dispersible granules or wettable powder or water disintegrable granules or extruded granules or spheronised granules) and to form an improved stable solid granular formulation comprising combination of flumioxazin and diclosulam. Among other things, and as also shown in more detail below, the solid granular formulation according to the present disclosure has advantageously improved storage stability, excellent product performance attributes namely dispersibility and suspensibility and synergistically improved herbicidal action.
[0030] Some embodiments of the present invention describe a solid granular formulation which comprises flumioxazin, diclosulam, sodium alkylnaphthalenesulfonate formaldehyde condensate as a first dispersing agent and sodium lignosulfonate as a second dispersing agent. The ensuing formulation has advantageously improved storage stability, without significant reduction in product performance indexes, such as suspensibility and spontaneous dispersibility after long-term storage and exhibits advantageous herbicidal activity profile. In some embodiments, the solid granular formulation is in the form of water dispersible granules (WDG). In some embodiments, the solid granular formulation is in the form of a wettable powder (WP). In some embodiments, the solid granular formulation is in the form of water disintegrable granules. In some embodiments, the solid granular formulation is in the form of spheronised granules. In some embodiments, the solid granular formulation is in the form of extruded granules.
[0031] In the formulation of the present invention, the flumioxazin and diclosulam weight ratio at which the herbicidal effect exhibits synergistic effect lies within the range of from about 1:20 to about 20:1. Preferably, the weight ratio of flumioxazin to diclosulam in the formulation ranges from about 1:10 to about 10:1. In certain embodiments, flumioxazin and diclosulam are present in a weight ratio of 4:1.
[0032] The active ingredients flumioxazin and diclosulam may be present in the solid granular formulation in a wide range of amounts. In some preferred embodiments, the formulation comprises, by weight, from 1% to 85% of flumioxazin and from 1% to 90% of diclosulam, based on the total weight of the formulation. Preferably, flumioxazin is used in the range of 1% to 50% by weight and diclosulam is used in the range of 1% to 30% by weight of the formulation. In some embodiments, flumioxazin is present in an amount of 40% by weight and diclosulam is present in an amount of 10% by weight, based on the total weight of the formulation. In some embodiments, flumioxazin is present in an amount of 8% by weight and diclosulam is present in an amount of 2% by weight, based on the total weight of the formulation. In some embodiments, flumioxazin is present in an amount of 48% by weight and diclosulam is present in an amount of 12% by weight, based on the total weight of the formulation.
[0033] As indicated above, the solid granular formulation of the present invention includes sodium alkylnaphthalenesulfonate formaldehyde condensate as a first dispersing agent and sodium lignosulfonate as a second dispersing agent. This specific combination of dispersing agents was found to overcome the stability issues of the composition resulting in excellent dispersion and suspension properties after extended storage of the solid granular formulation. Further, the dispersing agents help disperse the herbicide particles in water and prevent the particles in spray tank from flocculating or aggregating together. This ensures that the herbicide particles remain suspended in water during the spraying operation and can be effectively employed in drip irrigation. The weight ratio of the first dispersing agent to the second dispersing agent may range from 1:5 to 5:1, more preferably from 1:3 to 3:1. In some embodiments, the first dispersing agent and the second dispersing agent are used in a weight ratio of 1:1. The first dispersing agent can be employed in amounts ranging from 0.1-20% by weight, preferably from 0.5-10% by weight, more preferably from 1-10% by weight, based on the total weight of the formulation. The second dispersing agent is usually present in an amount of from 0.1-20% by weight, preferably from 0.5-10% by weight, more preferably from 1-10% by weight, based on the total weight of the formulation.
[0034] The solid granular formulation can further include a disintegrating agent. The choice and amounts of disintegrating agent are such that the granules break up or disintegrate completely upon contact with water and release the active ingredients into water within minutes for application by spraying. Non-limiting examples of disintegrating agent include lactose, starch, cross-linked polyvinylpyrrolidone, microcrystalline cellulose, cross-linked sodium carboxymethyl cellulose, sodium starch glycolate, soy polysaccharide, sodium sulphate, sodium citrate, polycarboxylates, sodium phenyl sulphonates, and a combination thereof. The disintegrating agent can be employed in amounts ranging from 1% to 40% by weight, preferably from 5% to 35% by weight, more preferably from 10% to 30% by weight, based on the total weight of the formulation.
[0035] In some embodiments, lactose monohydrate is used as the disintegrating agent.
[0036] The solid granular formulation can further include an inert carrier. Suitable inert carrier(s) for use in the formulation include, but not limited to, clay, talc, kaolin, diatomaceous silica, calcite, marble, pumice, sepiolite, dolomite, calcium silicate, magnesium silicate, titanium dioxide, calcium oxide, zinc oxide, calcium carbonate, magnesium carbonate, charcoal, and a combination thereof. Suitable inert carrier(s) for granules include, for example, kaolin, talc, 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 be used in an amount of from about 1% to about 95% by weight, including from about 10% to 90% by weight, from about 20% to 70% by weight, from about 30% to 60% by weight, from about 1% to 30% by weight, from about 2% to 20% by weight, based on a total weight of the formulation.
[0037] In some embodiments, talc is used as the inert carrier.
[0038] In some embodiments, the solid granular formulation can further include one or more of the following excipients: a spreading agent, a colorant, a binder, a pH adjuster, an antifoaming agent, an anti-settling agent, a penetrant, a preservative, an ultraviolet absorbent, an UV ray scattering agent, and a stabilizer.
[0039] According to embodiments of the present invention, the disclosed solid granular formulation 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 active ingredients flumioxazin and diclosulam.
[0040] In some embodiments, the solid granular formulation disclosed herein comprises, based on a total weight of the formulation:
1-85% by weight of flumioxazin;
1-90% by weight of diclosulam;
0.1-20% by weight of sodium alkylnaphthalenesulfonate formaldehyde condensate as a first dispersing agent; and
0.1-20% by weight of sodium lignosulfonate as a second dispersing agent.
[0041] In some embodiments, the solid granular formulation disclosed herein comprises, based on a total weight of the formulation:
1-85% by weight of flumioxazin;
1-90% by weight of diclosulam;
0.1-20% by weight of sodium alkylnaphthalenesulfonate formaldehyde condensate as a first dispersing agent;
0.1-20% by weight of sodium lignosulfonate as a second dispersing agent;
1-40% by weight of a disintegrating agent; and
1-95% by weight of an inert carrier.
[0042] According to embodiments of the present invention, the solid granular formulation disclosed herein can be in the form of water dispersible granules, water disintegrable granules, spheronised granules, a wettable powder, or extruded granules.
[0043] According to an embodiment, the solid granular formulation can be in the form of water dispersible granules (WDG), where the granules are in the size range of 0.075 mm to 3 mm. According to an embodiment, the solid granular formulation can be in the form of water dispersible granules, where the granules are in the size range of 0.075 mm to 2.5 mm. According to an embodiment, the solid granular formulation can be in the form of water dispersible granules, where the granules are in the size range of 0.075 mm to 2.0 mm. According to an embodiment, the solid granular formulation can be in the form of water dispersible granules, where the granules are in the size range of 0.075 mm to 1.5 mm.
[0044] According to an embodiment, the solid granular formulation can be in the form of water disintegrable granules, where the granules are in the size range of 0.075 mm to 6 mm. According to an embodiment, the solid granular formulation can be in the form of water disintegrable granules, where the granules are in the size range of 0.075 mm to 5 mm. According to an embodiment, the solid granular formulation can be in the form of water disintegrable granules, where the granules are in the size range of 0.075 mm to 4 mm. According to an embodiment, the solid granular formulation can be in the form of water disintegrable granules, where the granules are in the size range of 0.075 mm to 3.5 mm. According to an embodiment, the solid granular formulation can be in the form of water disintegrable granules, where the granules are in the size range of 0.075 mm to 1.5 mm
[0045] According to an embodiment, the solid granular formulation can be in the form of spheronised granules, where the granules are in the size range of 0.075 mm to 6 mm. According to an embodiment, the solid granular formulation can be in the form of spheronised granules, where the granules are in the size range of 0.075 mm to 5 mm. According to an embodiment, the solid granular formulation can be in the form of spheronised granules, where the granules are in the size range of 0.075 mm to 4 mm. According to an embodiment, the solid granular formulation can be in the form of spheronised granules, where the granules are in the size range of 0.075 mm to 3.5 mm. According to an embodiment, the solid granular formulation can be in the form of spheronised granules, where the granules are in the size range of 0.075 mm to 1.5 mm
[0046] According to an embodiment, the solid granular formulation can be in the form of extrudeded granules, where the granules are in the size range of 0.075 mm to 8 mm. According to an embodiment, the solid granular formulation can be in the form of extruded granules, where the granules are in the size range of 0.075 mm to 6 mm. According to an embodiment, the solid granular formulation can be in the form of extruded granules, where the granules are in the size range of 0.075 mm to 4 mm. According to an embodiment, the solid granular formulation can be in the form of extruded granules, where the granules are in the size range of 0.075 mm to 3.5 mm. According to an embodiment, the solid granular formulation can be in the form of extruded granules, where the granules are in the size range of 0.075 mm to 1.5 mm.
[0047] According to an embodiment, the solid granular formulation can comprise particles in the size range of 0.1 micron to 30 microns. According to further embodiment, the solid granular formulation can comprise particles in the size range of 0.1 micron to 20 microns. According to further embodiment, the solid granular formulation can comprise particles in the size range of 0.1 micron to 15 microns.
[0048] According to an embodiment, the solid granular formulation can be in the form of wettable powder (WP), where the particles are in the size range of 0.1 micron to 30 microns. According to further embodiment, the wettable powder can comprise particles in the size range of 0.1 micron to 20 microns. According to further embodiment, the wettable powder can comprise particles in the size range of 0.1 micron to 15 microns.
[0049] According to an embodiment, the solid granular formulation in the form of water dispersible granules (WDG) can comprise particles in the size range of 0.1 micron to 30 microns. According to an embodiment, the solid granular formulation in the form of water dispersible granules can comprise particles in the size range of 0.1 micron to 20 microns. According to an embodiment, the solid granular formulation in the form of water dispersible granules can comprise particles in the size range of 0.1 micron to 15 microns. The water dispersible granules disperse into particles in the size range of 0.1 micron to 30 microns, preferably in the size range of 0.1 micron to 15 microns.
[0050] According to an embodiment, the solid granular formulation in the form of water disintegrable granules can comprise particles in the size range of 0.1 micron to 30 microns. According to an embodiment, the solid granular formulation in the form of water disintegrable granules can comprise particles in the size range of 0.1 micron to 20 microns. According to an embodiment, the solid granular formulation in the form of water disintegrable granules can comprise particles in the size range of 0.1 micron to 15 microns. The water disintegrable granules disperse into particles in the size range of 0.1 micron to 30 microns, preferably in the size range of 0.1 micron to 15 microns.
[0051] According to an embodiment, the solid granular formulation in the form of spheronised granules can comprise particles in the size range of 0.1 micron to 30 microns. According to an embodiment, the solid granular formulation in the form of spheronised granules can comprise particles in the size range of 0.1 micron to 20 microns. According to an embodiment, the solid granular formulation in the form of spheronised granules can comprise particles in the size range of 0.1 micron to 15 microns. The spheronised granules disperse into particles in the size range of 0.1 micron to 30 microns, preferably in the size range of 0.1 micron to 15 microns.
[0052] According to an embodiment, the solid granular formulation in the form of extruded granules can comprise particles in the size range of 0.1 micron to 30 microns. According to an embodiment, the solid granular formulation in the form of extruded granules can comprise particles in the size range of 0.1 micron to 20 microns. According to an embodiment, the solid granular formulation in the form of extruded granules can comprise particles in the size range of 0.1 micron to 15 microns. The extruded granules disperse into particles in the size range of 0.1 micron to 30 microns, preferably in the size range of 0.1 micron to 15 microns.
[0053] In addition to the stability of the solid granular formulation, the inventors surprisingly found that the solid granular formulation comprising flumioxazin and diclosulam provides excellent control of weeds and improves crop yield when the particles in the formulation are present in the size range of 0.1 micron to 30 microns. The solid granular formulation comprising particles in the size range of 0.1 micron to 30 microns also enhances the physical nature of the formulation by providing improved suspensibility, dispersibility, instant dispersion of actives on application via soil or foliar route which provides effective control of weeds.
[0054] According to further embodiment, the solid granular formulation in the form of water dispersible granules (WDG) or spheronised granules, is made by various techniques such as spray drying, fluidized bed granulation, disc pelletization, pan granulation, pin agglomerator, spheronizer, freeze drying or combinations thereof. The granules can also be produced by extrusion methods to provide extruded granules.
[0055] Some embodiments describe a process for preparing the solid granular formulation in the form of water dispersible granules (WDG), the process comprising:
milling a blend of flumioxazin, diclosulam, sodium alkylnaphthalenesulfonate formaldehyde condensate, sodium lignosulfonate, a disintegrating agent, an inert carrier and water to provide a wet mix; and
drying the wet mix and optionally sieving the dried mix to remove undersized and oversized granules to obtain the water dispersible granules, wherein the water dispersible granules have a granule size in the range of 0.075 mm to 3 mm.
[0056] Some embodiments describe a process for preparing extruded granules, comprising the steps of:
providing a blend comprising flumioxazin, diclosulam, sodium alkylnaphthalenesulfonate formaldehyde condensate, sodium lignosulfonate, a disintegrating agent and an inert carrier;
milling the blend to obtain a powder mix;
adding water to the powder mix and blending to obtain a dough; and
extruding the dough through an extruder to obtain extruded granules, wherein the extruded granules have granule size in the range of from 0.075 mm to 8 mm and comprise particles in the size range of 0.1 micron to 30 microns.
[0057] Water-dispersible granules (WDG) are used by diluting the granules in a mix tank containing water to make a dispersion which can be subsequently sprayed. The dispersed particles formed on dilution should be no larger than 30 microns in their largest dimension to avoid nozzle clogging or premature settling which results in uneven application of the herbicides. In some embodiments, the water-dispersible granules (WDG) have a diameter in the range of 0.075 mm-3 mm and comprise particles in the size range of 0.1 micron to 30 microns. The water-dispersible granules (WDG) disperse into particles in the size range of 0.1 micron to 30 microns whereby the formulation exhibits improved dispersibility and suspensibility. It is also observed that the efficacy of the water-dispersible granule formulation is particularly higher with the formulation having particles in the size range of about 0.1-30 microns. Thus, the particle size of 0.1-30 microns was found to be important not only in terms of ease of application but also in terms of efficacy.
[0058] Some embodiments describe a process for preparing water disintegrable granules, the process comprising:
milling a blend of flumioxazin, diclosulam, sodium alkylnaphthalenesulfonate formaldehyde condensate, sodium lignosulfonate, a disintegrating agent, an inert carrier and water to provide a wet mix;
drying the wet mix to obtain a microgranule; and
agglomerating the microgranule in an agglomerator to obtain water disintegrable granules, wherein the water disintegrable granules have a granule size in the range of from 0.075 mm to 6 mm and comprise particles in the size range of 0.1 micron to 30 microns.
[0059] Some embodiments describe a process for preparing the solid granular formulation in the form of spheronised granules, the process comprising:
milling a blend of flumioxazin, diclosulam, sodium alkylnaphthalenesulfonate formaldehyde condensate, sodium lignosulfonate, a disintegrating agent, an inert carrier and water to provide a wet mix, wherein the particles are in the size range of 0.1 to 30 microns;
drying the wet mix to obtain a dried mix; and
adding water to the dried mix and blending to obtain a dough, which is extruded through an extruder to obtain extruded granules in a size range of 0.075 mm to 6 mm; or
agglomerating the wet mix or the dried mix obtained above in an agglomerator to obtain a spheronised granular composition in a size range of 0.075 mm to 6 mm.
[0060] The wet mix obtained is dried, for instance in a spray dryer, fluid bed dryer or any suitable granulating equipment, followed by sieving to remove undersized and oversized granules to obtain granules.
[0061] Some embodiments describe a process for preparing a wettable powder (WP), wherein the process involves mixing effective amount of flumioxazin with formulation excipients to obtain a first mixture. The process involves mixing effective amount of diclosulam with formulation excipients to obtain a second mixture. The two mixtures are then mixed using a suitable mass mixer for 30 minutes and passed through an air jet mill to obtain a wettable powder composition with the desired particle size range of 0.1 micron to 30 microns. Alternatively, the wettable powder composition is prepared by mixing effective amount of flumioxazin and diclosulam with formulation excipients using a suitable mass mixer for 30 minutes and then passing through an air jet mill to obtain a wettable powder composition with the desired particle size range of 0.1 micron to 30 microns.
[0062] Some embodiments describe a process for preparing a wettable powder, comprising the steps of:
providing a blend comprising flumioxazin, diclosulam, sodium alkylnaphthalenesulfonate formaldehyde condensate, sodium lignosulfonate, a disintegrating agent and an inert carrier; and
milling the blend to obtain the wettable powder, wherein the wettable powder comprises particles in the size range of 0.1 micron to 30 microns.
[0063] The solid granular formulation of the present invention is useful for both pre-emergence and post-emergence control of weeds. The term "control of weeds" refers to interference with normal growth and development of weeds. 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. In various embodiments, the formulation disclosed herein is suitable for selectively controlling weeds in crops of useful plants such as soybeans, rice, wheat, cereals, oilseed rape, sugar beet, sugarcane, cotton, maize, corn, and vegetables in general. Further, the formulation can exhibit a synergistic herbicidal activity against a broad spectrum of economically important weeds, including broadleaf, sedge, and grass weeds.
[0064] The present invention also provides a method of controlling weeds by applying the solid granular formulation of this invention to a place where weeds are growing or will grow. In some embodiments, the place where weeds are growing or will grow is a crop field. In some embodiments, the crop field is a field of soybeans, corn, or cotton.
[0065] The present invention also provides a method of killing or controlling weeds which comprises the steps of: providing a solid granular formulation of this invention; dispersing the solid granular formulation in water; and applying the resulting dispersion to the weeds or locus of the weeds. In some embodiments, the solid granular formulation is in the form of water dispersible granules (WDG), which disperse rapidly in water and form high quality dispersions in water.
[0066] The foregoing description of the invention has been set merely to illustrate the invention and is not intended to be limiting. Since modifications of the disclosed embodiments incorporating the substance of the invention may occur to persons skilled in the art, the invention should be construed to include everything within the scope of the disclosure.
EXAMPLES
[0067] 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.

Preparation of extruded granules
[0068] Extruded granule formulations were prepared according to the components and amounts shown in Table-1 and Table-2. Examples 1 to 3 are illustrative of the present invention, while Examples 4 to 7 are comparative examples.
Table-1
Ingredients Example 1
(% w/w) Example 2
(% w/w) Example 3
(% w/w)
Diclosulam 10.0 2.0 12.0
Flumioxazin 40.0 8.0 48.0
Sodium alkylnaphthalenesulfonate formaldehyde condensate 5.0 5.0 5.0
Sodium lignosulfonate 5.0 5.0 5.0
Lactose monohydrate 25.0 25.00 25.00
Talc Q.S to 100 Q.S to 100 Q.S to 100

Table-2
Ingredients Example 4
(% w/w) Example 5
(% w/w) Example 6
(% w/w) Example 7
(% w/w)
Diclosulam 10.0 10.0 10.0 10.0
Flumioxazin 40.0 40.0 40.0 40.0
Sodium alkylnaphthalenesulfonate formaldehyde condensate 10.0 0 0 0
Sodium lignosulfonate 0 10.0 0 0
Sodium polycarboxylate 0 0 10.0 0
Potassium polycarboxylate 0 0 0 10.0
Lactose monohydrate 25.0 25.0 25.0 25.0
Talc QS to 100 QS to 100 QS to 100 QS to 100

Manufacturing Process
Step 1: Blending of raw materials
Diclosulam, flumioxazin, dispersing agents, disintegrating agent and carrier were charged in a blender and dry-mixed to get uniform blend.
Step 2: Grinding of above blend
The above blend was milled using an air jet milling to get desired particle size (D50: 10 micron).
Step 3: Mixing of ground powder
The above milled powder was further blended in a blender to get homogenous powder.
Step 4: Preparation of dough
The above homogenous powder was transferred to a sigma mixer and required quantity of water was added and mixed to obtain uniform dough suitable for extrusion.
Step 5: Extrusion and drying
The above dough was passed through an extruder to get extruded granules which were then dried to get dry granules.
Step 6: Sieving of dried granules:
The dried granules were passed through a sieve to get extruded granules.
Stability Study (Extruded granules)
[0069] The extruded granules of Examples 1 to 3 and the Comparative Examples 4 to 7 were subjected to accelerated storage stability study and the results are presented in Table 3.

Table 3
Parameter Example 1 Example 2 Example 3
Initial At 54±2 ?C
(14 days) Initial At 54±2 ?C
(14 days) Initial At 54±2 ?C
(14 days)
Description Light brown granules Light brown granules Light brown granules Light brown granules Light brown granules Light brown granules
Diclosulam content (%) 10.20 10.11 2.05 2.03 12.20 12.10
Flumioxazin content (%) 40.20 40.10 8.02 8.01 48.10 48.05
Wettability (Sec.) 10 8 8 7 6 8
Wet sieve (% retention on 75 micron test sieve) 0.01 0.02 0.02 0.02 0.02 0.03
Degree of Dispersion (%) 100.4 100.1 99.8 99.5 99.3 99.6
Suspensibility (%) Diclosulam: 100.31
Flumioxazin: 97.40 Diclosulam: 99.78
Flumioxazin: 97.12 Diclosulam: 98.90
Flumioxazin: 97.80 Diclosulam: 98.10
Flumioxazin: 97.10 Diclosulam: 99.40
Flumioxazin: 98.30 Diclosulam: 99.78
Flumioxazin: 97.21
Persistent Foam (ml after one min.) 2 4 5 4 7 7
pH (1% aq. suspension) 6.61 6.38 6.61 6.38 6.61 6.38
Attrition resistance (%) 99.96 99.92 99.96 99.92 99.96 99.92
Dustiness – Dust (mg) 0.1 0.1 0.1 0.1 0.1 0.1
Table 3 - continued

Parameter Example 4 Example 5 Example 6
Initial At 54±2 ?C
(14 days) Initial At 54±2 ?C
(14 days) Initial At 54±2 ?C
(14 days)
Description Light brown granules Light brown granules Light brown granules Light brown granules Light brown granules Light brown granules
Diclosulam content (%) 10.24 10.02 10.11 10.02 10.07 9.56
Flumioxazin content (%) 40.20 40.10 40.09 40.01 40.02 39.59
Wettability (Sec.) 14 20 9 8 22 27
Wet sieve (% retention on 75 micron test sieve) 0.02 0.69 0.03 0.66 0.01 0.54
Degree of Dispersion (%) 97.90 80.01 96.22 79.22 98.50 60.56
Suspensibility (%) Diclosulam: 98.31
Flumioxazin: 96.40 Diclosulam: 77.52
Flumioxazin: 75.23 Diclosulam: 98.31
Flumioxazin: 96.40 Diclosulam: 76.52
Flumioxazin: 73.23 Diclosulam: 98.31
Flumioxazin: 98.40 Diclosulam: 70.31
Flumioxazin: 64.40
Persistent Foam (ml after one min.) 6 10 6 8 22 34
pH (1% aq. suspension) 6.90 6.87 7.10 7.15 8.61 8.69
Attrition resistance (%) 98.35 98.52 98.35 98.00 99.96 99.96
Dustiness – Dust (mg) 0.3 0.3 0.1 0.2 0.1 0.1

Table 3 - continued

Parameter Example 7
Initial At 54±2 ?C (14 days)
Description Light brown granules Light brown granules
Diclosulam content (%) 10.11 9.92
Flumioxazin content (%) 40.07 39.67
Wettability (Sec.) 21 20
Wet sieve (% retention on 75 micron test sieve) 0.02 0.4
Degree of Dispersion (%) 98.2 74.01
Suspensibility (%) Diclosulam: 98.87
Flumioxazin: 96.10 Diclosulam:67.98
Flumioxazin: 65.23
Persistent Foam (ml after one min.) 32 10
pH (1% aq. suspension) 8.4 8.89
Attrition resistance (%) 98.12 98..15
Dustiness – Dust (mg) 0.3 0.4

The results in Table 3 illustrate that the extruded granules containing both sodium alkylnaphthalenesulfonate formaldehyde condensate and sodium lignosulfonate have significantly improved product storage performance, wherein the suspensibility and degree of dispersion properties before storage and after storage are both 97% or more (Examples 1 to 3), which properties are not possessed by the extruded granules containing none or only one of said dispersing agents (Examples 4 to 7).
Preparation of water-dispersible granules (WDG)
[0070] Water-dispersible granule (WDG) formulations were prepared according to the components and amounts shown in Table 4.
Table 4
Ingredients Example 8
(% w/w)
Diclosulam 10.0
Flumioxazin 40.0
Sodium alkylnaphthalenesulfonate formaldehyde condensate 5.0
Sodium lignosulfonate 5.0
Lactose monohydrate 25.0
Talc Q.S to 100

Manufacturing Process
Step 1: Blending of raw materials
Diclosulam (10.5 part), flumioxazin (40.4 part), sodium alkylnaphthalenesulfonate formaldehyde condensate (5 part), sodium lignosulfonate (5 part), lactose monohydrate (25 part), talc (14.1 part) and water (to give 50% slurry concentration) were charged in a mixing vessel and mixed to provide a slurry.
Step 2: Grinding of above slurry
Above slurry was subjected to bead milling to get average particle size below 3 microns.
Step 3: Spray drying
The above milled slurry was spray dried using a spray dryer to get spray dried granules (water-dispersible granules) having granules size less than 3 mm.
Stability Study (Water-dispersible granules)
[0071] The water-dispersible granules of Example 8 were subjected to accelerated storage stability study and the results are presented in Table 5.
Table 5

Parameter Example 8
Initial At 54±2 ?C
(14 days)
Description Light brown granules Light brown granules
Diclosulam content (%) 10.11 10.12
Flumioxazin content (%) 40.19 40.04
Wettability (Sec.) 8 10
Wet sieve (% retention on 75-micron test sieve) 0.02 0.05
Degree of Dispersion (%) 99.22 97.12
Suspensibility (%) Diclosulam: 98.32
Flumioxazin: 97.66 Diclosulam: 97.53
Flumioxazin: 96.21
Persistent Foam (ml after one min.) 2 4
pH (1% aq. suspension) 6.77 6.53
Attrition resistance (%) 99.81 98.22
Dustiness – Dust (mg) 0.1 0.1

FIELD STUDY:
[0072] The following are abbreviations that have been used in this specification.
· WDG - Water dispersible granules
· % Weed Control
· g.a.i. ha. - gram active ingredient per hectare
· DAS - Days after spray
· DAA - Days after application
Field experiment:
[0073] Field experiment was conducted in the Madhya Pradesh (4 trials), Gujarat (1 trial) & Maharashtra (2 trials) in the farmers field where the soil is heavy black soil. The experiment was laid-out in randomized block design (RBD) comprising of eight treatments including one untreated control. As per treatments, individual applications of Flumioxazin 50 SC and Diclosulam 84 WDG and also Flumioxazin 40% + Diclosulam 10% WDG as pre-emergence within 0-2 days after sowing. The plastic sheets were used on both side of the plot to avoid drifting of spray droplets in adjoining plots.
[0074] In the current study, the observed weed flora spectrum at Madhya Pradesh, Gujarat and Maharashtra locations comprised of grasses: Echinocloa colona, Dinebra retroflexa, Cyanotis axillaris, broad leaf weeds: Commelina diffusa, Commelina benghalensis, Acalypha indica, Alternenthera sessilis, Amaranthus viridis, Parthenium hysterophorus, Trianthema portulacastrum, Portulaca oleracea, Ageratum conyzoides, Phyllanthus maderaspatensis and Celosia argentea (Table 6).
Experiment Details: Madhya Pradesh
Location Indore/Ujjain
Season Kharif 2023
Year 2023
Crop Soybean
Variety RBS-24/9560/1035/2034
Soil type Black Heavy soil
Irrigated/Rainfed Rainfed
No of treatments 6
Replication 3
Plot size 50 sqm
Date of Sowing 25/06/2023 to 29/06/2023
Date of Application 27/06/2023 to 30/06/2023 (0 to 2 DAS)
Type of Sprayer/Nozzle Knapsack Sprayer/Hollow Cone Nozzle

Experiment Details: Gujarat
Location Bhavnagar
Season Kharif 2023
Year 2023
Crop Soybean
Variety KDS-726
Soil type Black Heavy soil
Irrigated/Rainfed Rainfed
No of treatments 6
Replication 3
Plot size 50 sqm
Date of Sowing 29/06/2023
Date of Application 30/06/2023
Type of Sprayer/Nozzle Knapsack Sprayer/Hollow Cone Nozzle

Experiment Details: Maharashtra
Location Nanded
Season Kharif 2023
Year 2023
Crop Soybean
Variety KDS-726/992
Soil type Black Heavy soil
Irrigated/Rainfed Rainfed
No of treatments 6
Replication 3
Plot size 50 sqm
Date of Sowing 05/07/2023
Date of Application 06/07/2023
Type of Sprayer/Nozzle Knapsack Sprayer/Hollow Cone Nozzle

Observations recorded
[0075] Species wise weed control over untreated (visual observation) recorded at 30 and 45 days after application of herbicide and were expressed as % weed control.
Table: 6 Weeds observed in the trial plot in Madhya Pradesh, Gujarat and Maharashtra locations
EPPO Code Scientific Name
ECHOCO Echinocloa colona
DIMRE Dinebra retroflexa
COMEDI Commelina diffusa
COMBE Commelina benghalensis
ACCIN Acalypha indica
ALRSE Alternenthera sessilis
AMAVI Amaranthus viridis
PTNHY Parthenium hysterophorus
TRTPO Trianthema portulacastrum
POROL Portulaca oleracea
CYBAX Cyanotis axillaris
AGECO Ageratum conyzoides
PLYMP Phyllanthus maderaspatensis
CEOAR Celosia argentea

Experiment Results:
A. Bio-efficacy Results:
[0076] The application of composition of Flumioxazin 40% + Diclosulam 10% WDG @ 125 (100+25) GAI/ha (Treatment 1) as per the embodiment of present invention, was highly effective in controlling different weed species viz., ECHOCO, COMEDI, COMEBE, ACCIN, ALRSE, AMAVI at 30 & 45 days after application and significantly superior than individual treatments i.e., Flumioxazin 50 SC @ 100 GAI/ha (Treatment 4) and treatment 5 (T5) Diclosulam 84 WDG @ 25 GAI/ha (Table 7).
[0077] It is seen that Treatments T1 which comprises of a composition of Flumioxazin 40% + Diclosulam 10% WDG as per the embodiment of the present invention (Flumioxazin 40% + Diclosulam 10% WDG @ 125 (100+25) GAI/ha) exhibited higher % weed control at 30 & 45 days after application and also showed better percent weed control when compared to individual treatments of Flumioxazin 50 SC @ 100 GAI/ha (T4) and Diclosulam 84 WDG @ 25 GAI/ha ((T5). While comparing the similar strength of the individual treatments of Flumioxazin 50 SC (T4) and Diclosulam 84 WDG (T5) corresponding to composition of Flumioxazin 40% + Diclosulam 10% WDG @ 125 (100+25) GAI/ha (T1) expressed 90.47, 86.51, 89.11, 88.37, 89.85 & 83.42 per cent weed control at 30 Days after application and 81.93, 76.97, 89.30, 81.38, 81.47 & 79.31 per cent weed control at 45 Days after replication against grassy weed ECHOCO and Broad leaf weeds COMEDI, COMEBE, ACCIN, ALRSE, AMAVI, respectively which was statistically significant (when analysed through DMRT) over the individual treatments like Flumioxazin 50 SC (T4) which exhibited 80.84, 79.56, 80.04, 81.97, 81.92 & 77.50 per cent weed control at 30 Days after application and 71.71, 68.37, 71.75, 74.81, 76.52 & 69.07 per cent weed control at 45 Days after application against Grassy weed ECHOCO and Broad leaf weed COMEDI, COMEBE, ACCIN, ALRSE, AMAVI, respectively. Diclosulam 84 WDG (T5) exhibited 76.37, 74.67, 75.84, 79.82, 79.48 & 73.66 per cent weed control at 30 Days after Application and 66.42, 64.53, 69.86, 71.38, 73.87 & 66.60 per cent weed control at 45 Days after application against Grassy weed ECHOCO and Broad leaf weed COMEDI, COMEBE, ACCIN, ALRSE, AMAVI respectively. It is clear from the results that synergistic effect of Flumioxazin 40% + Diclosulam 10% WDG @ 125 (100+25) GAI/ha (T1) is attributed to the effectiveness of the composition as per the embodiments of the invention, where both actives are present in a single composition at a specific concentration. The enhanced efficacy is further attributed to the form of the composition, i.e. Water dispersible granule (WDG) composition as shown in the present study.
[0078] It is observed from Table 8 that the application of Flumioxazin 40% + Diclosulam 10% WDG @ 125 (100+25) GAI/ha (T1) as per the embodiment of present invention, was highly effective in controlling different weed species ECHOCO, DIMRE, TRTPO, POROL & ACCIN at 30 & 45 days after application and significantly superior than individual treatments i.e., Flumioxazin 50 SC @ 100 GAI/ha (T4) and Diclosulam 84 WDG @ 25 GAI/ha (T5).
[0079] It is seen that Treatments T1, which comprises of a composition of Flumioxazin 40% + Diclosulam 10% WDG as per the embodiment of the present invention exhibited higher % weed control at 30 & 45 days after application and showed better per cent weed control when compared to individual treatment Flumioxazin 50 SC @ 100 GAI/ha (T4) and treatment 5, Diclosulam 84 WDG @ 25 GAI/ha. While comparing the similar strength of the individual treatments Flumioxazin 50 SC (T4) and Diclosulam 84 WDG (T5) corresponding to composition of Flumioxazin 40% + Diclosulam 10% WDG @ 125 (100+25) GAI/ha (T1) expressed 96.29, 84.29, 91.07, 91.30 & 86.90% weed control at 30 DAA and 85.59, 77.58, 80.20, 85.53 & 82.56 per cent weed control at 45 days after application against grassy weeds, ECHOCO, DIMRE and broad leaf weeds TRTPO, POROL & ACCIN, respectively, which was statistically significant (when analysed through DMRT) over the individual treatments like T4 (Flumioxazin 50 SC) which exhibited 87.36, 75.61, 84.29, 83.69 & 79.43% weed control at 30 Days after application and 78.85, 67.23, 78.61, 76.63 & 69.63 per cent weed control at 45 Days after application against ECHOCO, DIMRE, TRTPO, POROL & ACCIN, respectively, and T5 (Diclosulam 84 WDG) exhibited 92.12, 69.51, 77.45, 77.53 & 73.35 per cent weed control at 30 Days after application and 75.69, 63.24, 67.53, 70.75 & 64.14% weed control at 45 Days after application against ECHOCO, DIMRE, TRTPO, POROL & ACCIN, respectively. The effective result of T1 is attributed to the synergistic effect of the composition as per the embodiments of the invention, where both actives are present in a single composition at a specific concentration. The enhanced efficacy is further attributed to the form of the composition, i.e. Water dispersible granule (WDG) composition formulated as per the embodiment of the present invention and as shown in the present study.
[0080] It is observed from Tables 9a & 9b that the application of Flumioxazin 40% + Diclosulam 10% WDG @ 125 (100+25) GAI/ha (T1) as per the embodiment of present invention, was highly effective in controlling different weed species ECHOCO, CEOAR, COMEBE, PTNHY, ACCIN, AMAVI, DIMRE, CYBAX, AGECO & PLYMP at 30 & 45 days after application and significantly superior than individual treatments i.e.,) Flumioxazin 50 SC @ 100 GAI/ha (T4) and Diclosulam 84 WDG @ 25 GAI/ha (T5).
[0081] It is seen that Treatments T1, which comprises of a composition of Flumioxazin 40% + Diclosulam 10% WDG as per the embodiment of the present invention exhibited higher % weed control at 30 & 45 days after application and also showed better % weed control when compared to individual treatment Flumioxazin 50 SC @ 100 GAI/ha (T4) and Diclosulam 84 WDG @ 25 GAI/ha 9T5). While comparing the similar strength of the individual treatments Flumioxazin 50 SC (T4) and Diclosulam 84 WDG (T5) corresponding to a composition of Flumioxazin 40% + Diclosulam 10% WDG @ 125 (100+25) GAI/ha as treatment 1 (T1) expressed 84.04, 91.95, 90.68, 89.56, 90.05, 91.09, 91.86, 75.45, 91.72 & 92.14 per cent weed control at 30 DAA and 73.01, 81.86, 73.54, 77.65, 77.45, 81.14, 83.90, 68.13, 83.57 & 82.67 per cent weed control at 45 Days after application against ECHOCO, CEOAR, COMEBE, PTNHY, ACCIN, AMAVI, DIMRE, CYBAX, AGECO & PLYMP, respectively, which was statistically significant (when analysed through DMRT) over the individual treatments like T4 (Flumioxazin 50 SC) which exhibited 70.10, 77.14, 71.23, 74.76, 67.65, 75.34, 74.47, 58.52, 75.53 & 74.80 per cent weed control at 30 DAA and 61.53, 64.81, 56.75, 65.46, 60.35, 63.43, 66.77, 45.36, 64.44 & 66.43 per cent weed control at 45 DAA against ECHOCO, CEOAR, COMEBE, PTNHY, ACCIN, AMAVI, DIMRE, CYBAX, AGECO and PLYMP, respectively & T5 (Diclosulam 84 WDG) exhibited 65.65, 76.99, 66.93, 71.35, 65.50, 71.17, 72.39, 54.06, 73.15 & 74.58% weed control at 30 DAA and 58.80, 63.36, 52.35, 60.90, 55.46, 58.33, 63.40, 43.14, 59.14 & 64.10 per cent weed control at 45 Days after application against ECHOCO, CEOAR, COMEBE, PTNHY, ACCIN, AMAVI, DIMRE, CYBAX, AGECO & PLYMP, respectively. The effective result of Flumioxazin 40% + Diclosulam 10% WDG @ 125 (100+25) GAI/ha (T1) is attributed to the synergistic effect of the composition as per the embodiments of the invention, where both actives are present in a single composition at a specific concentration. The enhanced efficacy is further attributed to the form of the composition, i.e. Water dispersible granule (WDG) composition formulated as per the embodiment of the present invention and as shown in the present study.

Table 7: Synergistic effect of WDG composition comprising Flumioxazin & Diclosulam for controlling weeds in Soybean at as Pre-emergence application at Madhya Pradesh location (Average of four trials)
S. No Treatments Dose
GAI/ha Weed control (%) at 30 Days after application (Average of 4 locations) Weed control (%) at 45 Days after application (Average of 4 locations)
ECHOCO* COMEDI COMEBE ACCIN ALRSE AMAVI ECHOCO COMEDI COMEBE ACCIN ALRSE AMAVI
1 Flumioxazin 40% + Diclosulam 10% WDG 125 90.47 b 86.51 c 89.11c 88.37 c 89.85 c 83.42 cd 81.93 c 76.97 c 79.30 c 81.38 cd 81.47 b 79.31 b
2 Flumioxazin 40% + Diclosulam 10% WDG 137.5 94.07 a 90.49 b 92.51 b 92.33 b 92.63 bc 87.89 bc 86.87 b 82.61 b 85.19 b 84.97 b 85.8 a 86.69 a
3 Flumioxazin 40% + Diclosulam 10% WDG 150 96.05 a 93.66 a 95.67 a 96.01 a 95.46 ab 95.86 a 90.68 a 86.23 a 89.31 a 88.61 a 88.82 a 89.04 a
4 Flumioxazin 50% SC 100 80.84 d 79.56 e 80.04 e 81.97 d 81.92 de 77.50 de 71.71 f 68.37 d 71.75 d 74.81 e 76.52 cd 69.07 c
5 Diclosulam 84% WDG 25 76.37 e 74.67 f 75.84 f 79.82 d 79.48 e 73.66 e 66.42 g 64.53 e 69.86 d 71.38 f 73.87 d 66.6 c
6 Untreated Control -- 0.00 f 0.00 g 0.00 g 0.00 f 0.00 f 0.00 f 0.00 h 0.00 f 0.00 e 0.00 g 0.00 e 0.00 d
* EPPO codes of Weed species given in Table 6; GAI/ha: Gram active ingredient/hectare; Mean data (weed control) with different grouping letter (alphabets) in a column are significantly different at (P < 0.05) by Duncan’s multiple range test DMRT) indicative of the effectiveness of the composition over the individual treatment

Table.8: Synergistic effect of WDG composition comprising Flumioxazin & Diclosulam for controlling weeds in Soybean at as Pre-emergence application at Gujarat location
Sl.No Treatments GAI/ha Product /ha Weed control (%) at 30 Days after application Weed control (%) at 45 Days after application
ECHOCO* DIMRE TRTPO POROL ACCIN ECHCO DIMRE TRTPO POROL ACCIN
1 Flumioxazin 40% + Diclosulam 10% WDG 125 250 96.29 b 84.29 b 91.07 b 91.30 bcd 86.90 bc 85.59 b 77.58 b 80.2 cd 85.53 b 82.56 bc
2 Flumioxazin 40% + Diclosulam 10% WDG 137.5 275 100.00 a 90.18 a 94.45 a 93.83 abc 91.16 ab 92.07 a 84.37 a 88.51 ab 90.22 a 87.22 ab
3 Flumioxazin 40% + Diclosulam 10% WDG 150 300 100.00 a 93.90 a 96.61 a 95.1 ab 95.58 a 95.11 a 87.07 a 92.66 a 92.28 a 90.79 a
4 Flumioxazin 50% SC 100 200 87.36 c 75.61 c 84.29 d 83.69 e 79.43 d 78.85 d 67.23 c 78.61 d 76.63 c 69.63 d
5 Diclosulam 84% WDG 25 29.76 92.12 c 69.51 d 77.45 e 77.53 f 73.35 e 75.69 d 63.24 c 67.53 e 70.75 d 64.14 d
6 Untreated Control -- -- 0.00 d 0.00 c 0.00 f 0.00 g 0.00 f 0.00 e 0.00 d 0.00 f 0.00 e 0.00 e

* EPPO codes of Weed species given in Table 6; GAI/ha: Gram active ingredient/hectare; Mean data (weed control) with different grouping letter (alphabets) in a column are significantly different at (P < 0.05) by Duncan’s multiple range test DMRT) indicative of the effectiveness of the composition over the individual treatment.

Table. 9a: Synergistic effect of WDG composition comprising Flumioxazin & Diclosulam for controlling weeds in Soybean at as Pre-emergence application at Maharashtra location (Average of two trials)
S.No Treatments GAI/ha Product /ha Weed control (%) at 30 Days after application (Average of 2 locations)
ECHOCO* CEOAR COMEBE PTNHY ACCIN AMAVI DIMRE CYBAX AGECO PLYMP
1 Flumioxazin 40% + Diclosulam 10% WDG 125 250 84.04 ab 91.95 ab 90.68 abc 89.56 bc 90.05 abc 91.09 abc 91.86 ab 75.45 a 91.72 a 92.14 a
2 Flumioxazin 40% + Diclosulam 10% WDG 137.5 275 88.48 ab 93.63 ab 92.19 ab 93.05 b 92.50 ab 93.45 ab 93.94 a 76.58 a 92.21 a 94.10 a
3 Flumioxazin 40% + Diclosulam 10% WDG 150 300 90.91 a 95.14 a 93.41 a 95.65 a 94.65 a 95.54 a 96.02 a 77.21 a 94.59 a 96.19 a
4 Flumioxazin 50% SC 100 200 70.10 c 77.14 de 71.23 e 74.76 de 67.65 ef 75.34 ef 74.47 cd 58.52 cd 75.53 bc 74.80 c
5 Diclosulam 84% WDG 25 29.76 65.65 c 76.99 de 66.93 e 71.35 de 65.50 ef 71.17 f 72.39 d 54.06 d 73.15 c 74.58 c
6 Untreated Control -- -- 0.00 d 0.00 f 0.00 f 0.00 f 0.00 g 0.00 g 0.00 e 0.00 e 0.00 d 0.00 d
* EPPO codes of Weed species given in Table 6; GAI/ha: Gram active ingredient/hectare; Mean data (weed control) with different grouping letter (alphabets) in a column are significantly different at (P < 0.05) by Duncan’s multiple range test DMRT) indicative of the effectiveness of the composition over the individual treatment.

Table. 9b: Synergistic effect of WDG composition comprising Flumioxazin & Diclosulam for controlling weeds in Soybean at as Pre-emergence application at Maharashtra location (Average of two trials)
S. No Treatments GAI/ha Product /ha Weed control (%) at 45 Days after application (Average of 2 locations)
ECHCG EOAR COMEBE PTNHY ACCIN AMAVI DIMRE CYBAX AGECO PLYMP
1 Flumioxazin 40% + Diclosulam 10% WDG 125 250 73.01 ab 81.86 ab 73.54 abc 77.65 abc 77.45 ab 81.14 abc 83.90 a 68.13 a 83.57 a 82.67ab
2 Flumioxazin 40% + Diclosulam 10% WDG 137.5 275 77.77 a 84.29 a 75.46 ab 81.23ab 78.55 ab 82.12 ab 85.46 a 69.04 a 84.37 a 83.93 ab
3 Flumioxazin 40% + Diclosulam 10% WDG 150 300 80.97 a 87.42 a 79.80 a 86.57 a 85.70 a 85.93 a 87.11 a 70.86 a 86.13 a 87.43 a
4 Flumioxazin 50% SC 100 200 61.53 cd 64.81 c 56.75 d 65.46 d 60.35 c 63.43 ef 66.77 b 45.36 c 64.44 cd 66.43 d
5 Diclosulam 84% WDG 25 29.76 58.80 d 63.36 c 52.35 e 60.90 d 55.46 c 58.33 f 63.40 b 43.14 c 59.14 d 64.10 d
6 Untreated Control -- -- 0.00 e 0.00 d 0.00 f 0.00 e 0.00 d 0.00 g 0.00 c 0.00 d 0.00 e 0.00 e
* EPPO codes of Weed species given in Table 6; GAI/ha: Gram active ingredient/hectare; Mean data (weed control) with different grouping letter (alphabets) in a column are significantly different at (P < 0.05) by Duncan’s multiple range test DMRT) indicative of the effectiveness of the composition over the individual treatment.

[0082] In the current study, it was observed that the composition of Flumioxazin 40%+Diclosulam 10% WDG @ 125 (100+25) GAI/ha recorded significantly superior efficacy (Tables 7, 8 & 9) against different weed flora spectrum comprised of grasses: Echinocloa colona, Dinebra retroflexa, Cyanotis axillaris, and broad leaf weeds: Commelina benghalensis, Commelina diffusa, Acalypha indica, Alternenthera sessilis, Amaranthus viridis, Parthenium hysterophorus, Trianthema portulacastrum, Portulaca oleracea, Ageratum conyzoides, Celosia argentea, Phyllanthus maderaspatensis. at 30 and 45 days after application at all the locations of Madhya Pradesh, Gujarat and Maharashtra from 6 trials than individual product Flumioxazin 50 SC @ 100 g ai/ha and Diclosulam 84 WDG @ 25 g ai/ha. No adverse effects on soybean crops were observed at any of the tested locations up to 30 days after application when the product was used as a pre-emergence treatment.
[0083] Overall, the present invention provides a composition comprising two herbicidal active ingredients that, at specific w/w ratios and various doses, exhibit an unexpected and remarkable synergistic ability to eliminate the growth of weeds and unwanted vegetation. Notably, while effectively targeting weeds, this composition does not adversely impact the agronomic characteristics of crop plants. Furthermore, it is non-phytotoxic to crops at recommended doses, making it an attractive and viable alternative to the use of individual herbicides.

INDUSTRIAL APPLICABILITY AND ECONOMICAL SIGNIFICANCE
[0084] The synergistic herbicidal composition, wherein Flumioxazin and Diclosulam are mixed in a distinctive strength in the formulated product, can be considered as a novel invention. The present formulation of two herbicides (in the distinctive strength as mentioned above) provides better performance (bioefficacy) than its individual components due to the following aspects: a) The present formulation is effective against a variety of weeds b) The formulation was found stable for two years. c) Both the individual molecules i.e. Flumioxazin and Diclosulam belong to different chemical groups and have different mode of actions, which make them ideal combination partners for using in Integrated Weed Management practices as well as resistance management strategies. d) There has not been any formulation commercialized in India based on Flumioxazin and Diclosulam. e) The present formulation exhibits its bioefficacy on soybean and other crops. f) The Indian Farmers come across with a lot of economic losses due to many types of weed problems in their crops, which could be tackled through this formulation. Therefore, this formulation can be considered worthy to farmers earning better profits from their farm outputs.
,CLAIMS:1. A solid granular formulation comprising, based on a total weight of the formulation:
1-85% by weight of flumioxazin;
1-90% by weight of diclosulam;
0.1-20% by weight of sodium alkylnaphthalenesulfonate formaldehyde condensate as a first dispersing agent; and
0.1-20% by weight of sodium lignosulfonate as a second dispersing agent; wherein flumioxazin and diclosulam are present in a weight ratio of from 1:20 to 20:1 and wherein the formulation comprises particles in a size range of from 0.1 micron to 30 microns.

2. The formulation as claimed in claim 1, wherein a weight ratio of the first dispersing agent to the second dispersing agent is 1:5 to 5:1.

3. The formulation as claimed in claim 1, further comprising:
1-40% by weight of a disintegrating agent; and
1-95% by weight of an inert carrier.

4. The formulation as claimed in claim 1 is in the form of water-dispersible granules, water disintegrable granules, spheronised granules, extruded granules, wettable powder.

5. The formulation as claimed in claim 4, wherein the water-dispersible granules have a granule size in the range of from 0.075 mm to 3 mm, and comprise particles in the size range of from 0.1 micron to 30 microns.

6. The formulation as claimed in claim 4, wherein the wettable powder has a particle size in the range of from 0.1 micron to 30 microns.
7. The formulation as claimed in claim 4, wherein the water disintegrable granules have a granule size in the range of from 0.075 mm to 6 mm, and comprise particles in the size range of from 0.1 micron to 30 microns.

8. The formulation as claimed in claim 4, wherein the spheronised granules have a granule size in the range of from 0.075 mm to 6 mm, and comprise particles in the size range of from 0.1 micron to 30 microns.

9. The formulation as claimed in claim 4, wherein the extruded granules have a granule size in the range of from 0.075 mm to 8 mm, and comprise particles in the size range of from 0.1 micron to 30 microns.

10. The formulation as claimed in claim 1, comprising:
1-85% by weight of flumioxazin;
1-90% by weight of diclosulam;
0.1-20% by weight of sodium alkylnaphthalenesulfonate formaldehyde condensate as a first dispersing agent;
0.1-20% by weight of sodium lignosulfonate as a second dispersing agent;
1-40% by weight of a disintegrating agent; and
1-95% by weight of an inert carrier wherein flumioxazin and diclosulam are present in a weight ratio of from 1:20 to 20:1 and wherein the formulation comprises particles is in a size range of from 0.1 micron to 30 microns.

11. The formulation as claimed in claim 3 or claim 10, wherein the disintegrating agent is selected from lactose, starch, cross-linked polyvinylpyrrolidone, microcrystalline cellulose, cross-linked sodium carboxymethyl cellulose, sodium starch glycolate, soy polysaccharide, sodium sulphate, sodium citrate, polycarboxylates, sodium phenyl sulphonates, and a combination thereof.

12. The formulation as claimed in claim 3 or claim 14, wherein the inert carrier is selected from clay, talc, kaolin, diatomaceous silica, calcite, marble, pumice, sepiolite, dolomite, calcium silicate, magnesium silicate, titanium dioxide, calcium oxide, zinc oxide, calcium carbonate, magnesium carbonate, charcoal, and a combination thereof.

13. The formulation as claimed in claim 1, further comprising one or more of the following excipients: a spreading agent, a colorant, a binder, a pH adjuster, an antifoaming agent, an anti-settling agent, a penetrant, a preservative, an ultraviolet absorbent, an UV ray scattering agent, and a stabilizer.