Description:TECHNICAL FIELD
[0001] The present invention relates to herbicides. In particular, the present invention relates to a ternary herbicidal composition, which provides synergistic control of weeds in cultivated crops and on non-crop area.

BACKGROUND
[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] Weed infestation is a major problem in the productivity of various crop plants such as wheat, triticale, sugarcane, soybean, rice, barley, oats, rye etc. Weeds are undesirable due to competitive and allelopathic behavior. A weed is a plant species which grows as a wild plant and generally has no aesthetic and economic values. Weeds compete with the cultivated crop for nutrients, sunlight and moisture. Some weeds may also release compounds that are toxic to crop growth.
[0004] Rice is commonly consumed as food around the world. Rice is the seed of the grass species Oryza sativa (Asian rice) or, less commonly, Oryza glaberrima (African rice). There are many varieties of rice, and culinary preferences tend to vary regionally. In 2020, world production of rice was 756.7 million metric tons (834.1 million short tons), led by China and India with a combined 52% of this total. Other major producers were Bangladesh, Indonesia and Vietnam. As a cereal grain, domesticated rice is the most widely consumed staple food for over half of the world's human population, particularly in Asia and Africa. Weed infestation is one of the major impediments to rice yield, besides disease, pest and climatic influences. Weeds consume available nutrients and compete for space and sunlight with crop plants. They compete for available nitrogen supply and light during the early growth stage. Therefore, uncontrolled growth of weed plants in rice crop is most important factor for reduction in rice yield. To help combat this problem, researchers in the field of synthetic chemistry have produced an extensive variety of chemicals and chemical formulations effective in the control of such unwanted plants called weeds. Chemical herbicides of many types have been reported in the literature and a large number are in commercial use.
[0005] Weeds are considered as a major constraint for higher production of rice. In recent years, a number of chemicals having herbicidal activity have been used to control weeds in rice fields. The most commonly used herbicides in rice fields to manage the weeds are Anilofos, Bentazone, Butachlor, Carfentrazone ethyl, Cyhalofop butyl, 2,4-D, Fenoxaprop-p-ethyl, Flucetasulfuron, Metamifop, Metsulfuron methyl, Oxadiargyl, Penoxsulam, Pertilachlor, Pyrazosulfuron ethyl, Propanil, Azimsulfuron, Bispyribac sodium, Bensulfuron methyl, Chlorimuron ethyl, Pendimethalin, Ethoxysulfuron, Ethoxysulfuron, and Triafamone etc.
[0006] Since weeds are diversified in kind viz. grassy weeds, broad leaf weeds, sedges and vines, and their emergence extends over a long period of time, the herbicidal effects of conventional single herbicidal agents are restricted in general as most of the available herbicides can control only one type of weed i.e. either grassy weeds or broad leaf weeds, having affectivity when applied before germination of weeds or after germination of weeds. Some of the weed species, like grassy weed such as Echinochloa colonum, Echinochloa crusgalli, Eleusine indica, Leptochloa chinensis, Barnyard grass, Paspalum dilatatum, Digiteria, Dactyloctenium, Panicum repens; broad leaf weed such as Eclipta alba, Marsilea quadrifolia, Ludwigia parviflora, Monochoria vaginalis, Sphenoclcea zeylanica, Sphenoclea pongatium, Digera arevensis, Phyllanthus niruri, Ammania baccifera, Alternanthera philoxeroides, Commelina benghalinsis, Bergia capensis, Caesulia axillaris, and sedges weeds such as Cyperus difformis, Cyperus iria, Cyperus rotundus, Fimbristylis miliacea in rice crop are difficult to kill by single or even mixtures of two herbicidal active ingredients. Moreover, most of the herbicides do not protect the germination of weeds after killing of standing weeds, therefore, new weeds again emerge out and start competing with the cultivated crop plants.
[0007] Compositions of herbicidal combinations offer significant advantages over individual applications including improved and extended weed control, reduced herbicide rates and application costs, shorter contact times for improved results in flowing water, less stringent use restrictions, improved selectivity, improved spectrum of weeds controller reduced cost and reduced residue problems. In some cases, the herbicidal active ingredients have been shown to be more effective in combination than when applied individually. However, identifying appropriate herbicide combinations having chemical and physical stability while combining two or three herbicidal actives remains a challenge.
[0008] In view of such situation, it is desirable to develop a herbicidal composition having broad herbicidal activity spectrum against a wide variety of weeds and a long residual effect to prevent subsequent germination of weeds without any phytotoxicity to the crop plants. In contrast, it is also more sensible to be able to employ herbicidal combinations which have proven sufficiently effective and able to control multiple types of weeds for as long as possible, especially when it has shown itself to be environmentally compatible to a particularly high degree and to possess only minimal side-effects.
[0009] Patent document CN 102342280 and CN 102326560 both describe herbicidal formulations containing bispyribac-sodium and metamifop along with and different adjuvants for control of weeds in rice fields.
[0010] Research paper Weed Technology, 27(3), pg-459-462 (2013) describes use of a combination of Bispyribac-sodium and metamifop, which is followed by additional use of MCPA for weed control.
[0011] PCT application WO2019244088 describes herbicidal composition comprising of bispyribac sodium, metsulfuron methyl and chlorimuron ethyl, and method of preparation, and use thereof as herbicides for the control of weeds in agricultural crops.
[0012] WO2003024224 describes a herbicidal composition which, in addition to comprising customary inert formulation adjuvants, comprises as active ingredient a mixture of at least two compounds selected from the group oxadiargyl, oxadiazon, fentrazamide, ethoxysulfuron, quinclorac, pyrazolate, amicarbazone, bromobutide, carfentrazone-ethyl, pyrazolate, pyraflufen-ethyl, sulfentrazone, tepraloxydim, clodinafop-propargyl, pretilachlor, butachlor, oxaziclomefone, fentrazamide, benzobicyclon, molinate, quinclorac, bentazone, pyrazolynate, pentoxazone, metamifop, cinosulfuron, imazosulfuron, pyrazosulfuron-ethyl, azimsulfuron, bensulfuron-methyl, triasulfuron, prosulfuron, halosulfuron-methyl, sulfometuron-methyl, sulfosulfuron, chlorimuron-ethyl, cyclosulfamuron, tritosulfuron and iodosulfuron
[0013] WO2023058040 describes herbicidal combination comprising bispyribac sodium; Chlorimuron ethyl; and Penoxsulam, which at particular concentration and dosage ranges for controlling weeds in agricultural crops such as rice.
[0014] The use of herbicides to control undesired weeds in crops has become almost a universal practice. Effective use of different herbicides requires sound management. For instance, time and method of application and stage of weed plant development are critical to getting good weed control with herbicides. Unfortunately, herbicides that exhibit greater potency, broader weed spectrum and more rapid degradation in soil also have greater crop phytotoxicity. Various weed species are also resistant to herbicides. So the development of new and effective herbicidal composition becomes increasingly important.
[0015] In view of the available art described above, only a binary combination is reported and that also having one or more drawbacks as far as application and efficacy results are concerned. Despite the presence of single and binary compositions in the market, there are still no availability of any ternary formulations, which exhibits excellent synergistic effect. Hence, there is a clear need for improved formulations to reliably deliver solid or liquid formulations of improved chemical stability.
[0016] Therefore, there remains a long-standing need in the art for better combination of herbicidal active compounds exhibiting efficient and accelerated control of broad-spectrum weeds, an advantageous activity profile, high stability, low toxicity to humans or other mammals, improved ecological compatibility, and synergistic action which causes the combination to be more effective than any of the individual compounds applied separately.

OBJECTS
[0017] An object of the present invention is to provide a new and better composition of herbicidal active compounds having greater potency.
[0018] Another object of the present invention is to provide a ternary herbicidal composition.
[0019] Another object of the present invention is to provide a ternary herbicidal composition which is more effective than any of the individual compounds applied separately.
[0020] Another object of the present invention is to provide a ternary herbicidal composition, which enables a reduction in the application rate in comparison with the individual application of the active compounds.
[0021] Another object of the present invention is to provide an herbicidal composition that demonstrates broader weed spectrum.
[0022] Another object of the present invention is to provide a stable herbicidal composition.
[0023] Another object of the present invention is to provide an herbicidal composition, which exhibits low toxicity to humans or other mammals.
[0024] Another object of the present invention is to provide an herbicidal composition that has improved ecological compatibility.
[0025] Another object of the present invention is to provide an herbicidal composition that rapidly degrades in soil, and has lesser crop phytotoxicity.
[0026] Another object of the present invention is to provide an herbicidal composition, which shows better herbicidal effect against developed resistance in broad range of weed species specially grown along with rice.
[0027] Another object of the present invention is to provide an herbicidal composition, which is easy to handle and can be easily applied on crops.
[0028] Another object of the present invention is to provide an herbicidal composition, which is highly effective for a long duration on broad range of weed species in rice.
[0029] Another object of the present invention is to provide an herbicidal composition, which is useful for controlling undesired weeds in cultivated crop plants, particularly rice.
[0030] Another object of the present invention is to provide an herbicidal composition, which affords selective controlling of undesired weeds in rice crop.
[0031] Yet another object of the present invention is to provide an herbicidal composition, which can control different weeds at post emergent stage in rice crop.
[0032] The other objects and preferred embodiments and advantages of the present invention will become more apparent from the following description of the present invention when read in conjunction with the accompanying examples, which are not intended to limit scope of the present invention in any manner.

SUMMARY
[0033] The present invention relates to a ternary herbicidal composition, which provides synergistic control of weeds in crops of cultivated plants and on non-crop area. The ternary herbicidal composition comprises:
a) 2,6-Bis[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzoic acid sodium salt (commonly known as “bispyribac sodium”, and hereinafter referred to as Herbicide-A);
b) (2R)-2-[4-[(6-chloro-2-benzoxazolyl)oxy]phenoxy]-N-(2-fluorophenyl)-N-methylpropanamide (commonly known as “metamifop”, and hereinafter referred to as Herbicide-B);
c) Ethyl 2-[[[[(4-Chloro-6-methoxy-2-pyrimidinyl)amino]carbonyl]amino] sulfonyl] benzoate (commonly known as “chlorimuron-ethyl”, and hereinafter referred to as Herbicide-C); and
d) one or more agriculturally acceptable excipients.
[0034] In an embodiment, the ternary herbicidal composition disclosed herein comprises (a) bispyribac sodium (Herbicide-A) in an amount ranging from 0.5% to 10% by weight of the composition, (b) metamifop (Herbicide-B) in an amount ranging from 1% to 20% by weight of the composition, (c) chlorimuron-ethyl (Herbicide-C) in an amount ranging from 0.1% to 5% by weight of the composition, and (d) one or more agriculturally acceptable excipients.
[0035] As indicated above, the ternary herbicidal composition of the present invention comprises one or more agriculturally acceptable excipients. Preferably, the one or more agriculturally acceptable excipients are selected from the group consisting of emulsifying agents, dispersing agents, wetting agents, antifoaming agents, binding agents, fillers, rheology modifiers, surfactants, anti-freezing agents, biocides, and solvents.
[0036] In various embodiments, the ternary herbicidal composition disclosed herein can be formulated as a solid formulation or a liquid formulation.
[0037] In some embodiments, the ternary herbicidal composition can be formulated as a water soluble powder (SP), a water soluble granule (SG), a granule (GR), a dispersible concentrate (DC), an emulsifiable concentrate (EC), a wettable powder (WP), a water dispersible granule (WDG), a suspension concentrate (SC), a microemulsion (ME), a suspo-emulsion (SE), an oil-in-water emulsion (EW), or an oil dispersion (OD).
[0038] The ternary herbicidal composition disclosed herein is effective against a variety of harmful weeds. In some embodiments, the ternary herbicidal composition disclosed herein can be used for controlling weeds in rice crops.
[0039] Other aspects of the invention will be set forth in the description which follows, and in part will be apparent from the description, or may be learnt by the practice of the invention.

DETAILED DESCRIPTION
[0040] 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.
[0041] The terms "herbicide" and "herbicidal" are used herein to denote the inhibitive control or modification of undesired plant growth. Inhibitive control and modification include all deviations from natural development, such as total killing, growth retardation, defoliation, desiccation, regulation, stunting, tillering, stimulation, leaf burn and dwarfing.
[0042] As described in the ‘Herbicide Handbook of the Weed Science Society of America’, Ninth Edition, 2007, p. 429, ‘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”. Synergism in the herbicide context can mean that the use of composition having Herbicide A, B, and C as described herein results in an enhanced, greater than additive weed control effect compared to the weed control effect of herbicidal mixtures (A+B), (B+C) or (C+A) individually.
[0043] The present invention relates to a ternary herbicidal composition, which provides synergistic control of weeds in crops of cultivated plants and on non-crop area. The ternary herbicidal composition comprises:
a) 2,6-Bis[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzoic acid sodium salt (commonly known as “bispyribac sodium”, and hereinafter referred to as Herbicide-A);
b) (2R)-2-[4-[(6-chloro-2-benzoxazolyl)oxy]phenoxy]-N-(2-fluorophenyl)-N-methylpropanamide (commonly known as “metamifop”, and hereinafter referred to as Herbicide-B);
c) Ethyl 2-[[[[(4-Chloro-6-methoxy-2-pyrimidinyl)amino]carbonyl]amino] sulfonyl] benzoate (commonly known as “chlorimuron-ethyl”, and hereinafter referred to as Herbicide-C); and
d) one or more agriculturally acceptable excipients.
[0044] Herbicide-A is bispyribac sodium, and it is a branched chain amino acid synthesis (ALS or AHAS) inhibitor. It is a selective, systemic post-emergence herbicide, absorbed by foliage and roots. It is used for control of grass, sedges and broad-leaved weeds. Its herbicidal activity is described in book entitled ‘The Pesticide Manual’, seventeenth edition, 2015, page-116, contents whereof are incorporated herein, in its entirety, by way of reference.
[0045] Herbicide-B is metamifop, and it is an Acetyl-CoA carboxylase (ACCase) inhibitor. It acts as a selective contact post-emergence herbicide to control annual and perennial grass weeds in various crops. Its herbicidal activity is described in book entitled ‘The Pesticide Manual’, thirteenth edition, 20, page-638, contents whereof are incorporated herein, in its entirety, by way of reference.
[0046] Herbicide-C is chlorimuron-ethyl, that inhibits branched chain amino acid synthesis (ALS or AHAS). It acts by inhibiting biosynthesis of the essential amino acids, valine and isoleucine, hence stopping cell division and plant growth. It belongs to sulfonylurea chemistry and can be used for post-emergence control of important broadleaf weeds. Its herbicidal activity is described in book entitled ‘The Pesticide Manual’, seventeenth edition, 2015, page-186.
[0047] In still another embodiment, the present invention discloses unexpected and surprising effect of a herbicidal composition comprising Herbicides A+B+C. The herbicidal composition disclosed herein not only exhibits synergistic weed control effect, but also has broad applicability to various weeds, and is effective over a longer duration of time.
[0048] The herbicidal composition disclosed herein has little or no phytotoxicity against crops of useful plants and is useful for controlling weeds in the locus where crops are cultivated or will be cultivated. In one embodiment, there is provided a method for controlling weeds in a rice crop comprising applying to the locus where the control is desired an herbicidally effective amount of a composition comprising Herbicides A+B+C.
[0049] In various embodiments, the ternary herbicidal composition disclosed herein comprises (a) Herbicide-A in an amount ranging from 0.5% to 10% by weight of the composition, (b) Herbicide B in an amount ranging from 1% to 20% by weight of the composition, (c) Herbicide C in an amount ranging from 0.1% to 5% by weight of the composition, and (d) one or more agriculturally acceptable excipients.
[0050] In some embodiments, the ternary herbicidal composition disclosed herein comprises one or more agriculturally acceptable excipients in an amount ranging from 50 to 95 % by weight of the composition.
[0051] In a preferred embodiment, the w/w concentration of Herbicide A in the composition is about 1.5%.
[0052] In a preferred embodiment, the w/w concentration of Herbicide B in the composition is about 8.0%.
[0053] In a preferred embodiment, the w/w concentration of Herbicide C in the composition is about 0.5%.
[0054] In an embodiment, the composition comprises Herbicide A, Herbicide B and Herbicide C in a weight ratio of 1-5 : 10-25 : 1.
[0055] The ternary herbicidal composition disclosed herein is effective against a variety of harmful weeds. In some embodiments, the herbicidal composition disclosed herein can be used for controlling weeds in rice crops. Exemplary weeds include, but not limited to, Echinochloa species (Echinochloa colonum, Echinochloa crusgalli), Physalis species (Physalis minima), Phyllanthus species (Phyllanthus niruri), Leptochola species (Leptochola chinensis), Ludwigia species (Ludwigia parviflora), Commelina species (Commelina benghalensis), Cyperus species (Cyperus iria, Cyperus difformis), Fimbristylis species (Fimbristylis miliacea), Eclipta species (Eclipta alba), Bergia species (Bergia capensis), Ammania species (Ammania bassifera), Alternanthera species (Alternanthera philoxeroides), Monochoria species (Monochoria vaginalis), and Marsilia species (Marsilia quadrifolia).
[0056] In an embodiment, the herbicidal composition can be employed for selective control of weeds, such as annual or perennial grass weed, broad leaf weed and sedges, present in useful crop fields, such as but not limited to rice. Exemplary grassy weeds include Echinochloa colonum, Echinochloa crusgalli, Eleusine indica, Leptochloa chinensis, Barnyard grass, Paspalum dilatatum, Digiteria, Dactyloctenium, and Panicum repens. Exemplary broad leaf weeds include Eclipta alba, Marsilea quadrifolia, Ludwigia parviflora, Monochoria vaginalis, Sphenoclcea zeylanica, Sphenoclea pongatium, Digera arevensis, Phyllanthus niruri, Ammania baccifera, Alternanthera philoxeroides, Commelina benghalinsis, Bergia capensis, and Caesulia axillaris. Exemplary sedges weeds include Cyperus difformis, Cyperus iria, Cyperus rotundus, and Fimbristylis miliacea.
[0057] In another embodiment of the present invention, the ternary composition comprising Herbicides A+B+C shows good crop compatibility [i.e. their use in crops does not result in increased damage to crops when compared to the binary mixture of the herbicides (A+B), (B+C) or (C+A)] even though showing synergistic effect against weeds or undesirable plants.
[0058] In another embodiment, the present invention relates to the application of said composition comprising Herbicides A+B+C, which shows a remarkable improvement in residual activity. Further, the herbicidal composition of the present invention is very useful in a practical application, since it is capable of controlling, for example, hard to kill weeds in rice crop fields.
[0059] In another embodiment of the present invention, the ternary herbicidal composition of Herbicides A+B+C can be applied in a conventional manner by using techniques familiar to a person skilled in the art. The type of application depends on the intended purpose; in any case, it should be ensured that the finest possible distribution or exposing to harmful plant or unwanted plant or locus to be treated by active ingredients according to the invention. The herbicidal composition is applied to unwanted plant or weed locus primarily by spraying, in particular foliar spraying of an aqueous solution of the said composition. Application can be carried out by customary spraying techniques using, for example, water as a carrier.
[0060] In an embodiment, the composition of the present invention can be applied by any one of the methods selected from atomization, spreading, dusting, spraying, diffusion, immersion, irrigation, injection, mixing, sprinkling (water immersion), foaming, dressing, coating, blasting, fumigation, smoking, smog and painting.
[0061] In yet another embodiment of the present invention, the required application rate of the ternary composition comprising Herbicides A+B+C depends on various factors such as density of the undesired vegetation, type of soil, development stage of the plants, climatic conditions of the location, and on the application method. In general, the post-emergence application rate of the ternary premix formulation of the present invention ranges from 500 to 8000 g/ha, preferably from 2000 to 5000 g/ha.
[0062] In yet another embodiment of the present invention, application of the herbicidal composition comprising Herbicides A+B+C results in a remarkable synergistic improvement in the application window (post-emergence in weeds under different agronomical cultivation practices of rice) compared to application of binary mixture of herbicides (A+B), (B+C) or (C+A) individually.
[0063] According to embodiments of the present invention, compositions containing Herbicide-A, Herbicide-B, and Herbicide-C can be formulated in the form of a single package solid or liquid formulation containing a homogeneous mixture of Herbicides A, B, and C. In various embodiments, the herbicidal composition disclosed herein can be formulated as a water soluble powder (SP), a water soluble granule (SG), a granule (GR), a dispersible concentrate (DC), an emulsifiable concentrate (EC), a wettable powder (WP), a water dispersible granule (WDG), a suspension concentrate (SC), a microemulsion (ME), a suspo-emulsion (SE), an oil-in-water emulsion (EW), or an oil dispersion (OD). Such formulations may be prepared by any method known in the art, for example by bringing into association the Herbicides A, B, and C with one or more agriculturally acceptable excipients. Preferably, the one or more agriculturally acceptable excipients are selected from the group consisting of emulsifying agents, dispersing agents, wetting agents, antifoaming agents, binding agents, fillers, rheology modifiers, surfactants, anti-freezing agents, biocides, and solvents.
[0064] In some embodiments, the ternary herbicidal composition as described herein can be formulated in the form of a solid formulation, such as water dispersible granule (WDG), granules (GR), wettable powder (WP), water soluble granule (SG), or water soluble powder (SP). Such solid formulations can have the composition as shown in the following Table 1a.

Table 1a
Ingredient Weight % Range
Herbicide A* 0.5% to 10%
Herbicide B* 1% to 20%
Herbicide C* 0.1% to 5%
one or more surfactants 4% to 25%
one or more binding agents 0.1% to 4%
one or more antifoaming agents 0.1% to 3%
one or more fillers 40% to 85%
*Weight percentage range of active ingredient is calculated based on the purity of the active ingredient.

[0065] In some embodiments, the ternary herbicidal composition as described herein can be formulated in the form of a liquid formulation, such as emulsifiable concentrate (EC), dispersible concentrate (DC), suspension concentrate (SC), microemulsion (ME), suspo-emulsion (SE), or oil dispersion (OD). Such liquid formulations can have the composition as shown in the following Table 1b.

Table 1b
Ingredient Weight % Range
Herbicide A* 0.5% to 10%
Herbicide B* 1% to 20%
Herbicide C* 0.1% to 5%
one or more emulsifying agents 2 to 20%
one or more surfactants 1% to 15%
one or more solvents 10% to 80%
one or more rheology modifiers 0.1% to 10%
one or more dispersing agents 1% to 15%
one or more antifoaming agents 0.1% to 2%
one or more anti-freezing agents 1% to 8%
one or more biocides 0.1% to 2%
one or more fillers 20% to 80%
*Weight percentage range of active ingredient is calculated based on the purity of the active ingredient.

[0066] In an embodiment, the herbicidal composition further comprises at least one surfactant (such as wetting agents, tackifiers, dispersants and/or emulsifiers) which is usually employed in agrochemical compositions. Preferred surfactants are selected from ionic and non-ionic products which include organo-modified polyacrylates, polyacrylates, polysaccharides, alkyl or aryl sulfonates, polyoxyethylene fatty glyceride, phosphoric acid ester, modified polyethers, polyurethanes, sodium or potassium polycarboxylate, alkyl or aryl sulfates, tristyrylphenol ethaoxylated, ethoxylated propoxylated nonylphenyl ether dialkylsulfosuccinates, alkyl or lauryl ether sulfates, sodium or potassium lauryl sulfate, silicon alkoxylates, alkoxylated alkyl phenols, calcium or amine dodecylbenzenesulfonate, castor oil ethoxylate, sodium dodecyl sulfate, acetylene glycols, polyoxyethylene alkyl ether and salts, polyoxyethylene alkyl phenyl ether and salts, polyoxyethylene alkyl aryl ether and salts, polyoxyethylene styryl phenyl ether and salts, polyoxyethylene alkyl ester, derivatives of polyglycol ether, polyoxyethylene sorbitan alkylate, calcium or sodium lignosulfonate, kraft lignin, polyoxyethylene styrylphenyl ether polymer, polyoxyalkylene glycol, polyoxyethylene fatty alcohol ethers, alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids such as ligninsoulfonic acid (Borresperse® types, Borregard, Norway), phenolsulfonic acid, naphthalenesulfonic acid (Morwet® types, Akzo Nobel, U.S.A.), dibutylnaphthalene sulfonic acid (Nekal® types, BASF, Germany), condensates of alkylnaphthalene sulfonate or of naphthalenesulfonic acid with phenol and formaldehyde such as naphthalene sulfonate-formaldehyde condensate, alkyl naphthalene sulfonate-formaldehyde condensate, phenolsulfonic acid formaldehyde polycondensate as sodium salt, fatty alcohol sulfates, sodium or calcium salts of alkyl benzene sulphonate, C12-C15 alkoxylated alcohol, alkoxyoxylated tri, di or monostyryl phenol, ethoxylated polyarylphenol and sulfated hexa-, hepta- and octadecanolates, sulfated fatty alcohol glycol ethers ethoxylated alkyl aryl phosphate esters, taurates, styrene acrylic co-polymer, acrylic polymer, polyalkylene oxide block copolymer, EO-PO block copolymers as such, any fatty alcohols, esters of fatty acids, alcohols or compounds containing at least one OH group, and a suitable mixtures thereof.
[0067] In one embodiment, the herbicidal composition further comprises optionally one or more solvents selected from the group consisting of water, aromatic hydrocarbons (e.g. toluene, xylene, naphthalene, tetrahydronaphthalene, alkylated naphthalenes or their derivatives), methyl soyate, petroleum naphtha, mineral oil, biodegradable fluid, aliphatic hydrocarbons, kerosene, diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aromatic solvents (e.g. solvesso products), paraffins (e.g. mineral fractions), alcohols (e.g. methanol, ethanol, isopropanol, n-butanol, pentanol, 2-ethylhexanol, cyclohexanol, benzyl alcohol), ketones (e.g. cyclohexanone, gamma-butyrolactone), pyrrolidones (e.g. N-methyl pyrrolidone, NOP), DMSO, acetates (glycol diacetate), glycols, fatty acid dimethylamides, fatty acids, fatty acid esters, and a suitable mixture thereof.
[0068] In an embodiment, the herbicidal composition further comprises at least one antifoaming agent selected from the group consisting of polydimethylsiloxane, sodium fatty acid tallowate, magnesium stearate, silicone emulsions (such as e.g. Silikon® SRE, Wacker, Germany or Rhodorsil®, Rhodia, France), long chain alcohols, fatty acids, fatty acid esters, salts of fatty acids, fluoro organic compounds, silicone oils, mineral oils, polyether siloxane copolymer containing fumed silica, silicone defoamers, non-silicone defoamers (such as polyethers, polyacrylates), arylalkyl modified polysiloxanes, polyethylene glycol, glycerin and a suitable mixture thereof.
[0069] In one embodiment, the herbicidal composition further comprises optionally one or more stabilizing agents selected from the group consisting of diethylamine, dimethylamine, diethanolamine, isopropylamine, and a suitable mixture thereof.
[0070] In one embodiment, the herbicidal composition further comprises one or more rheology modifiers which are usually employed for this purpose in agrochemical compositions. Suitable rheology modifiers include, but not limited to, both natural and man-made modifiers, such as, for example, natural gums (xanthan gum, gum arabic, gun ghatti, gum karaya, gum tragacanth, guar gum, locust bean gum etc.), attagel, agar, alginic acid, alginate salt, chitin, pectin, casein, dextran, sodium carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydrophilic and hydrophobic silicas, fumed silica or silicon dioxide, fumed aluminium oxide, colloidal silicon dioxides, hydrogenated castor oils, polyvinylalcohol, sodium alginate, sodium poly acrylate, welan gum, lignosulfonates, hydroxy methyl cellulose, dextrin, heteropolysaccharides, organic and inorganic clays, montmorillonite, bentonite clay or its organic derivatives, oxidized waxes, carboxy methylcellulose, carrageen, fucoidan, laminaran, HEUR (hydrophobically modified, ethoxylated urethane), HMPE (hydrophobically modified polyethers), HASE (hydrophobically modified, alkali-swellable emulsion), polyacrylates, polyamides, 2-aminoethyl starch, 2-hydroxy ethyl cellulose, cellulose sulfate salt, polyacrylamide, polyvinylpyrrolidinones, alkali metal salts of the maleic anhydride copolymers, alkali metal salts of poly(meth)acrylate, and starch or a suitable mixtures thereof. This list is not intended to be exhaustive, however, and a wide variety of other rheology modifiers can be employed. A wide variety of rheology modifiers are available commercially, including, for example, the following: Kelzan® (CP Kelco, USA), Rhodopol® 23 (Rhodia, France), Veegum® (R.T. Vanderbilt, USA) and Attaclay® (Engelhard Corp., NJ; USA).
[0071] In an embodiment, the herbicidal composition further comprises optionally one or more anti-freezing agents selected from the group consisting of ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,4-pentanediol, 3-methyl-1,5-pentanediol, 2,3-dimethyl-2,3-butanediol, trimethylol propane, mannitol, sorbitol, glycerol, pentaerythritol, 1,4-cyclohexanedimethanol, xylenol, bisphenols such as bisphenol A or the like. In addition, ether alcohols such as diethylene glycol, triethylene glycol, urea, tetraethylene glycol, polyoxyethylene or polyoxypropylene glycols of molecular weight up to about 4000, diethylene glycol monomethylether, diethylene glycol monoethylether, triethylene glycol monomethylether, butoxyethanol, butylene glycol monobutylether, dipentaerythritol, tripentaerythritol, tetrapentaerythritol, diglycerol, triglycerol, tetraglycerol, pentaglycerol, hexaglycerol, heptaglycerol and octaglycerol or a suitable mixture thereof may also be employed.
[0072] In an embodiment, the herbicidal composition further comprises optionally one or more fillers selected from the group consisting of sucrose, lactose, methyl soyate, vegetable oil, urea, thiourea, kaolin, corn starch, clays, talc, chalk, glass fiber, highly disperse silica, precipitated silica, diatomite, calcite, talcum, wood flour, cellulose, pulverized wood, diatomaceous earth, montmorillonite, sodium sulfate, salts of alkali earth metals with any strong or weak acid (e.g. sodium chloride, potassium, magnesium chloride etc.), citric acid and its salts, ammonium sulfate, ammonium chloride, potash, glycols salts of dibasic acid, ammonium carbonate, salt of alkali or alkaline earth metal carbonate or hydroxide, water and a suitable mixture thereof.
[0073] In an embodiment, the herbicidal composition further comprises optionally a binding agent such as polyvinylpyrolidone or the like, and/or a biocide such as benzisothiazolinone or the like, which are known in the prior art and usually employed for this purpose in agrochemical compositions.
[0074] The compositions and methods of the appended claims are not limited in scope by the specific compositions and methods described herein, which are intended as illustrations of a few aspects of the claims and any compositions and methods that are functionally equivalent are intended to fall within the scope of the claims. Various modifications of the compositions and methods in addition to those shown and described herein are intended to fall within the scope of the appended claims. Further, while only certain representative compositions and method steps disclosed herein are specifically described, other combinations of the compositions and method steps also are intended to fall within the scope of the appended claims, even if not specifically recited.
[0075] 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 scope of the invention is determined by the claims that follow. 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
[0076] The invention is now being illustrated with working examples, which is intended to illustrate the working of disclosure and not intended to take restrictively to imply any limitations on the scope of the present disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood to one skilled in the art to which this disclosure belongs.
[0077] Several ternary herbicidal formulations were prepared with different weight percentage of active ingredients and tested for their stability and suitability, compositions whereof are provided in the Table 2a and 2b as below:
Table 2a
Example

Ingredients 1 2 3 4 5 6 7 Role
Herbicide A 0.5 1.5 3.0 0.5 3.0 1.5 1.5 Active Ingredient
Herbicide B 6.0 8.0 12.0 8.0 8.0 12.0 8.0
Herbicide C 1.0 0.5 0.1 0.5 1.0 0.5 1.0
Modified styrene acrylic polymer 10.0 10.0 10.0 - 5.0 - 5.0 Surfactant (such as Dispersing agent or Wetting agent)
Sodium polycarboxylate - - - - - 3.0 -
Potassium polycarboxylate - - - - - 2.0 -
Alkylnaphthalene sulfonate condensate - - - 4.0 - - -
Calcium lignosulfonate - - - 2.0 - - -
Sodium lignosulfonate - - - 3.0 - - 5.0
Kraft Lignin - - - 5.0 - - 5.0
Calcium dodecylbenzene sulfonate - - - - - 1.0 -
Sodium lauryl sulfate 4.0 4.0 4.0 2.0 4.0 - 3.0
Polydimethyl siloxanes - - - 1.0 0.5 - - Antifoaming agent
Sodium fatty acids tallowate 1.0 1.0 1.0 - - 1.0 -
Polyvinyl
pyrolidone - - - - 2.0 - 5.0 Binding agent
Precipitated silica - - - 2.0 - - 2.0 Filler
Kaolin 77.5 75.0 69.9 72.0 - - 5.0
Sand - - - - - - 59.5
Sodium sulfate - - - - - 25.0 -
Ammonium sulfate - - - - 30.0 30.0 -
Corn Starch - - - - 46.5 24.0 -
Total 100g 100g 100g 100g 100g 100g 100g --
Formulation WDG WDG * WDG WP SG SP GR --
* Resulting Product was used for conducting field trials.

Table 2b
Example

Ingredients 8 9 10 11 12 13 Role
Herbicide-A 3.0 3.0 1.5 1.5 1.5 3.0 Active Ingredient
Herbicide-B 12.0 8.0 6.0 8.0 8.0 8.0
Herbicide-C 1.0 0.1 1.0 0.5 1.0 1.0
Tristyrylphenol ethaoxylated 6.0 - - - - - Emulsifying agent
Calcium dodecyl
benzenesulfonate 4.0 - - - - -
Dodecylbenzene sulfonate, amine salt - - - - - 3.0
Alcohol alkoxylates - - - - - 3.0
Castor oil Ethoxylates - - 10.0 - - -
Polyoxyethylene fatty glyceride. - - - - 10.0 -
sodium di-octyl sulphosuccinate - - - - - 2.0 Surfactant
Acrylic polymer - - - 8.0 - 2.0
Alcohols, C12-15, ethoxylated - - 5.0 - - -
Polyalkylene oxide block copolymer - - 5.0 4.0 - 2.0
Cyclohexanone 68.0 - - - 49.5 - Solvent or solubilizer
Solvent naphtha(Petroleum) - - - - 15.0 -
N-methyl pyrolidone 6.0 - - - 10.0 -
Soya methyl ester - - 64.5 - - -
Biodegradable fluid - 76.9 - - - -
Mineral oil - - - - - 20.0
Bentonite clay - - 5.0 - - - Rheology modifier
Fumed silica - 5.0 2.0 - - -
Xanthan gum - - - 2.5 - 0.2
Modified polyether - 7.0 - - - - Dispersing agent
Alkylnaphthalene sulfonate - - - - - 3.0
Ethoxylated Propoxylated Nonylphenyl Ether - - - - 5.0 -
Polydimethyl
siloxanes - - - 1.0 - 1.0 Antifoaming agent
Propylene glycol - - - 5.0 - 5.0 Anti-freezing agent
Benzisothiazolinone - - - 0.5 - 0.1 Biocide
Water - - - 69.0 - 46.7 Filler
Total 100g 100g 100g 100 100g 100g --
Formulation EC DC OD SC ME SE --

Example 14: Process for the preparation of water dispersible granule (WDG):
[0078] Desired amount (recited herein-above in Table 2a, Example 2) of kaolin, Herbicide-A, Herbicide-B, Herbicide-C, modified styrene acrylic polymer, sodium lauryl sulfate and sodium fatty acid tallowate, were charged in a premix blender and blended till a uniformly blended mixture was obtained. The mixture was ground utilizing an air jet mill for which the feed rate was adjusted according to the desired particle size. After the grinding process, the mixture was blended in the post blender till uniformly blended mixture was obtained. In-process sample was check and then the mass was transferred to a sigma blender or ploughshare mixer to get a uniform dough using water. The dough was extruded in an extruder through desire sized jar to get required granules. The WDG product was then dried in a fluidized bed dryer (FBD).
Example 15: Process for the preparation of wettable powder (WP):
[0079] Desired amount (recited herein-above in Table 2a, Example 4) of kaolin, Herbicide-A, Herbicide-B, Herbicide-C, alkylnaphthalene sulfonate condensate, calcium lignosulfonate, sodium lignosulfonate, kraft lignin, sodium lauryl sulfate, precipitated silica and polydimethylsiloxanes were charged in a premix blender and blended till a uniformly blended mixture was obtained. The mixture was ground utilizing an air jet mill for which the feed rate was adjusted according to the desired particle size. After the grinding process, the mixture was blended in the post blender till uniformly blended mixture was obtained.
Example 16: Process for the preparation of water soluble granule (SG):
[0080] Desired amount (recited herein-above in Table 2a, Example 5) of corn starch, ammonium sulfate, Herbicide-A, Herbicide-B, Herbicide-C, modified styrene acrylic polymer, sodium lauryl sulfate, polydimethylsiloxanes and polyvinylpyrrolidone were charged in a premix blender and blended till a uniformly blended mixture was obtained. The mixture was ground utilizing an air jet mill for which the feed rate was adjusted according to the desired particle size. After the grinding process, the mixture was blended in the post blender till uniformly blended mixture was obtained. In-process sample was check and then the mass was transferred to a sigma blender or ploughshare mixer to get a uniform dough using water. The dough was extruded in an extruder through desire sized jar to get required granules. The product was then dried in a fluidized bed dryer (FBD).
Example 17: Process for the preparation of soluble powder (SP):
[0081] Desired amount (recited herein-above in Table 2a, Example 6) of corn starch, ammonium sulfate, sodium sulfate, Herbicide-A, Herbicide-B, Herbicide-C, sodium polycarboxylate, potassium polycarboxylate, calcium dodecylbenzenesulfonate and sodium fatty acid tallowate were charged in a premix blender and blended till a uniformly blended mixture was obtained. The mixture was ground utilizing an air jet mill for which the feed rate was adjusted according to the desired particle size. After the grinding process, the mixture was blended in the post blender till uniformly blended mixture was obtained.
Example 18: Process for the preparation of granule (GR):
[0082] Desired amount (recited herein-above in Table 2a, Example 7) of kaolin, precipitated silica, sodium lauryl sulphate, kraft lignin, sodium lignosulfonate, modified styrene acrylic polymer, Herbicide-A, Herbicide-B and Herbicide-C were charged in a premix blender and blended till a uniformly blended mixture was obtained. The mixture was ground utilizing an air jet mill for which the feed rate was adjusted according to the desired particle size. After the grinding process, the mixture was blended in the post blender till uniformly blended mixture was obtained. In-process sample was check and then the mass was transferred to a post blender. Then add Sand and Polyvinylpyrrolidone solution and mix well till uniformly blended mixture was obtained.
Example 19: Process for the preparation of suspension concentrate (SC):
[0083] Desired amount (recited herein-above in Table 2b, Example 11) of water was charged in a vessel followed by charging of acrylic graft copolymer, polyalkylene oxide block copolymer, polydimethylsiloxanes, propylene glycol, and benzisothiazolinone under stirring and mix well using high speed homogenizer. Then charged desired quantity of Herbicide-A, Herbicide-B, and Herbicide-C under stirring. The mixture was stirred till uniformly mixture was obtained. The mixture was ground utilizing bead mill for which the feed rate was adjusted according to the desired particle size maintaining temperature between 15°C to 20°C. The in-process sample was checked. Then filter the material and add xanthan gum gel and stirred the mixture till uniformly mixture was obtained to get final SC formulation without any extraneous matter.
Example 20: Process steps for the preparation of emulsifiable concentrate (EC) composition
[0084] Desired quantity (recited herein-above in Table 2b, Example 8) of solvent n-methyl pyrrolidone, cyclohexanone, Herbicide-A, Herbicide B and Herbicide C were charged in a vessel slowly under stirring at room temperature (~35°C). Stir till clear solution obtained. Charge desired quantity of tristyrylphenol ethoxylated and calcium dodecylbenzenesulfonate and stir till it gets miscible in the solvents. Filter the product to get to get final EC formulation without any extraneous matter.
Example 21: Process for the preparation of Oil dispersion (OD):
[0085] Desired amount (recited herein-above in Table 2b, Example 10) of soya methyl ester was charged in a vessel followed by charging of alcohol, C12-15, ethoxylated, castor oil ethoxylates and polyalkylene oxide block copolymer under stirring and mix well using high speed homogenizer. Then charged Herbicide-A, Herbicide-B, Herbicide-C and bentonite clay under stirring. The mixture was stirred till uniformly mixture was obtained. The mixture was ground utilizing bead mill for which the feed rate was adjusted according to the desired particle size maintaining temperature between 15°C to 20°C. The in-process sample was checked. Then filter the material and add fumed silica. The mixture was stirred again till uniformly mixture was obtained to get final OD formulation without any extraneous matter.
Example 22: Process for the preparation of dispersible concentrate (DC):
[0086] Desired quantity (recited herein-above in Table 2b, Example 9) of biodegradable fluid, Herbicide-A, Herbicide B and Herbicide C were charged in a vessel slowly under stirring at room temperature (~35°C). Mix well by using high speed homogenizer. Stir till it gets miscible in the solvents. Charge desired quantity of modified polyether (oxirane, phenyl-polymer with oxirane, monomethyl ether, and block) and stir till it gets miscible in the solvents. The in-process sample was checked for particle size. Then filter the material and add fumed silica. The mixture was stirred again till uniformly mixture was obtained to get final DC formulation without any extraneous matter.
Example 23: Process for the preparation of microemulsion (ME):
[0087] Desired quantity (recited herein-above in Table 2b, Example 12) of solvent cyclohexanone, solvent naphtha (Petroleum), N-methyl pyrrolidone, Herbicide-A, Herbicide-B and Herbicide-C were charged in a vessel slowly under stirring at room temperature (~35°C). Stir till clear solution obtained. Charge desired quantity of polyoxyethylene fatty glyceride, ethoxylated propoxylated nonylphenyl ether and stir till it gets miscible in the solvents. Filter the product to get to get final ME formulation without any extraneous matter.
Example 24: Process for the preparation of suspo-emulsion (SE):
[0088] Desired amount (recited herein-above in Table 2b, Example 13) of water was charged in a vessel followed by charging of alkylnaphthalene sulfonate, acrylic polymer, polyalkylene oxide block copolymer, propylene glycol, polydimethylsiloxanes and benzisothiazolinone under stirring and mix well using high speed homogenizer. Then charged desired quantity of Herbicide-A and Herbicide-B, under stirring. The mixture was stirred till uniformly mixture was obtained. The mixture was ground utilizing bead mill for which the feed rate was adjusted according to the desired particle size maintaining temperature between 15°C to 20°C. The in-process sample was checked. Then filter the material to get mixture-A.
[0089] In another vessel, desired amount of mineral oil, dodecylbenzene sulfonate, amine salt, alcohol alkoxylates, sodium di-octyl sulphosuccinate under stirring and mix well using high speed homogenizer. Then charged desired quantity of Herbicide-C under stirring. The mixture was stirred till uniformly mixture was obtained as mixture-B.
[0090] In further step, add mixture-B in mixture-A by maintain the flow rate and use of high speed inline homogenizer. The in-process sample was checked for particle size. Then filter the material and add xanthan gum gel and stirred the mixture till uniformly mixture was obtained to get final SE formulation without any extraneous matter.
Bio-efficacy study (in-house):
[0091] The synergistic herbicidal composition of the present disclosure Herbicide-(A+B+C), prepared in accordance with Example 2 (WDG formulation) was used for conducting field trials at a given concentrations, and efficacy was compared with binary possible tank mix combinations i.e.,
i) Herbicide-A 10% SC + Herbicide-C 25% WP or (A+C),
ii) Herbicide-A 10% SC + Herbicide-B 10% EC or (A+B), and
iii) Herbicide-B 10% EC + Herbicide-C 25% WP or (B+C),
against various grassy weeds, broad leaf weeds and sedges weeds in rice crop as per predetermined doses at 2-5 leaf stage.
[0092] Binary mixture were prepared by mixing commercially available formulation of Herbicide-A (Nominee Gold® 10% SC- manufactured by PI Industries), Herbicide-B (Critel® 10% EC- manufactured by FMC), and Herbicide-C (Cyno® 25% WP- manufactured by Atul Ltd) as per predetermined doses.
Field experiment methodology
[0093] Two field trials were conducted in cultivated rice field under naturally occurring weed populations in the trial fields. The trial sites were located at:
a) Field Trial-1 at VPO-Katunga, District-East Godavari (Andhra Pradesh); Crop variety: MTU-1271; Time period from December 2020 to May 2021.
b) Field Trial-2 at VPO-Kurud, District-Dhamtari (Chhattisgarh); Crop variety: Mahamaya; Time period from July 2021 to December 2021.
Experimental Design and Treatments:
[0094] The trials were conducted on different varieties of rice crop using normal research methodology. Treatments were randomized in block wise having plot area of 5.0 x 5.0 sq. m. and replicated thrice. The experimental plots were one meter apart to prevent cross-contamination of treatments and other research activities. Soil type for trial-1 is sandy loam and for trial-2, it is loam soil. Battery operated Knapsack sprayer with flat fan nozzle is used for application. The timely observations from the trial field were recorded, using standard methodology of observations.
Observations:
[0095] Below examples 25 to 27 summarizes the percentage control observations based on post-emergence field trials and phytotoxicity observations in rice crop.
[0096] In Examples 25 to 27, herbicidal composition (A+B+C) used in Plot number T1, T2 and T3 referred to WDG formulation prepared in accordance with Examples 2 and 14.

[00097] Example 25: Percentage control observations based on field trials performed at VPO-Katunga , District-East Godavari (Andhra Pradesh) [FIELD TRIAL-1]

Plot Herbicidal Composition Use Rate (g.a.i. /ha) % Control Observed at 30 DAA
Grassy weed Broad leaf weed Sedges
Echinochloa colonum Echinochloa crusgalli Leptochloa chinensis Bergia capensis Sphenoclea Species Ludwigia perviflora Cyperus difformis
T1 (A+B+C) 15+80+5 92 96 96 100 100 98 94
T2 (A+B+C) 15+75+5 90 93 93 100 100 94 93
T3 (A+B+C) 20+70+5 95 98 97 100 100 100 97
T4 A+C 20+6 69 63 66 96 100 90 98
T5 A+B 20+100 91 90 97 80 93 67 37
T6 B+C 100+6 89 83 85 40 60 69 80
T7 A 20 67 65 61 74 90 63 35
T8 B 100 87 78 85 22 24 19 13
T9 C 6 12 6 13 43 52 64 78
T10 UTC - 0 0 0 0 0 0 0

Plot Herbicidal Composition Use Rate (g.a.i. /ha) % Control Observed at 60 DAA
Grassy weed Broad leaf weed Sedges
Echinochloa colonum Echinochloa crusgalli Leptochloa chinensis Bergia capensis Sphenoclea Species Ludwigia perviflora Cyperus difformis
T1 (A+B+C) 15+80+5 90 94 97 100 100 100 93
T2 (A+B+C) 15+75+5 88 90 94 100 100 97 92
T3 (A+B+C) 20+70+5 94 96 98 100 100 100 96
T4 A+C 20+6 67 60 65 98 100 94 95
T5 A+B 20+100 89 92 95 78 91 66 36
T6 B+C 100+6 87 86 87 43 55 72 75
T7 A 20 65 61 60 78 85 65 39
T8 B 100 89 75 87 19 22 15 8
T9 C 6 9 3 9 41 50 62 74
T10 UTC - 0 0 0 0 0 0 0
Here DAA=Days After Application

[00098] Example 26: Percentage control observations based on field trials performed at VPO-Kurud , District-Dhamtari (Chhattisgarh) [FIELD TRIAL-2]
Plot Herbicidal Composition Use Rate (g.a.i. /ha) % Control Observed at 30 DAA
Grassy weed Broad leaf weed Sedges
Echinochloa colonum Echinochloa Crusgalli Paspalum dilatatum Digera arvensis Marsilia quadrifolia Ludwigia perviflora Cyperus difformis
T1 (A+B+C) 15+80+5 100 100 93 95 100 100 96
T2 (A+B+C) 15+75+5 100 100 89 92 100 100 92
T3 (A+B+C) 20+70+5 100 100 95 98 100 100 98
T4 A+C 20+6 69 65 61 98 100 97 97
T5 A+B 20+100 100 100 96 71 93 68 30
T6 B+C 100+6 85 80 76 63 65 65 78
T7 A 20 70 67 60 67 88 60 29
T8 B 100 85 75 72 19 27 22 15
T9 C 6 10 5 17 60 56 68 75
T10 UTC - 0 0 0 0 0 0 0

Plot Herbicidal Composition Use Rate (g.a.i./ha) % Control Observed at 60 DAA
Grassy weed Broad leaf weed Sedges
Echinochloa colonum Echinochloa Crusgalli Paspalum dilatatum Digera arvensis Marsilia quadrifolia Ludwigia perviflora Cyperus difformis
T1 (A+B+C) 15+80+5 100 100 91 93 100 100 95
T2 (A+B+C) 15+75+5 100 100 90 90 100 100 90
T3 (A+B+C) 20+70+5 100 100 93 96 100 100 100
T4 A+C 20+6 70 68 60 96 100 98 100
T5 A+B 20+100 100 100 94 69 95 65 34
T6 B+C 100+6 83 78 72 60 66 63 80
T7 A 20 65 60 59 65 83 59 32
T8 B 100 84 78 68 14 22 16 10
T9 C 6 12 4 14 63 53 63 77
T10 UTC - 0 0 0 0 0 0 0
Here DAA=Days After Application

[00099] Example 27: Phytotoxicity Observation for [FIELD TRIAL-1] and [FIELD TRIAL-2]

Plot Herbicidal Composition Use Rate (g.a.i./ha) % Phytotoxicity observed
5 DAA 10 DAA 15 DAA 20 DAA 30 DAA
T1 (A+B+C) 15+80+5 0 0 0 0 0
T2 (A+B+C) 15+75+5 0 0 0 0 0
T3 (A+B+C) 20+70+5 0 0 0 0 0
T4 A+C 20+6 0 0 0 0 0
T5 A+B 20+100 0 0 0 0 0
T6 B+C 100+6 0 0 0 0 0
T7 A 20 0 0 0 0 0
T8 B 100 0 0 0 0 0
T9 C 6 0 0 0 0 0
T10 UTC - 0 0 0 0 0

[000100] It can be appreciated from the observed results presented hereinabove that in each case, for any of the 3 doses of the combination of Herbicides A+B+C tested, the effect of the composition in post-emergence application is unexpectedly and surprisingly synergistic over the effect of binary mixture of herbicides (A+B), (B+C) or (C+A) and also over the individual herbicides A, B and C.
[000101] The combination has the potential of controlling the cross-spectrum weeds (broad leaf weeds, grassy weeds, and sedges) in rice. All the selected molecules are safe to transplanted and direct seeded rice when applied in post-emergence (15-20 days after transplanting) application timing.
[000102] Visual observations were recorded on percent weed control for individual weeds on whole plot basis at 30 and 60 days after application (DAA). These observations are to be taken from entire plot. The field trials were carried out in India at different locations.
[000103] The results in Trial-1 (Example 25) and Trial-2 (Example-26), clearly demonstrates efficacy of combination of Herbicides A+B+C against weeds like, Echinochloa colonum, Echinochloa crusgalli, Leptochloa chinensis, Paspalum dilatatum, Digera arvensis, Marsilia quadrifolia, Ludwigia perviflora, Bergia capensis, Sphenoclea Species, and Cyperus difformis at both after 30DDA and after 60DDA. The field studies were conducted to compare the weed controlling activity of the combination of Herbicides (A+B+C) over the effect of binary mixture of herbicides (A+B), (B+C) or (C+A) and individual herbicides A, B and C.
[000104] The results in both Trial-1 (Example 25) and Trial-2 (Example-26), clearly demonstrates that efficacy of combination of Herbicides (A+B+C) in Plot numbers T1 to T3 have better efficacy over the other treatments.
[000105] To assess the phytotoxic effect of the herbicidal composition on rice crop viz. leaf burning, yellowing, stunting, scorching, epinasty, hyponasty etc., trials were laid out in Randomized Black Design (RBD) replicated three times. For each treatment, plot size was maintained at 25 sq. meter. To raise the crops, all the agronomical practices were followed as usually adopted for rice cultivation. The said binary and ternary herbicidal compositions were applied in prescribed recommended doses by battery operated Knapsack sprayer with flat fan nozzle.
[000106] Observation on phytotoxicity viz. growth stunting, yellowing, scorching, epinasty, hyponasty etc. was recorded at 5 to 30 ‘Days after Application’ (DAA) of post emergence treatments from ten plants which were randomly selected from each plot.
[000107] It can be appreciated from the observed results presented hereinabove that in each case i.e. Trial-1 and Trial-2, for any of the treatment T1 to T9, the percentage phytotoxicity observed is zero even after 30 DAA (refer to Example-27).
[000108] Accordingly, by the practice of the present invention, herbicide compositions having heretofore unrecognized characteristics are prepared. These herbicides exhibit exceptionally synergetic effect for control of common weeds, especially growing in the rice field and is used in a post-emergence herbicide application.
[000109] It can be appreciated from the observed results presented hereinabove that the herbicidal premix formulation of the present invention as tested exhibits no phytotoxicity to rice crop up to 5000 g or ml/ha dose amount.
[000110] Overall, the present invention provides a composition comprising three herbicidal active ingredients, which at particular w/w ratios, and in various doses exhibit an unexpected and surprising synergism in ability to eliminate growth of weeds and unwanted vegetation. Of particular importance is that the said composition, while it is detrimental to the growth of weeds, does not particularly affect agronomic characteristics of crop plant such as rice. The said composition is not phytotoxic to the crop plants up to recommended doses, which makes the said composition an attractive and suitable alternative to usage of individual herbicides.
[000111] 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
[000112] The present invention provides a ternary herbicidal composition that synergistically controls weeds and unwanted vegetation.
[000113] The present invention provides a ternary herbicidal composition which is more effective than any of the individual compounds applied separately.
[000114] The present invention provides a ternary herbicidal composition which enables a reduction in the application rate in comparison with the individual application of the active compounds.
[000115] The present invention provides a ternary herbicidal composition that has greater potency and demonstrates broader weed spectrum.
[000116] The present invention provides a ternary herbicidal composition that is detrimental to the growth of weeds, does not particularly affect agronomic characteristics of crop plant such as rice.
[000117] The present invention provides a ternary herbicidal composition that is not phytotoxic to the crop plants up to recommended doses, which makes the composition an attractive and suitable alternative to usage of individual herbicides.
[000118] The present invention provides a ternary herbicidal composition that is highly stable and has low toxicity to humans or other mammals.
[000119] The present invention provides a ternary herbicidal composition that has improved ecological compatibility.
[000120] The present invention provides a ternary herbicidal composition that rapidly degrades in soil and has lesser crop phytotoxicity.
[000121] The present invention provides a ternary herbicidal composition which shows better herbicidal effect against the developed resistance in broad range of weed species specially grown along with rice crop.
[000122] The present invention provides a ternary herbicidal composition which is easy to handle and can be easily applied on crops.
[000123] The present invention provides a ternary herbicidal composition which is highly effective for a long duration on broad range of weed species in rice crop.
[000124] The present invention provides a ternary herbicidal composition which is useful for controlling undesired weeds in cultivated crop plants particularly rice.
[000125] The present invention provides a ternary herbicidal composition which can control weed at post emergent stage.
, Claims:1. A herbicidal composition comprising:
a) bispyribac sodium in an amount ranging from 0.5% to 10% by weight of the composition;
b) metamifop in an amount ranging from 1% to 20% by weight of the composition;
c) chlorimuron-ethyl in an amount ranging from 0.1% to 5% by weight of the composition; and
d) one or more agriculturally acceptable excipients.

2. The composition as claimed in claim 1, wherein the composition comprises 1.5% by weight of bispyribac sodium, 8% by weight of metamifop and 0.5% by weight of chlorimuron-ethyl.

3. The composition as claimed in claim 1, wherein the one or more agriculturally acceptable excipients are selected from the group consisting of surfactants, dispersing agents, emulsifying agents, antifoaming agents, binding agents, fillers, rheology modifiers, anti-freezing agents, biocides, and solvents.

4. The composition as claimed in claim 3, wherein
the surfactant is selected from acrylic polymer, C12-C15 ethoxylated alcohols, polyalkylene oxide block copolymer, sodium di-octyl sulfosuccinate, alkylnaphthalene sulfonate condensate, sodium lauryl sulfate, calcium or sodium lignosulfonate, sodium or potassium polycarboxylate, kraft lignin, and a mixture thereof;
the emulsifying agent is selected from calcium or amine salt of dodecylbenzenesulfonate, tristyrylphenol ethoxylated, and a mixture thereof;
the solvent is selected from petroleum naphtha, cyclohexanone, methyl soyate, N-methyl-2-pyrrolidone, mineral oil, and a mixture thereof;
the antifoaming agent is selected from polydimethyl siloxanes, sodium fatty acid tallowate, silicone emulsions, long chain alcohols, fatty acids, fatty acid esters, salts of fatty acids, silicone oils, mineral oils, and a mixture thereof;
the binding agent is polyvinylpyrolidone;
the filler is selected from precipitated silica, kaolin, sand, sodium or ammonium sulfate, corn starch, water, and a mixture thereof;
the dispersing agent is selected from modified polyether, alkylnaphthalene sulfonate, ethoxylated propoxylated nonylphenyl ether, and a mixture thereof;
the rheology modifier is selected from bentonite clay, fumed silica, xanthan gum, and a mixture thereof;
the biocide is benzisothiazolinone; and
the anti-freezing agent is propylene glycol.

5. The composition as claimed in claim 1, wherein the composition is in the form of a water soluble powder (SP), a water soluble granule (SG), a granule (GR), a dispersible concentrate (DC), an emulsifiable concentrate (EC), a wettable powder (WP), a water dispersible granule (WDG), a suspension concentrate (SC), a microemulsion (ME), a suspo-emulsion (SE), an oil-in-water emulsion (EW), or an oil dispersion (OD).

6. The composition as claimed in claim 5, wherein the composition is a water dispersible granule or a wettable powder.

7. The composition as claimed in claim 1, which is a solid composition comprising, by weight:
0.5-10% of bispyribac sodium;
1-20% of metamifop;
0.1-5% of chlorimuron-ethyl;
4-25% of one or more surfactants;
0.1-4% of one or more binding agents;
0.1-3% of one or more antifoaming agents; and
40-85% of one or more fillers.

8. The composition as claimed in claim 1, which is a liquid composition comprising, by weight:
0.5-10% of bispyribac sodium;
1-20% of metamifop;
0.1-5% of chlorimuron-ethyl;
2-20% of one or more emulsifying agents;
1-15% of one or more surfactants;
10-80% of one or more solvents;
0.1-10% of one or more rheology modifiers;
1-15% of one or more dispersing agents;
0.1-2% of one or more antifoaming agents;
1-8% of one or more anti-freezing agents;
0.1-2% of one or more biocides; and
20-80% of one or more fillers.

9. The composition as claimed in any one of claims 1 to 9, for use in controlling weeds in a rice crop.

10. The composition as claimed in claim 10, wherein the weeds are selected from the group consisting of Echinochloa species (Echinochloa colonum, Echinochloa crusgalli), Physalis species (Physalis minima), Phyllanthus species (Phyllanthus niruri), Paspalum species (Paspalum dilatatum), Leptochola species (Leptochola chinensis), Digera specis (Digera arvensis), Ludwigia species (Ludwigia parviflora), Commelina species (Commelina benghalensis), Cyperus species (Cyperus iria, Cyperus difformis), Sphenoclea species (Sphenoclcea zeylanica, Sphenoclea pongatium) Fimbristylis species (Fimbristylis miliacea), Eclipta species (Eclipta alba), Bergia species (Bergia capensis), Ammania species (Ammania bassifera), Alternanthera species (Alternanthera philoxeroides), Monochoria species (Monochoria vaginalis), and Marsilia species (Marsilia quadrifolia).