Description:FIELD OF THE INVENTION
The present invention relates to novel synergistic herbicidal compositions and methods related thereto. More particularly, the present invention relates to a synergistic herbicidal composition comprising Bispyribac-sodium, Fenoxaprop-p-ethyl, Polycarboxylate salt and agriculturally acceptable formulation additives, and the method of preparation and use thereof as herbicides for the control of weeds in agricultural crops, in particular weeds flora in rice.

BACKGROUND OF THE INVENTION
Weeds are undesirable plants that can severely damage yield in crops. Further, weeds are a persistent problem that needs constant monitoring. Several herbicides and methods of using such herbicides to control weed species are known in the art. Chemical herbicides are typically categorized according to the time of application (e.g., pre-emergence or post-emergence herbicides). Pre-emergence herbicides are applied prior to germination of weed for control of germinating seeds without harming the desired plant species. Post-emergence herbicides are applied after planting and over the top of establishing or established plants for control of weed species.
Moreover, current methods of attempting to control weeds include applications of pre-emergent herbicides followed by post emergent herbicides i.e. sequential applications of herbicides to address the issue of weeds in agricultural crop cultivation. Most of the rice lands under cultivation are weeded by hand, hence, significant human effort and time are expended in raising rice. Most of the times, the dosage used varies as the herbicide selection is not based on the technical knowhow which results in poor weed control affecting the productivity of the crop. Additionally, farmers are using different herbicidal combinations without knowing the mode of action and the weed spectrum. Due to lack of knowledge, there is inappropriate and/or under dosage of the weed products and this frequently leads to resistance development or poor control of the weeds. Similarly, other conventional methods of producing agricultural crops include the use of different combinations of herbicides such as tank mix herbicides to address the issue of emerged weeds without having proper application knowledge of the weed spectrum individual herbicides. In such usage the chances of varied dosage of individual herbicides end up with poor weed control, phytotoxicity on rice crop resulting in poor productivity. Therefore, successful weed management is essential for economical rice production. Furthermore, environmental considerations increasingly require that lower amounts of herbicidal active substances be used in the control of undesired vegetation.
It is known to overcome this type of problem to some extent by the use of herbicidal compositions in which more than one type of herbicide is present. Such compositions, however, should preferably still show the advantageous properties of the individual herbicide constituents and display a synergistic effect between them, whilst maintaining selectivity of herbicidal action with respect to the crop. It is, nonetheless, difficult to determine appropriate combinations of herbicides in view of the considerable number of different types of herbicides available and the plurality of individual herbicides within each such type.
Herbicides used in rice weed management and the issues related with the weed control are shown in the below Table 1:
Table-1:
Herbicide Trade name Formulation Formulation
Dosage/ha Rice segment Usage Issues
Pretilachlor Rifit 50 % EC 1-1.25L Transplanted Weed control is poor if water management is not good
Butachlor Machette 50% EC 2.5 L Transplanted Not good on Broad leaved weeds
Metasulfuron Methyl 10% + Chlorimuron Ethyl 10% WP Almix 20% WP 20 gm Transplanted and nursery and DSR Weak on grasses
Cyhalofop butyl Clincher 10% EC 800 ml Nursery Does not control Broadleaved weeds and sedges
Pretilachlor Sofit 30% EC 1.25 L Nursery and direct seeded Weed control is poor if water management is not good
Ethoxysulfuron Sunrice 15% WDG 100 gm Transplanted, DSR Does not control grasses
Pyrazosulfuron Saathi 10% WP 200 gm Transplanted, Nursery, DSR Weak on grasses
2,4 D Sodium salt Weedmar 80% WP 1KG Transplanted, DSR Weak on grasses
2,4 D ethyl ester Weedmar38 38% EC 2.5 L Transplanted, DSR Weak on grasses
Oxadiargyl Topstar 80% WP 87.5 Transplanted Weed control is poor if water management is not good
Bensulfuron methyl 0.6 % + Pretilachlor 6 % Londax Power 6.6% 10 kg Transplanted Weed control is poor if water management is not good
Bispyribac sodium Bispyribac sodium 10% SC 200 ML Transplanted, DSR, Nursery
Fenoxyprop-P-ethyl Whipsuper 10% EC 750 ML DSR Only good on grasses but phytotoxicity issues are there.

It is known that when herbicides are used to control the growth of undesired plants, there may be some damage to the cultivated plants. The amount of damage will depend on a number of factors but, in some cases, the cultivated plants can be protected from the effect of the herbicide by using a compound termed as a safener. A safener is a compound which eliminates or lessens the phytotoxic properties of a herbicide toward crop plants without substantially reducing the herbicidal action toward weed plants.
Identifying a safener for a particular group of herbicides is still a difficult task, since the precise mechanisms by which a safener lessens the noxious effect of herbicides are unknown. Consequently, the fact that a compound acts as safener in combination with one particular herbicide does not permit conclusions as to the safener action of such a compound with other groups of herbicides.

Bispyribac-Sodium was first disclosed in EP021846. Chemically know as sodium 2,6-bis[(4,6-dimethoxypyrimidin-2-yl)oxy]benzoate.

Mode of action: selective, systemic action post-emergence herbicide, absorbed by foliage and roots.
Bispyribac sodium is a systemic herbicide that moves throughout the plant tissue and works by interfering with production of a plant enzyme necessary for growth, acetolactate synthase (ALS). It is used to control grasses, sedges and broad-leaved weeds, especially Echinochloa spp., in direct seeded rice. It is also used to stunt growth of weeds in non-crop situations. Bispyribac sodium is broken down by microbes and has a half-life (the time it takes for half of the active ingredient to degrade) of 42-115 days. The primary degradation product of bispyribac sodium is sodium 2-(4,6dimethoxypyrimidin-2-yl) oxy-6-(4-hydroxy-6- methoxy pyrimidin -2-yl) benzoate. Bispyribac sodium does not bind to soil, is moderately persistent and somewhat mobile through the soil. Testing indicates that the aquatic formulation of Bispyribac sodium is non-toxic to fish and invertebrates. Bispyribac sodium is also non-toxic to both birds and mammals.

Fenoxaprop-p-ethyl is a selective herbicide with contact and systemic action, absorbed principally by the leaves, with translocation both acropetally and basipetally to the roots or rhizomes.

Fenoxaprop-p-ethyl is used for post-emergence controlling of annual and perennial grass weeds in potatoes, beans, soya beans, beets, vegetables, peanuts, flax, oilseed rape, and cotton; and (when applied with the herbicide safener mefenpyr-diethyl) and wild oats in wheat, rye, triticale and, depending on ratio, in some varieties of barley.

Isoxadifen-ethyl is the common name for ethyl 4,5- dihydro-5,5-diphenyl-3-isoxazole-carboxylate. It is used as a safener in maize.

Indian patent application 3381/DEL/2015 discloses a stable synergistic agrochemical composition for management of weed flora in rice comprising sodium 2,6-bis[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzoate (A) and ethyl (2R)2[4[(6-chloro-1,3-benzoxazol-2-yl)oxy]phenoxy] propanoate(B) and agriculturally acceptable formulation additives (C) wherein the weight percentage of (A) is 5 to 25%, weight percentage of (B) is 10 to 50% and weight percentage of (C) is 5 to 90%.
The combination demonstrates an effect which is superior to that of the herbicides used individually.

However, still there is a need to develop a novel synergistic herbicidal composition which overcomes some of the existing problems and which will exhibit better effectiveness with optimum use of both actives at minimum herbicide application rate or concentration. A minimum application rate reduces not only the amount of an active substance required for the application but generally also reduces the amounts of formulation auxiliaries necessary. Both reduce the economic cost and improve the ecological compatibility of the herbicide treatment.
Surprisingly, the inventors of the present invention found that the novel synergistic herbicidal composition of Bispyribac-sodium, Fenoxaprop-p-ethyl, and Polycarboxylate salt with agriculturally acceptable formulation additives which supplies the right amount of the Bispyribac-sodium, Fenoxaprop-p-ethyl at the right time to assure ample consumption of said Bispyribac-sodium and Fenoxaprop-p-ethyl which can be used for herbicidal activity or supportive use of Isoxadifen-ethyl as a safener and Polycarboxylate salt as an adjuvant to provide synergies in controlling undesired vegetation or weeds in Rice crop with a lower concentration of Bispyribac-sodium and Fenoxaprop-p-ethyl and also contributes in Herbicide Resistance Management (HRM).
The inventors of the present invention also found that the novel synergistic herbicidal composition of Bispyribac-sodium, Fenoxaprop-p-ethyl and Polycarboxylate salt with agriculturally acceptable formulation additives exhibit qualities such as but not limited to stability, easy application, easy dose adjustment, no phytotoxicity, broad spectrum, better efficacy, minimal impact on environment, and better compliance, wherein said composition is designated for its use for controlling undesired vegetation in rice crop.

OBJECTIVE OF THE INVENTION:
The main objective of the present invention is to provide a novel synergistic herbicidal composition comprising Bispyribac-sodium, Fenoxaprop-p-ethyl, Polycarboxylate salt and one or more inactive excipient.
Another objective of the present invention is to provide a process for the preparation of a novel synergistic herbicidal composition comprising a combination of Bispyribac-sodium, Fenoxaprop-p-ethyl, Polycarboxylate salt and one or more inactive excipient.
Another objective of the present invention is to provide a novel synergistic herbicidal composition comprising a combination of Bispyribac-sodium, Fenoxaprop-p-ethyl, Polycarboxylate salt, herbicide safener and one or more inactive excipient.
Another objective of the present invention is to provide a process for the preparation of a novel synergistic herbicidal composition comprising a combination of Bispyribac-sodium, Fenoxaprop-p-ethyl, Polycarboxylate salt, herbicide safener and one or more inactive excipient.
Yet another objective of the present invention is to provide a novel synergistic herbicidal composition which exhibit better effectiveness with optimum use of both actives at lower herbicide application rate or concentration for management and control of weeds in rice.
Yet another objective of the present invention is to provide an herbicidal composition that efficaciously contributes in Herbicide Resistance Management (HRM).
Yet another objective of the present invention is to provide an economical and cost-effective composition for management and control of weeds.
Yet another objective of the present invention is to provide a cost-effective and convenient method for the preparation of said composition, which is effective against a wide variety of weeds in crops, especially for management of weed flora in rice.
Yet another objective of the present invention is to provide a stable synergistic herbicidal composition which meets the environmental and economic requirements imposed on modern-day herbicides which are continually increasing, with regard, for example, to the spectrum of action, toxicity, selectivity, application rate, formation of residues, low costs and favorable preparation ability.
The present invention, described hereinafter, achieves at least one, and preferably more than one, of the above mentioned objectives of the invention.

SUMMARY OF THE INVENTION:
Accordingly, the present invention provides a novel synergistic herbicidal composition comprising Bispyribac-sodium, Fenoxaprop-p-ethyl, Polycarboxylate salt and agriculturally acceptable formulation additives.
In one aspect, the present invention provides a novel synergistic composition comprising Bispyribac-sodium, Fenoxaprop-p-ethyl, Polycarboxylate salt and one or more inactive excipient.
In another aspect, the present invention provides a process for the preparation of a novel synergistic herbicidal composition comprising Bispyribac-sodium, Fenoxaprop-p-ethyl, Polycarboxylate salt and one or more inactive excipient.
In another aspect, the present invention provides a novel synergistic herbicidal composition comprising Bispyribac-sodium, Fenoxaprop-p-ethyl, Polycarboxylate salt, herbicide safener and one or more inactive excipient.
In another aspect, the present invention provides a process for the preparation of a novel synergistic herbicidal composition comprising Bispyribac-sodium, Fenoxaprop-p-ethyl, Polycarboxylate salt, herbicide safener and one or more inactive excipient.
In yet another aspect, the present invention provides a novel synergistic herbicidal composition which exhibit better effectiveness with optimum use of both actives at minimal herbicide application rate or concentration for management and control of weeds in rice.
In yet another aspect, the present invention provides a composition comprising Bispyribac-sodium, Fenoxaprop-p-ethyl, Polycarboxylate salt, and one or more inactive excipient to control a wide variety of weeds in crops.
In yet another aspect, the present invention provides a composition that achieves increased yield in the crops to which it is applied.
In yet another aspect, the present invention provides a composition of Bispyribac-sodium, Fenoxaprop-p-ethyl, Isoxadifen-ethyl, Polycarboxylate salt and one or more inactive excipient that causes an enhanced herbicidal activity.

DETAILED DESCRIPTION OF THE INVENTION:
ABBREVIATIONS
AE: Aerosol SG: Water soluble granule
CS: Capsule suspension SP: Water soluble powder
DP: Dustable powder SU: Ultra-low volume (ULV) suspension
EC: Emulsifiable concentrate ME: Micro-emulsion
EG: Emulsifiable granule OD: Oil dispersion
EW: Emulsion-in-water UL: Ultra-low volume liquid
e.g.: Example WDG/WG: Water dispersible granule
GR: Granule WP: Wettable powder
SC: Suspension concentrate WT: Water dispersible tablet
SE: Suspo-emulsion

DEFINITIONS
The foregoing definitions provided herein for the terminologies used in the present disclosure are for illustrative purpose only and in no manner limit, the scope of the present invention disclosed in the present disclosure.
It will be understood that the terminology used herein is for the purpose of describing embodiments only, and is not intended to be limiting. As used in this specification, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, the reference to "a surfactant" includes one or more of such surfactants.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one ordinary skilled in the art to which the invention pertains. Although other methods and materials similar, or equivalent, to those described herein can be used in the practice of the present invention, the preferred materials and methods are described herein.
As used herein, the terms "comprises", "comprising", "includes", "including", or any other variation thereof, are intended to cover a non-exclusive inclusion, subject to any limitation explicitly indicated. For example, a composition or a method that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, or method.
As used herein, the term "agrochemically acceptable salts" are typically acid addition salts of inorganic or organic acids, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, malonic acid, toluenesulfonic acid or benzoic acid.
As used herein, the term “additive(s)” or "auxiliary agent(s)" or “agriculturally acceptable carrier(s)” can be used interchangeably and refers to inert substances which are commonly used as diluent, to provide stability or to increase the activity profile of the composition or formulation with or without having agrochemical activity.
As used herein, the term “surfactant(s)” means a compound that, when dissolved in a liquid, reduces the surface tension of the liquid, which reduces the interfacial tension between two liquids or which reduces surface tension between a liquid and a solid.
As used herein, the term “stabilizer(s)” refers to a substance capable of imparting resistance against physical or chemical deterioration or deformulation.
As used herein, the term “defoaming agent(s)” refers to a chemical additive that reduces and hinders the formation of foam in the industrial process liquids, semi-solids, or solids. The terms defoaming agent and anti-foaming agent can be used interchangeably.
As used herein, the term “thickener(s)” refers to a polymeric material, which at a low concentration increases the viscosity of an aqueous solution and helps to stabilize the composition.
Unless otherwise specified, % refers to % weight; and % weight refers to % of the weight of the respective component with respect to the total weight of the composition.
As used herein, the term “herbicide” shall mean an active ingredient that kills, controls or otherwise adversely modifies the growth of plants. As used herein, a herbicidally effective or vegetation controlling amount is an amount of active ingredient that causes a "herbicidal effect," i.e., an adversely modifying effect and includes deviations from natural development, killing, regulation, desiccation, retardation. The terms "plants" and "vegetation" include, but are not limited to, germinant seeds, emerging seedlings, plants emerging from vegetative propagules, and established vegetation.
As used herein, the term “plant parts” are understood to mean all above-ground and below-ground parts and organs of plants, such as shoot, leaf, flower and root, examples including leaves, needles, stems, stalks, flowers, fruit-bodies, fruits and seeds, and also roots, tubers and rhizomes. The plant parts also include harvested plants and vegetative and generative propagation material, for example seedlings, tubers, rhizomes, cuttings and seeds.
As used herein, the term “locus" means a plant, plant parts, plant propagation material (preferably seed), soil, area, material or environment in which a pest is growing or may grow. Also, denote the vicinity of a desired crop in which weed control, typically selective weed control is desired. The locus includes the vicinity of desired crop plants wherein the weed infestation has either emerged or is yet to emerge. The term crop shall include a multitude of desired crop plants or an individual crop plant growing at a locus.
As used herein, the term “polymorph” encompasses the different crystal forms of compound. When a compound recrystallizes from a solution or slurry, it may crystallize with different spatial lattice arrangements, a property referred to as “polymorphism”. Different polymorphic forms of a given substance may differ from each other with respect to one or more physical properties, such as solubility and dissociation, true density, crystal shape, compaction behavior, flow properties, and/or solid state stability.
As used herein, the term "effective amount" means the amount of the active substances in the compositions to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The effective amount can vary for the various compositions used in the present invention. An effective amount of the compositions will also vary according to the prevailing conditions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.
As used herein, the term “agriculturally acceptable additives” means it contains additional additives selected from: solid carrier(s), liquid carrier(s), gaseous carrier(s), surfactant(s), binder(s), disintegrating agent(s), antioxidant(s), osmotic agent(s), wetting agent(s), pH adjuster(s), thickener(s), preservative(s), filler(s), diluent(s), emulsifier(s), anti-caking agent(s), anti-freezing agent(s), defoaming agent(s), viscosifying agent(s), extender(s), buffering agent(s), solubilizer(s), chelating agent(s), stabilizer(s) and/or coloring agent(s) or combination thereof.
As used herein, the term “lower” or “minimal” or “minimum” can be used interchangeably and refers to the optimum concentration of active or inactive ingredients of formulation to achieve the expected efficacy.
The novel synergistic herbicidal composition of the present invention advantageously exhibits better effectiveness with optimum use of both actives at lower herbicide application rate or concentration. A lower application rate reduces not only the amount of an active substance required for the application but generally also reduces the amounts of formulation auxiliaries necessary. Both reduce the economic cost and improve the ecological compatibility of the herbicide treatment.

In one embodiment, the present invention relates to a novel synergistic herbicidal composition comprising Bispyribac-sodium, Fenoxaprop-p-ethyl, Polycarboxylate salt and one or more inactive excipient.
In another embodiment, the present invention relates to a novel synergistic herbicidal composition comprising Bispyribac-sodium, Fenoxaprop-p-ethyl, Polycarboxylate salt, herbicide safener and one or more inactive excipient.
In another embodiment, the present invention relates to a herbicidal composition comprising Bispyribac-sodium, Fenoxaprop-p-ethyl, Polycarboxylate salt, herbicide safener and one or more inactive excipient.
In yet another embodiment of the present invention, the Polycarboxylate salt is a water soluble alkali metal salt of polycarboxylic acid preferably selected from Sodium Polycarboxylate or Potassium Polycarboxylate or combination thereof.
Potassium polycarboxylate of the present invention comprises a polymer of maleic acid potassium salt. Sodium polycarboxylate of the present invention comprises a polymer of maleic acid sodium salt.

In a preferred embodiment of the present invention, the molecular weight of the Polycarboxylate salt is from 1500 to 50000, more preferably from 1500 to 10000, most preferably from 1500 to 5000.
Polycarboxylate salts tends to increase the suspensibility of the novel synergistic formulation. Suspensibility is important parameter for crop protection product, if suspensibility of the formulation is optimum, it will lead to better dispersion, better droplet size distribution that will ensure better foliar surface coverage and that would result better efficacy, high disease control and better crop yield.
Surprisingly, the inventors of the present invention found that the novel synergistic herbicidal composition of Bispyribac-sodium, Fenoxaprop-p-ethyl, and Polycarboxylate salt supplies the right amount of the Bispyribac-sodium, Fenoxaprop-p-ethyl at the right time to assure ample consumption of said Bispyribac-sodium and Fenoxaprop-p-ethyl which can be used for herbicidal activity or supportive use of Isoxadifen-ethyl as a safener and Polycarboxylate salt as an adjuvant to provide synergies in controlling undesired vegetation or weeds in Rice crop with a minimal concentration of Bispyribac-sodium and Fenoxaprop-p-ethyl.
In yet another embodiment of the present invention, the herbicide safener is Isoxadifen-ethyl.
In yet another embodiment of the present invention, the Polycarboxylate is Geropon.

In another embodiment, the present invention may be a composition which is formulated as a dusts, a water dispersible granule (WDG)/(WG), a tablet (TB), a wettable powder (WP), a water dispersible tablet (WT), a water soluble powder (SP) or a granule (GR).

In yet another embodiment, the present invention relates to wettable powder (WP) composition of bispyribac-sodium, fenoxaprop-p-ethyl, Polycarboxylate salt and agriculturally acceptable formulation additives.

In a preferred embodiment, the present invention relates to a water dispersible granule (WDG)/(WG) composition of bispyribac-sodium, fenoxaprop-p-ethyl, Polycarboxylate salt and agriculturally acceptable formulation additives.

In another preferred embodiment, the present invention relates to a water dispersible granule (WDG)/(WG) composition of bispyribac-sodium, fenoxaprop-p-ethyl, Polycarboxylate salt and agriculturally acceptable formulation additives.
In another preferred embodiment, the present invention relates to a novel synergistic herbicidal composition for management of weed flora in rice comprising bispyribac-sodium, fenoxaprop-p-ethyl, Polycarboxylate salt and agriculturally acceptable formulation additives wherein the weight percentage of bispyribac-sodium is 5-10 %, weight percentage of fenoxaprop-p-ethyl is 10-15%, weight percentage of Polycarboxylate salt is 1-25 % and weight percentage of agriculturally acceptable formulation additives is 30-70%.
In a more preferred embodiment, the present invention relates to a novel synergistic water dispersible granule (WG/WDG) herbicidal composition for management of weed flora in rice comprising bispyribac-sodium, fenoxaprop-p-ethyl, isoxadifen-ethyl, Polycarboxylate salt and agriculturally acceptable formulation additives wherein the weight percentage of bispyribac-sodium is 5-10 %, weight percentage of fenoxaprop-p-ethyl is 10-15%, weight percentage of Isoxadifen-ethyl is 5-25%, weight percentage of Polycarboxylate salt is 1-25 % and weight percentage of agriculturally acceptable formulation additives is 30-70%.
In a most preferred embodiment, the present invention relates to a water dispersible granule (WG/WDG) herbicidal composition for management of weed flora in rice comprising bispyribac-sodium, fenoxaprop-p-ethyl, isoxadifen-ethyl, Polycarboxylate salt and agriculturally acceptable formulation additives wherein the weight percentage of bispyribac-sodium is 5-10 %, weight percentage of fenoxaprop-p-ethyl is 10-15%, weight percentage of Isoxadifen-ethyl is 5-25%, weight percentage of Polycarboxylate salt is 1-25 % and weight percentage of agriculturally acceptable formulation additives is 30-70%.
In one embodiment, the present invention relates to a combination comprising bispyribac-sodium, fenoxaprop-p-ethyl, isoxadifen-ethyl, Polycarboxylate salt which can be mixed in a wide ratio, in relation to various factors such as, for example the weeds to be controlled, the degree of infestation, the climatic conditions, the characteristics of the soil and the application method.
For practical use in agriculture, the composition or formulation of the present invention can be applied in such quantities as to guarantee applicative dosages of the synergistic combination.
In one embodiment, it is a particular benefit of the compositions of the present invention that they have a very good post-emergence herbicidal activity. Thus, in a preferred embodiment of invention, the compositions are applied post-emergence, i.e. during and/or after, the emergence of the weeds. It is particularly advantageous to apply the mixtures according to the invention as post emergent when the weeds start with leaf development up to flowering. Since the composition show good crop tolerance, even when the crop has already emerged, they can be applied after seeding of the crop plants and in particular during or after the emergence of the crop plants.
In one embodiment, the present invention relates to a composition of bispyribac-sodium, fenoxaprop-p-ethyl and Polycarboxylate salt comprising organic or inorganic carrier material, including agriculturally acceptable additive(s) selected from the group comprising of solid carrier(s), surfactant(s), binder(s), disintegrating agent(s), wetting agent(s), pH adjuster(s), thickener(s), filler(s), diluent(s), anti-caking agent(s), defoaming agent(s), buffering agent(s), and/or coloring agent(s) or combination thereof. The composition may also contain if desired, one or more auxiliaries customary for crop protection compositions.
Solid carrier(s) are selected from the group comprising of, but are not limited to, pyrophyllite clay, silica, precipitated silica, kaolin clay, kieselguhr, chalk, diatomaceous earth, lime, calcium carbonate, bentonite clay, Fuller's earth, talc, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, attapulgite, walnut shell flour, lignin, cellulose etc. These solid carriers may be used alone or in combination thereof. On the other hand, solid carriers may act as structurants.
Surfactant(s) are nonionic or anionic surfactants or a combination of these surfactants. It is preferred to use one or more than one kind of surfactant. Surfactant(s) is selected from the group comprising of, but not limited to, sugar esters such as sorbitan monolaurate, polyoxyethylene sorbitan monolaurate; sodium alkylethersulfate, sodium lauryl sulfate, sodium dodecyl sulfate; C1-C30 alkylcarboxylate, C1-C20 hydroxyalkylcarboxylate, polymer containing carboxylate, arylcarboxylate, alkylx (e.g. aliphatic di- and tricarboxylates) having 2 to 32 carbon atoms, such as aconitic acid, adipic acid, aspartic acid, citric acid, fumaric acid, galactaric acid, glutamic acid, glutaric acid, oxoglutaric acid, maleic acid, malic acid, malonic acid, oxalate, sebacic acid, succinic acid, tartaric acid; alkyl polyglucoside such as decyl glucoside; polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, or polyoxyethylene coconut fatty alcohol ether; polyoxyethylene alkynyl ether such as polyoxyethylene 2,4,7,9-tetramethyl-5-decyn-4,7-diol ether; polyoxyethylene aryl ethers such as polyoxyethylene nonylphenyl ether or polyoxyethylene tristyrylphenyl ether; polyoxyethylene vegetable oil ethers such as polyoxyethylene castor oil or polyoxyethylene hydrogenated castor oil; vegetable oil ethoxylate; C6-C20 linear and branched alcohol ethoxylates, C6-C20 alcohol propoxylates, C6-C20 propoxylated and ethoxylated alcohols; polyoxyethylene fatty acid esters such as polyoxyethylene monolaurate, polyoxyethylene distearate or polyoxyethylene resin acid ester; polyoxyethylene polyoxypropylene (EO-PO) block copolymers such as Pluronic®; polyoxyethylene polyoxypropylene alkyl ether such as polyoxyethylene polyoxypropylene lauryl ether; polyoxyethylene polyoxypropylene aryl ether such as polyoxyethylene polyoxypropylene styrylphenyl ether; a modified styrene acrylic polymer, polyoxyethylene alkyl amines such as polyoxyethylene stearyl amine; polyoxyethylene fatty acid amide such as lauric acid diethanolamid; fluorinated surfactant; alkyl sulfates such as sodium lauryl sulfate; sodium alkylbenzene sulfonate, calcium alkylbenzene sulphonate; polyoxyethylene alkyl ether sulfates such as sodium polyoxyethylene lauryl ether sulfate; polyoxyethylene aryl ether sulfates such as sodium polyoxyethylene nonylphenyl ether sulfate or ammonium polyoxyethylene tristyrylphenyl ether sulfate; aryl sulfonate such as calcium benzene sulfonate calcium dodecyl benzene sulfonate, sodium naphthalene sulfonate, sodium salt of naphthalene sulfonate condensate (MORWET® D-425) or sodium naphthalene sulfonate formaldehyde condensate; poly aryl phenyl ether sulphate ammonium salt; ‘alpha’-olefin sulfonate; lauryl sulfosuccinate, laureth sulfosuccinate, laureth-5 sulfosuccinate, ricinoleamide MEA sulfosuccinate, undecylenearnide MEA sulfosuccinate, diisobutyl sulfosuccinate, dioctyl sulfosuccinate, dihexyl sulfosuccinate, dicyclohexyl sulfosuccinate, diisodecyl sulfosuccinate, diisotridecyl sulfosuccinate, di-2-ethylhexyl sulfosuccinate, di-2-methylamyl sulfosuccinate, dimethylamyl sulfosuccinate, dibutylhexyl sulfosuccinate, diisooctyl sulfosuccinate or their alkali metal salts, sodium lignosulfonate; polycarboxylic acid sodium salt; N-methyl fatty acid sarcosinate; polyoxyethylene alkyl ether phosphate; polyoxyethylene aryl ether phosphates such as polyoxyethylene phenyl ether phosphate; polyoxyethylene alkyl phenyl ether phosphate; graft co-polymers such as polymethyl methacrylate-polyethylene glycol graft copolymer. These surfactants may be used alone or in combination thereof.

Suitable stabilizing surfactants include anionic, cationic, nonionic and amphoteric surfactants, block polymers and polyelectrolytes. Further on, polysaccharide (e.g. starch, starch derivatives, cellulose derivatives, xanthan gum, and gelatin) may be used as stabilizing surfactants. Preferred stabilizing surfactants are nonionic surfactants (preferably alkoxylates, such as comb polymers) and/or block polymers, and EO-PO block copolymers. Mixtures of aforementioned stabilizing surfactants are also suitable. On the other hand, surfactants may act as detergents, wetting agents, emulsifiers, foaming agents, dispersants/dispersing agents, spreader, adjuvant for penetration enhancement, rain fastness, or soil leaching control etc.

Wetting agent(s) is selected from the group comprising of, but not limited to, one or more of dioctyl sulfosuccinate, poly oxy alkylene alkyl ether, poly oxy alkylene alkyl phenyl ether sulfonates, dialkylsuccinate, Sodium blend of alkyl naphthalene sulfonate, sodium dioctyl sulphosuccinate & sodium lauryl sulfonate preferably sodium lauryl sulfate, sodium lauryl ether sulfate blend of alkyl naphthalene sulfonate etc.

Binder(s) is selected from the group comprising of, but not limited to, one or more of polyvinyl alcohol, dextrin, denatured dextrin, soluble starch, sodium polycarbonate, carboxymethyl cellulose, lactose, Polyvinylpyrrolidone, polyacrylates and bentonite.
pH adjuster(s) is selected from the group comprising of, but not limited to, one or more of sodium or potassium carbonate, sodium or potassium hydrogen carbonate, sodium or potassium dihydrogenphosphate, disodium or dipotassium hydrogenphosphate, citric acid, malic acid and triethanolamine, or a combination thereof.
Filler(s) is selected from the group comprising of, but not limited to, bentonite, perlite, talc, kaolin, sodium sulphate, aluminium silicate, diatomaceous earth, attapulgite, barium sulfate, mica, zeolites, calcium carbonate, fused sodium potassium, precipitated silica, precipitated silicates, aluminium silicate, sodium citrate, potassium citrate, magnesium citrate, and clay. These fillers may be used alone or in combination thereof.

In another embodiment, the present invention comprises wetting agent and Polycarboxylate salt in a weight ratio of 1:15 to 15:1, more preferably from 1: 7.5 to 7.5:1, most preferably from 1:5 to 5:1.

The herbicidal combination of the present invention maybe used to target weeds among the crops such corn, rice, wheat, barley, rye, oat, sorghum, cotton, soybean, common bean, hemp, peanut, buckwheat, beet, rapeseed, sunflower, sugar cane, tobacco, etc.; vegetables: solanaceous vegetables such as eggplant, tomato, pimento, pepper, potato, etc., cucurbit vegetables such as cucumber, pumpkin, zucchini, water melon, melon, squash, etc., cruciferous vegetables such as radish, white turnip, horseradish, kohlrabi, Chinese cabbage, cabbage, leaf mustard, broccoli, cauliflower, etc., asteraceous vegetables such as burdock, crown daisy, artichoke, lettuce, etc, liliaceous vegetables such as green onion, onion, garlic, and asparagus, ammiaceous vegetables such as carrot, parsley, celery, parsnip, etc., chenopodiaceous vegetables such as spinach, Swiss chard, etc., lamiaceous vegetables such as Perilla frutescens, mint, basil, etc, strawberry, sweet potato, Dioscorea japonica, colocasia, etc., flowers, foliage plants, turf grasses, fruits: pome fruits such apple, pear, quince, etc, stone fleshy fruits such as peach, plum, nectarine, Prunus mume, cherry fruit, apricot, prune, etc., citrus fruits such as orange, lemon, rime, grapefruit, etc., nuts such as chestnuts, walnuts, hazelnuts, almond, pistachio, cashew nuts, macadamia nuts, etc. berries such as blueberry, cranberry, blackberry, raspberry, etc., vines, kaki fruit, olive, plum, banana, oil palm, coffee, date palm, coconuts, etc., trees other than fruit trees; tea, mulberry, flowering plant, trees such as ash, birch, dogwood, Eucalyptus, Ginkgo biloba, lilac, maple, Quercus, poplar, Judas tree, Liquidambar formosana, plane tree, zelkova, Japanese arborvitae, fir wood, hemlock, juniper, Pinus, Picea, and Taxus cuspidate, etc.
Thus, in another aspect, the present invention provides a method of controlling weeds at a locus, the method comprising applying a combination comprising bispyribac-sodium, fenoxaprop-p-ethyl and Polycarboxylate salt to the locus.
In an embodiment, the present invention provides a method of controlling weeds at a locus for the burndown of weeds, said method comprising application at the locus of the weed a synergistic combination of bispyribac-sodium, fenoxaprop-p-ethyl and isoxadifen-ethyl.
In one embodiment, the compositions of the present invention are in particular suitable for controlling weeds of rice crop (direct seeded rice as well as transplanted rice). The compositions can be applied post-emergence, i.e. after emergence of the weeds.
The target weeds may be selected from Urticaceae weeds: Urtica urens Polygonaceae weeds: Polygonum convolvulus, Polygonum lapathifolium, Polygonum pensylvanicum, Polygonum persicaria, Polygonum longisetum, Polygonum aviculare, Polygonum arenastrum, Polygonum cuspidatum, Rumex japonicus, Rumex crispus, Rumex obtusifolius, Rumex acetosa; Portulacaceae weeds: Portulaca oleracea; Caryophyllaceae weeds: Stellaria media, Cerastium holosteoides, Cerastium glomeratum, Spergula arvensis, Silene gallica Molluginaceae weeds: Mollugo verticillata; Chenopodiaceae weeds: Chenopodium album, Chenopodium ambrosioides, Kochia scoparia, Salsola kali, Atriplex spp.; Amaranthaceae weeds: Echinochloa colona, Echinochloa Crus-galli, Leptochloa chinensis, Cyperus iria Cyperus difformis, Fimbristylis Spp., Monochoria vaginalis, Eclipta alba, Ludwigia Spp., Sagittaria Spp. and Marsilea Spp.; Amaranthus retroflexus, Amaranthus viridis, Amaranthus lividus, Amaranthus spinosus, Amaranthus hybridus, Amaranthus palmeri, Amaranthus rudis, Amaranthus patulus, Amaranthus tuberculatos, Amaranthus blitoides, Amaranthus deflexus, Amaranthus quitensis, Alternanthera philoxeroides, Alternanthera sessilis, Alternanthera tenella; Papaveraceae weeds: Papaver rhoeas, Argemone Mexicana; Brassicaceae weeds: Raphanus raphanistrum, Raphanus sativus, Sinapis arvensis, Capsella bursa-pastoris, Brassica juncea, Brassica campestris, Descurainia pinnata, Rorippa islandica, Rorippa sylvestris, Thlaspi arvense, Myagrum rugosum, Lepidium virginicum, Coronopus didymus; Dinebra weeds: Dinebra Americana, Dinebra aquatic, Dinebra aristidoides, Dinebra bromoides, Dinebra calycina, Dinebra caudata, Dinebra chinensis, Dinebra chloride, Dinebra chondrosioides, Dinebra coerulescens, Dinebra cristata, Dinebra curtipendula, Dinebra decipiens, Dinebra divaricate, Dinebra divaricatissima, Dinebra dura, Dinebra guineensis, Dinebra hirsute, Dinebra hirta, Dinebra juncifolia, Dinebra ligulata, Dinebra lima, Dinebra melicoides, Dinebra nealleyi, Dinebra neesii, Dinebra panicea, Dinebra panicoides, Dinebra pubescens, Dinebra repens, Dinebra scabra, Dinebra secunda, Dinebra simoniana, Dinebra southwoodii, Dinebra squarrosa, Dinebra srilankensis, Dinebra tuaensis, Dinebra verticillate, Dinebra retroflexa. Dinebra haareri, Dinebra marquisensis, Dinebra perrieri, Dinebra polycarpha, Dinebra somalensis Capparaceae weeds: Cleome affinis; Fabaceae weeds: Aeschynomene indica, Aeschynomene rudis, Sesbania exaltata, Cassia obtusifolia, Cassia occidentalis, Desmodium tortuosum, Desmodium adscendens, Trifolium repens, Pueraria lobata, Vicia angustifolia, Indigofera hirsuta, Indigofera truxillensis, Vigna sinensis; Oxalidaceae weeds: Oxalis corniculata, Oxalis strica, Oxalis oxyptera; Geraniaceae weeds: Geranium carolinense, Erodium cicutarium; Euphorbiaceae weeds: Euphorbia helioscopia, Euphorbia maculate, Euphorbia humistrata, Euphorbia esula, Euphorbia heterophylla, Euphorbia brasiliensis, Acalypha australis, Croton glandulosus, Croton lobatus, Phyllanthus corcovadensis, Ricinus communis; Malvaceae weeds: Abutilon theophrasti, Sida rhombiforia, Sida cordifolia, Sida spinosa, Sida glaziovii, Sida santaremnensis, Hibiscus trionum, Anoda cristata, Malvastrum coromandelianum Sterculiaceae weeds: Waltheria indica; Violaceae weeds: Viola arvensis, Viola tricolor; Cucurbitaceae weeds: Sicyos angulatus, Echinocystis lobata, Momordica charantia; Lythraceae weeds: Lythrum salicaria, Ammania baccifera; Apiaceae weeds: Hydrocotyle sibthorpioides; Sapindaceae weeds: Cardiospermum halicacabum; Primulaceae weeds: Anagallis arvensis; Asclepiadaceae weeds: Asclepias syriaca, Ampelamus albidus; Rubiaceae weeds: Galium aparine, Galium spurium var. echinospermon, Spermacoce latifolia, Richardia brasiliensis, Borreria alata; Convolvulaceae weeds: Ipomoea nil, Ipomoea hederacea, Ipomoea purpurea, Ipomoea hederacea var. integriuscula, Ipomoea lacunosa, Ipomoea triloba, Ipomoea acuminata, Ipomoea hederifolia, Ipomoea coccinea, Ipomoea quamoclit, Ipomoea grandifolia, Ipomoea aristolochiafolia, Ipomoea cairica, Convolvulus arvensis, Calystegia hederacea, Calystegia japonica, Merremia hedeacea, Merremia aegyptia, Merremia cissoides, Jacquemontia tamnifolia; Boraginaceae weeds: Myosotis arvensis; Lamiaceae weeds: Lamium purpureum, Lamium amplexicaule, Leonotis nepetaefolia, Hyptis suaveolens, Hyptis lophanta, Leonurus sibiricus, Stachys arvensis; Solanaceae weeds: Datura stramonium, Solanum nigrum, Solanum Americanum, Solanum ptycanthum, Solanum sarrachoides, Solanum rostratum, Solanum aculeatissimum, Solanum sisymbriifolium, Solanum carolinense, Physalis angulata, Physalis subglabrata, Nicandra physaloides; Scrophulariaceae weeds: Veronica hederaefolia, Veronica persica, Veronica arvensis; Plantaginaceae weeds: Plantago asiatica; Asteraceae weeds: Xanthium pensylvanicum, Xanthium occidentale, Helianthus annuus, Matricaria chamomilla, Matricaria perforata, Chrysanthemum segetum, Matricaria matricarioides, Artemisia princeps, Artemisia vulgaris, Artemisia verlotorum, solidago altissima, Taraxacum officinale, Galinsoga ciliata, Galinsoga parviflora, Senecio vulgaris, Senecio brasiliensis, Senecio grisebachii, Conyza bonariensis, Conyza canadensis, Ambrosia artemisiaefolia, Ambrosia trifida, Bidens pilosa, Bidens frondosa, Bidens subalternans, Cirsium arvense, Cirsium vulgare, Silybum marianum, Carduus nutans, Lactuca serriola, Sonchus oleraceus, Sonchus asper, Wedelia glauca, Melampodium perfoliatum, Emilia sonchifolia, Tagetes minuta, Blainvillea latifolia, Tridax procumbens, Porophyllum ruderale, Acanthospermum australe, Acanthospermum hispidum, Cardiospermum halicacabum, Ageratum conyzoides, Eupatorium perfoliatum, Eclipta alba, Erechtites hieracifolia, Gamochaeta spicata, Gnaphalium spicatum, Jaegeria hirta, Parthenium hysterophorus, Siegesbeckia orientalis, Soliva sessilis; Liliaceae weeds: Allium canadense, Allium vineale; Commelinaceae weeds: Commelina communis, Commelina bengharensis, Commelina erecta; Poaceae weeds: Echinochloa crus-galli, Setaria viridis, Setaria faberi, Setaria glauca, Setaria geniculata, Digitaria ciliaris, Digitaria sanguinalis, Digitaria horizontalis, Digitaria insularis, Eleusine indica, Poa annus, Alospecurus aequalis, Alopecurus myosuroides, Avena fatua, Sorghum halepense, Sorghum vulgare, Agropyron repens, Lolium multiflorum, Lolium perenne, Lolium rigidum, Bromus secalinus, Bromus tectorum, Hordeum jubatum, Aegilops cylindrica, Phalaris arundinacea, Phalaris minor, Apera spica-venti, Panicum dichotomiflorum, Panicum texanum, Panicum maximum, Brachiaria platyphylla, Brachiaria ruziziensis, Brachiaria plantaginea, Brachiaria decumbens, Brachiaria brizantha, Brachiaria humidicola, Cenchrus echinatus, Cenchrus pauciflorus, Eriochloa villosa, Pennisetum setosum, Chloris gayana, Eragrostis pilosa, Rhynchelitrum repens, Dactyloctenium aegyptium, Ischaemum rugosum, Oryza sativa, Paspalum notatum, Paspalum maritimum, Pennisetum clandestinum, Pennisetum setosum, Rottboellia cochinchinensis; Cyperaceae weeds: Cyperus microiria, Cyperus iria, Cyperus odoratus, Cyperus rotundus, Cyperus esculentus, Kyllinga gracillima, Equisetaceae weeds: Equisetum arvense, Equisetum palustre, Trianthema weeds, Onagraceae weeds: Ludwigia parviflora and the like.

The herbicidal combination of the present invention maybe used to control the target weeds among the crops such as GMO (Genetically Modified Organism) and Non GMO varieties of Cotton (Gossypium spp.), Paddy (Oryza sativa), Wheat (Triticum aestavum), Barley (Hordeum vulgare), Maize (Zea mays), Sorghum (Sorghum bicolor), Oat (Avena sativa), Pearl millet (Pennisetum glaucum), Sugarcane (Saccharum officinarum), Sugarbeet (Beta vulgaris), Soybean (Glycin max), Peanut (Arachis hypogaea), Sunflower (Helianthus annuus), Mustard (Brassica juncea), Rape seed (Brassica napus), Linseed (Linum usitatissimum), Sesame (Sesamum indicum), Green gram (Vigna radiata), Black gram (Vigna mungo), Chickpea (Cicer aritinum), Cowpea (Vigna unguiculata), Redgram (Cajanus cajan), Frenchbean (Phaseolus vulgaris), Indian bean (Lablab purpureus), Horse gram (Macrotyloma uniflorum), Field pea (Pisum sativum), Cluster bean (Cyamopsis tetragonoloba), Lentils (Lens culinaris), Brinjal (Solanum melongena), Cabbage (Brassica oleracea var. capitata), Cauliflower (Brassica oleracea var. botrytis), Okra (Abelmoschus esculentus), Onion (Allium cepa L.), Tomato (Solanum lycopersicun), Potato (Solanum tuberosum), Sweet potato (Ipomoea batatas), Chilly (Capsicum annum), Garlic (Allium sativum), Cucumber (Cucumis sativus), Muskmelons (Cucumis melo), Watermelon (Citrullus lanatus), Bottle gourd (Lagenaria siceraria), Bitter gourd (Momordica charantia), Radish (Raphanus sativus), Carrot (Dacus carota subsp. sativus), Turnip (Brassica rapa subsp rapa), Apple (Melus domestica), Banana (Musa spp.), Citrus groups (Citrus spp.), Grape (Vitis vinifera), Guava (Psidium guajava), Litchi (Litchi chinensis), Mango (Mangifera indica), Papaya (Carica papaya), Pineapple (Ananas comosus), Pomegranate (Punica granatum), Sapota (Manilkara zapota), Tea (Camellia sinensis), Coffea (Coffea Arabica), Turmeric (Curcuma longa), Ginger (Zingiber officinale), Cumin (Cuminum cyminum), Fenugreek (Trigonella foenum-graecum), Fennel (Foeniculum vulgare), Coriander (Coriandrum sativum), Ajwain (Trachyspermum ammi), Psyllium (Plantago ovate), Black Pepper (Piper nigrum), Stevia (Stevia rebaudiana), Safed musli (Chlorophytum tuberosum), Drum stick (Moringa oleifera), Coconut (Coco nucifera), Mentha (Mentha spp.), Rose (Rosa spp.), Jasmine (Jasminum spp.), Marigold (Tagetes spp.), Common daisy (Bellis perennis), Dahlia (Dahlia hortnesis), Gerbera (Gerbera jamesonii), Carnation (Dianthus caryophyllus).
In an embodiment, combination of the present invention may be applied either pre- or post-emergent. In a preferred embodiment, the combination of the present invention may be used post-emergent or 2-5 leaf stage of weed. The advantage of the combination is surprisingly good residual effects, Broad spectrum and quick burndown of the weeds when applied post-emergent.
In an another embodiment, the present invention relates to a process for preparing the novel synergistic composition comprising at least the step of granulating the components of the herbicidal formulation to obtain the desired granule size. The water dispersible granule formulation can be prepared by mixing the active ingredients, Polycarboxylate salt, safener, surfactant, binder, filler, wetting agent, pH adjusters and carrier. Usually all dry ingredients except starch are mixed uniformly in a mixer and milled by a mill such as an air jet mill to obtain particle size of 3 to 10 micrometer. The milled mixture is then kneaded by adding remaining ingredients and a mixture of starch and water, extruded and dried. Other granulation method such as spray dry or fluidized bed granulation may be used. In this case, the milled mixture is well mixed with enough amount of water to get slurry. EXAMPLES:
The present invention is further illustrated by the following examples. These examples describe possible preferred embodiments for illustrative purposes only, but they do not limit the scope of the invention. These laboratory scale experiments can be scaled up to industrial/ commercial scale.
Table:1 Different formulations comprising Bispyribac-sodium + Fenoxaprop -p-Ethyl, according to present invention, in different ratios were prepared.
Example 1 Example 2 Example 3 Example 4 Example 5 Example 6
Ingredients (% w/w) (% w/w) (% w/w) (% w/w) (% w/w) (% w/w)
Bispyribac-sodium (100%) 7.60 7.60 7.60 7.60 7.60 7.60
Fenoxaprop -p-Ethyl (100%) 11.40 11.40 11.40 11.40 11.40 11.40
Isoxadifen -Ethyl (100%) 12.80 12.80 12.80 12.80 12.80
Ppt. Silica 1.00 1.00 1.00 1.00 1.00 1.00
Dioctyl Sulfosuccinate 3.00 3.00 3.00 3.00 3.00
Sodium Polycarboxylate 8.00 8.00 8.00 8.00 8.00
Clay 45.20 53.20 58.00 48.20 51.20 48.20
Sodium Lignosulfonate 6.00 6.00 6.00 6.00 6.00
Starch 3.00 3.00 3.00 3.00 3.00
Citric acid 2.00 2.00 2.00 2.00 2.00 2.00
Total 100.00 100.00 100.00 100.00 100.00 100.00
Formulation Test Data
Suspensibility (MT 184); %w/w 92.8 56 87.3 72.1 84.7 92.2
Wettability (MT 53.3); seconds 8 26 11 48 16 11
Degree of Dispersion (MT 174); %w/w 88.30 48.1 82.4 68.6 76.8 87.9
Wet Sieve test (MT 185); %w/w 0.06 2.36 0.06 0.93 0.32 0.08
Dustiness (MT 171.1); mg 12 14 13 16 18 46

Formulation Evaluation Test Studies:
Suspensibility, Wettability, Degree of Dispersion, Wet Sieve test and Dustiness all the tests on all of the above formulations were carried out as per CIPAC guidelines set forth and the results has been provided in the table.
Stability studies of all of the above mentioned formulations were carried out as per CIPAC guidelines set forth and the same has been found to be stable.
Suspensibility property of the formulation: Surprisingly it is observed that in the Example 1 Sodium Polycarboxylate provides 92.8% w/w suspensibility properties as compared to Example 2 56% w/w; Example 3 also provides 87.3% w/w suspensibility property when Isoxadifen –Ethyl is not used in the formulation; Example 4 provides 72.1% w/w suspensibility property; Example 5 and 6 provides 84.7% w/w and 92.2% w/w suspensibility property respectively indicating other inactive excipients does not significantly affecting the suspensibility property of the formulation.

Field Experiments and Bio-efficacy Data:
Various field experiments of novel synergistic formulations of Bispyribac Sodium + Fenoxaprop –p-ethyl were carried on rice crop to evaluate their phytotoxicity and bioefficacy against different weed flora existing in rice field.
Trial 1: Phytotoxicity and Bio efficacy on direct seed rice (Oryza sativa L.)
The field experiments were conducted on rice and experimental details as below:
Location Name: Hansi, Haryana
Crop & Variety: Rice, Pusa-1121(direct seeded rice)
Experimental design: Randomized block design (R.B.D)
Replications: Three
No. of Treatments: Eight (08)
Plot size: 5m x 4m.
Application Time: 20 DAS (Days after sowing)
Spray Volume: 500 liter water per hectare
Application Equipment: Manually operated knap sack sprayer fitted with flat fat nozzle
Observations: 1, 3, 5, 7 and 10 DAA for phytotoxicity; and 14 and 28 DAA (Days after Application) for bio efficacy against weeds.
Experimental Methodology:
Rice crop was raised as per the standard agronomic practices in the field to conduct a trial to assess phytotoxicity of novel synergistic herbicidal mixtures of bispyribac sodium + fenoxaprop-p-ethyl. The trial was laid out in Randomized Block Design (RBD) with nine treatments including untreated check (UTC), replicated three times. For each treatment plot size of was 5m x 4m maintained. The application of different treatments with prescribed doses was done with manually operated knapsack sprayer fitted with flat fan nozzle. The spray volume was used at 500 l/h for spraying. The Untreated check plot was sprayed with water alone. Observations on phytotoxicity viz., yellowing, leaf tip burning and stunting, necrosis, wilting, epinasty, hyponasty was recorded at 1, 3, 5,7 and 10 days after spraying, by adopting 0-10 rating scale as below
0= No phytotoxicity, 1 =1-10%, 2=11-20%, 3=21-30%, 4=31-40%, 5=41-50%, 6=51-60%, 7=61-70%, 8=71-80%, 9=81-90% and 10=91-100% phytotoxicity.
Percent phytotoxicity was calculated by following formula:
Sum of all scores
% Phytotoxicity = ------------------------------------------------------------- X 100
Number of samples x highest rating scale
Table 3.1: Phytotoxicity on direct seeded rice
The results of the field trial presented in table 3.1 indicates that the novel synergistic herbicidal composition of Bispyribac sodium 7.60% + Fenoxaprop-p-ethyl 11.40 % WG Example 1 did not show shows any kind of Phytotoxicity to direct seeded rice. Bispyribac sodium 7.60% + Fenoxaprop-p-ethyl 11.40 % WG Example 2, 3, 4 shows minimal phytotoxicity on 3 DAA which was completely recovered on 7 DAA without affecting normal plant growth.
Table 3.1: Phytotoxicity on direct seeded rice
Sr. No. Treatment Dose/ha % Phytotoxicity in terms of yellowing, leaf tip burning, stunting, necrosis, wilting, epinasty, hyponasty etc.
(g a.i./ha) (g or ml) 1 DAA 3 DAA 5 DAA 7 DAA 10 DAA
1. Bispyribac Sodium 10% SC 38 380 0.0 0.0 0.0 0.0 0.0
2. Fenoxaprop –p-ethyl 6.9 % w/v EC 57 825 0.0 15.0 10.0 5.0 5.0
3. Bispyribac sodium 10% SC+ Fenoxaprop-P-Ethyl 6.9% EC (tank mix) 38.0 + 57 380 + 825 0.0 15.0 10.0 5.0 5.0
4. Bispyribac sodium 7.60% + Fenoxaprop-p-ethyl 11.40 % WG Example 1 38.0 + 57 500 0.0 0.0 0.0 0.0 0.0
5. Bispyribac sodium 7.60% + Fenoxaprop-p-ethyl 11.40 % WG Example 2 38.0 + 57 500 0.0 5.0 0.0 0.0 0.0
6. Bispyribac sodium 7.60% + Fenoxaprop-p-ethyl 11.40 % WG Example 3 38.0 + 57 500 0.0 10.0 5.0 0.0 0.0
7. Bispyribac sodium 7.60% + Fenoxaprop-p-ethyl 11.40 % WG Example 4 38.0 + 57 500 0.0 5.0 0.0 0.0 0.0
8. Control - - 0.0 0.0 0.0 0.0 0.0

DAA – Days after Application

Bio-efficacy Evaluation:
A synergistic effect exists wherever the action of a combination of active ingredient is greater than the sum of the action of each of the components alone. Therefore, a synergistically effective amount or an effective amount of a synergistic composition or combination is an amount that exhibits greater herbicidal activity than the sum of the herbicidal activities of the individual components.
In the field of agriculture, it is often understood that the term “synergy” is as defined by Colby S.R. in an article entitled “Calculation of the synergistic and antagonistic responses of herbicide combinations” published in the journal Weeds,1967, 15, p.20-22, incorporated herein by reference in its entirety. The action expected for a given combination of actives can be calculated as follows:
E = X + Y – (XY/100)
Where,
E = Expected % control by mixture of A and B.
X = Observed % control by product A
Y = Observed % control by product B
Ratio = Observed Control %/ Expected Control %
Ratio of O/E > 1, means synergism observed.
The synergistic herbicidal action of the novel synergistic composition can be demonstrated by the experiments below.
Post-emergence herbicide application was done around 20 days after sowing. The target weeds of rice viz., Grasses -Echinochloa colonum, Leptochloa Chinensis; Sedges-Cyperus Difformis; Broad leaf weeds- Eclipta alba, Sphenoclea Zeylanica, Ludwigia parviflora and Ammania baccifera were counted at 14 DAA and 28 DAA (Days After Application) to determine the efficacy of the products. Bio-efficacy, in terms of species wise weed count and total weed count were taken up. The % weed control was calculated by using formula mentioned below:

The % weeds control data used in Colby’s formula to calculate the synergism between the herbicide.

Table 3.2: Bio efficacy of different treatments on the weed flora in direct seeded rice
The results of the field trial presented in table 3.2 indicates that the novel synergistic herbicidal composition of Bispyribac sodium 7.60% + Fenoxaprop-p-ethyl 11.40 % WG Example 1 and Bispyribac sodium 7.60% + Fenoxaprop-p-ethyl 11.40 % WG Example 3 at 38.0 + 57 a. i./ha recorded more than 90% weed control on 14 DAA and more than 91% weed control on 28 DAA are superior for the best control of weed flora i.e. grasses, Sedges, and broadleaf weeds in rice over the other treatments of Bispyribac sodium + Fenoxaprop-P-Ethyl including tank mix i.e. Bispyribac sodium 10% SC+ Fenoxaprop-P-Ethyl 6.9% EC (tank mix). Results also indicates that novel synergistic herbicidal composition of Bispyribac sodium + Fenoxaprop-p-ethyl has improved long term bio efficacy as compared to the other treatments of Bispyribac sodium + Fenoxaprop-P-Ethyl including tank mix i.e. Bispyribac sodium 10% SC+ Fenoxaprop-P-Ethyl 6.9% EC (tank mix). Bio efficacy of novel synergistic herbicidal composition of Bispyribac sodium + Fenoxaprop-p-ethyl has increased the bio efficacy on 28DAA than 14 DAA as compared to the other treatments of Bispyribac sodium + Fenoxaprop-P-Ethyl including tank mix i.e. Bispyribac sodium 10% SC+ Fenoxaprop-P-Ethyl 6.9% EC (tank mix) where the bio efficacy has decreased on 28 DAA than 14 DAA. Colby ratios endorses that there is a synergistic effect of novel synergistic herbicidal composition of Bispyribac sodium + Fenoxaprop-p-ethyl.

Table 3.2: Bio efficacy of different treatments on the weed flora in direct seeded rice
Sr. No. Treatment Dose/ha % Weed Control Observed % Weed Control Expected Colby Ratio
o/e Yield (q/ha)
(g a. i./ha) (g or ml) 14 DAA 28 DAA 14 DAA 28 DAA 14 DAA 28 DAA
1. Bispyribac Sodium 10% SC 38 380 60.10 57.63 32.8
2. Fenoxaprop –p-ethyl 6.9 % w/v EC 57 825 48.25 43.00 30.1
3. Bispyribac sodium 10% SC+ Fenoxaprop-P-Ethyl 6.9% EC (tank mix) 38.0 + 57 380 + 825 75.01 72.33 79.35 75.85 0.95 0.95 34.9
4. Bispyribac sodium 7.60% + Fenoxaprop-p-ethyl 11.40 % WG Example 1 38.0 + 57 500 93.59 97.07 79.35 75.85 1.17 1.27 37.1
5. Bispyribac sodium 7.60% + Fenoxaprop-p-ethyl 11.40 % WG Example 2 38.0 + 57 500 74.72 70.00 79.35 75.85 0.94 0.92 34.6
6. Bispyribac sodium 7.60% + Fenoxaprop-p-ethyl 11.40 % WG Example 3 38.0 + 57 500 91.00 92.33 79.35 75.85 1.14 1.21 36.2
7. Bispyribac sodium 7.60% + Fenoxaprop-p-ethyl 11.40 % WG Example 4 38.0 + 57 500 87.50 85.02 79.35 75.85 1.10 1.12 35.1
8. Control - - 0.0 0.0 0.0 0.0 0.0 0.0 29

Weed flora (Grasses -Echinochloa colonum, Leptochloa Chinensis; Sedges-Cyperus Difformis; Broad leaf weeds- Eclipta alba, Sphenoclea Zeylanica, Ludwigia parviflora and Ammania baccifera)
DAA - Days after Application

Trial 2: Phytotoxicity and Bioefficacy on transplanted rice (Oryza sativa)
Location Name: Barabanki, Utter Pradesh
Crop & Variety: Rice, Pusa-1121(Transplanted)
Experimental design: Randomized block design (R.B.D)
Replications: Three
No. of Treatments: Eight (08)
Plot size: 5m x 4m.
Application Time: 20 DAS (Days after transplanting)
Spray Volume: 500 liter water per hectare
Application Equipment: Manually operated knap sack sprayer fitted with flat fat nozzle
Observations: 1, 3, 5, 7 and 10 DAA for phytotoxicity; and 14 and 28 DAA (Days after Application) for bio efficacy against weeds.
Experimental Methodology: Same as mentioned in Trial 1
Table 4.1: Phytotoxicity on Transplanted Rice
The results of the field trial presented in table 4.1 indicates that the novel synergistic herbicidal composition of Bispyribac sodium 7.60% + Fenoxaprop-p-ethyl 11.40 % WG Example 1 did not show any kind of Phytotoxicity to transplanted rice. Bispyribac sodium 7.60% + Fenoxaprop-p-ethyl 11.40 % WG Example 3 shows minimal phytotoxicity on 3 DAA which was completely recovered on 7 DAA without affecting normal plant growth.
Table 4.2: Bio efficacy of different treatments on the weed flora in transplanted rice
The results of the field trial presented in table 4.2 indicates that the novel synergistic herbicidal composition of Bispyribac sodium 7.60% + Fenoxaprop-p-ethyl 11.40 % WG Example 1 and Bispyribac sodium 7.60% + Fenoxaprop-p-ethyl 11.40 % WG Example 3 at 38.0 + 57 a. i./ha recorded more than 90 % weed control on 14 DAA and more than 95% weed control on 28 DAA are superior for the best control of weed flora i.e. grasses, Sedges, and broadleaf weeds in rice over the other treatments of Bispyribac sodium + Fenoxaprop-P-Ethyl including tank mix i.e. Bispyribac sodium 10% SC+ Fenoxaprop-P-Ethyl 6.9% EC (tank mix). Results also indicates that novel synergistic herbicidal composition of Bispyribac sodium + Fenoxaprop-p-ethyl has improved long term bio efficacy as compared to the other treatments of Bispyribac sodium + Fenoxaprop-P-Ethyl including tank mix i.e. Bispyribac sodium 10% SC+ Fenoxaprop-P-Ethyl 6.9% EC (tank mix). Bio efficacy of novel synergistic herbicidal composition of Bispyribac sodium + Fenoxaprop-p-ethyl has increased the bio efficacy on 28DAA than 14 DAA as compared to the other treatments of Bispyribac sodium + Fenoxaprop-P-Ethyl including tank mix i.e. Bispyribac sodium 10% SC+ Fenoxaprop-P-Ethyl 6.9% EC (tank mix) where the bio efficacy has decreased on 28 DAA than 14 DAA. Colby ratios endorses that there is a synergistic effect of novel synergistic herbicidal composition of Bispyribac sodium + Fenoxaprop-p-ethyl.

Yield:
Yield data was also recorded and presented in Table-3.2 and Table-4.2. Highest yield was recorded in the combination involving Bispyribac sodium 7.60% + Fenoxaprop-p-ethyl 11.40 % WG Example 1 @ 38.0 + 57 g a.i/ha which provided a yield of 37.1 q/ha and 35.4 q/ha at both trial locations respectively; followed by Bispyribac sodium 7.60% + Fenoxaprop-p-ethyl 11.40 % WG Example 3 @ 38.0 + 57 g a.i/ha which provided a yield of 36.2 q/ha and 34.1 q/ha at both trial locations respectively; followed by Bispyribac sodium 7.60% + Fenoxaprop-p-ethyl 11.40 % WG Example 4 @ 38.0 + 57 g a.i/ha which provided a yield of 35.1 q/ha and 34 q/ha at both trial locations respectively. In the control, lowest yield was recorded (29 q/ha and 28.8 q/ha) at both the location respectively. It is evident from the table that the combination developed for the control of weeds of rice gave good control on weeds and thereby increased the yield. Advantages to the end user customers for parameters like broaden the spectrum of activity for the control of grasses, sedges and broad leaf weeds.

Table 4.1: Phytotoxicity on transplanted rice
Sr. No. Treatment Dose/ha % Phytotoxicity in terms of yellowing, leaf tip burning, stunting, necrosis, wilting, epinasty, hyponasty etc.
(g a.i./ha) (g or ml) 1 DAA 3 DAA 5 DAA 7 DAA 10 DAA
1. Bispyribac Sodium 10% SC 38 380 0.0 0.0 0.0 0.0 0.0
2. Fenoxaprop –p-ethyl 6.9 % w/v EC 57 825 0.0 10.0 5.0 5.0 0.0
3. Bispyribac sodium 10% SC+ Fenoxaprop-P-Ethyl 6.9% EC (tank mix) 38.0 + 57 380 + 825 0.0 10.0 10.0 5.0 5.0
4. Bispyribac sodium 7.60% + Fenoxaprop-p-ethyl 11.40 % WG Example 1 38.0 + 57 500 0.0 0.0 0.0 0.0 0.0
5. Bispyribac sodium 7.60% + Fenoxaprop-p-ethyl 11.40 % WG Example 2 38.0 + 57 500 0.0 0.0 0.0 0.0 0.0
6. Bispyribac sodium 7.60% + Fenoxaprop-p-ethyl 11.40 % WG Example 3 38.0 + 57 500 0.0 10.0 5.0 0.0 0.0
7. Bispyribac sodium 7.60% + Fenoxaprop-p-ethyl 11.40 % WG Example 4 38.0 + 57 500 0.0 0.0 0.0 0.0 0.0
8. Control - - 0.0 0.0 0.0 0.0 0.0
DAA - Days after Application

Table 4.2: Bioefficacy of different treatments on the weed flora in transplanted rice
Sr. No. Treatment Dose/ha % Weed Control Observed % Weed Control Expected Colby Ratio
o/e Yield (q/ha)
(g a. i./ha) (g or ml) 14 DAA 28 DAA 14 DAA 28 DAA 14 DAA 28 DAA
1. Bispyribac Sodium 10% SC 38 380 58.6 49.8 31.2
2. Fenoxaprop –p-ethyl 6.9 % w/v EC 57 825 45.2 40.05 29.7
3. Bispyribac sodium 10% SC+ Fenoxaprop-P-Ethyl 6.9% EC (tank mix) 38.0 + 57 380 + 825 74.71 68.67 77.31 69.91 0.97 0.98 33.8
4. Bispyribac sodium 7.60% + Fenoxaprop-p-ethyl 11.40 % WG Example 1 38.0 + 57 500 90.59 97.60 77.31 69.91 1.17 1.39 35.4
5. Bispyribac sodium 7.60% + Fenoxaprop-p-ethyl 11.40 % WG Example 2 38.0 + 57 500 75.63 69.00 77.31 69.91 0.97 0.98 33.3
6. Bispyribac sodium 7.60% + Fenoxaprop-p-ethyl 11.40 % WG Example 3 38.0 + 57 500 90.50 95.30 77.31 69.91 1.17 1.36 34.1
7. Bispyribac sodium 7.60% + Fenoxaprop-p-ethyl 11.40 % WG Example 4 38.0 + 57 500 88.60 86.75 77.31 69.91 1.14 1.24 34
8. Control - - 0.0 0.0 0.0 0.0 0.0 0.0 28.8

Weed flora (Grasses -Echinochloa colonum, Leptochloa Chinensis; Sedges-Cyperus Difformis; Broad leaf weeds- Eclipta alba, Sphenoclea Zeylanica, Ludwigia parviflora and Ammania baccifera)
DAA - Days after Application
, Claims:WE CLAIM:

1. A herbicidal composition comprising:
a) bispyribac-sodium;
b) fenoxaprop-P-ethyl; and
c) Polycarboxylate salts.

2. The herbicidal composition as claimed in claim 1, wherein bispyribac-sodium is in range of 5-10 wt.%, fenoxaprop-P-ethyl in range of 10-15 wt.%, and Polycarboxylate salt in the range of 1-25 wt.% of the total composition.

3. The herbicidal composition as claimed in claim 1, wherein the Polycarboxylate salt is a water soluble alkali metal salt of polycarboxylic acid preferably selected from sodium Polycarboxylate or potassium polycarboxylate or combination thereof.

4. The herbicidal composition as claimed in claim 1, wherein the molecular weight of the polycarboxyalte salt is from 1500 to 10000, preferably from 1500 to 5000.

5. The herbicidal composition as claimed in claim 1, wherein the herbicidal composition further comprises 5 wt. % to 25 wt.% of at least one safener Isoxadifen Ethyl.

6. The herbicidal composition as claimed in claim 1, wherein the herbicidal composition further comprises 30 wt. % to 70 wt.% of at least one organic or inorganic carrier material including agriculturally acceptable formulation additives such as surfactant, solid carrier, binder, disintegrating agent, wetting agent, pH adjuster, and thickener, and/or a mixtures thereof.

7. The herbicidal composition as claimed in claim 1 , wherein the composition is in the form of solid formulations such as wettable powder (WP), dustable powder (DP), or Water Dispersible Granules (WDG/WG).

8. The herbicidal composition as claimed in claim 6, wherein the suitable solid carriers includes natural minerals (such as talc, kaolinite, kaolin clay, pyrophyllite, montmorillonite, attapulgite, bentonite, calcite, diatomaceous earth), synthetic minerals (such as precipitated silica, fumed silica and calcium carbonate), inorganic salts (such as calcium carbonate, ammonium sulfate, sodium sulfate, potassium chloride) and organic materials (such as urea, lactose, starch, cellulose, plant powders) , or a combination thereof.

9. The herbicidal composition as claimed in claim 6, wherein the pH adjusters is selected from sodium or potassium carbonate, sodium or potassium hydrogen carbonate, sodium or potassium dihydrogenphosphate, disodium or dipotassium hydrogenphosphate, citric acid, malic acid and triethanolamine, or a combination thereof.

10. The herbicidal composition as claimed in claim 6, wherein the wetting agent is selected from dioctyl sulfosuccinate, poly oxy alkylene alkyl ether, poly oxy alkylene alkyl phenyl ether sulfonates, dialkylsuccinate, Sodium blend of alkyl naphthalene sulfonate, sodium dioctyl sulphosuccinate, sodium lauryl sulfonate, sodium lauryl ether sulfate, blend of alkyl naphthalene sulfonate, or combination thereof.

11. The herbicidal composition as claimed in claim 1, wherein the weight ratio of wetting agent to Polycarboxylate salt is weight ratio of 1:15 to 15:1, more preferably from 1: 7.5 to 7.5:1, most preferably from 1:5 to 5:1.

12. The herbicidal composition as claimed in claim 6, wherein the filler is selected from bentonite, perlite, talc, kaolin, sodium sulphate, aluminium silicate, diatomaceous earth, attapulgite, barium sulfate, mica, zeolites, calcium carbonate, fused sodium potassium, precipitated silica, precipitated silicates, aluminium silicate, sodium citrate, potassium citrate, magnesium citrate, clay or combination thereof.

13. The herbicidal composition as claimed in claim 6, wherein the binder is selected from polyvinyl alcohol, dextrin, denatured dextrin, soluble starch, sodium polycarbonate, carboxymethyl cellulose, bentonite, lactose, Polyvinylpyrrolidone, polyacrylates or combination thereof.

14. The herbicidal composition as claimed in claim 6, wherein the suitable surfactants is selected from sugar esters (such as sorbitan monolaurate, polyoxyethylene sorbitan monolaurrate), polyoxyethylene alkyl ethers (such as polyoxyethylene lauryl ether or polyoxyethylene coconut fatty alcohol ether), polyoxyethylene aryl ethers (such as polyoxyethylene nonylphenyl ether or polyoxyethylene trystyrylphenyl ether), polyoxyethylene vegetable oil ethers (such as polyoxyethylene castor oil), polyoxyethylene fatty acid esters (such as polyoxyethylene monolaurate), polyoxyethylene polyoxypropylene block co-polymers, polyoxyethylene polyoxypropylene alkyl ether (such as polyoxyethylene polyoxypropylene lauryl ether), polyoxyethylene alkyl amines (such as polyoxyethylene stearyl fatty amine), alkyl sulfates (such as sodium lauryl sulfate), polyoxyethylene alkyl ether sulfates (such as sodium polyoxyethylene lauryl ether sulfate), polyoxyethylene aryl ether sulfates (such as sodium polyoxyethylene nonylphenyl ether sulfate or ammonium polyoxyethylene tristyrylphenyl ether sulfate), alkane sulfonates (such as sodium dodecyl sulfonate), ‘alpha’-olefin sulfonate, aryl sulfonates (such as sodium dodecylbenzene sulfonate, sodium naphthalene sulfonate sodium alkylnaphthalene sulfonate, sodium naphthalene sulfonate formaldehyde condensate or sodium alkyl diphenyl ether sulfonate), alkylsulfosuccinates (such as sodium dioctylsulfosuccinate), sodium lignosulfonates, polyoxyethylene alkyl ether phosphate, polyoxyethylene aryl ether phosphates (such as polyoxyethylene phenyl ether phosphate), polyoxyethylene polyoxypropylene block co-polymer phosphate, alkyl polyglucoside or combination thereof.

15. A process for the preparation of the herbicidal composition as claimed in claim 1, wherein said process comprising the step of:
a) mixing the active ingredients and agriculturally acceptable formulation additives,
b) pulverizing the resulting mixture by air jet mill or colloidal mill to obtain particle size of 3 to 10 micrometer;
c) Mixing the pulverized mixture by blender uniformly; and
d) Optionally mixing the above mixture with water and extruding the resulting mixture to form granules.

16. The herbicidal composition as claimed in claim 1, wherein the said composition is to be used in management of target weeds of rice viz., Grasses -Echinochloa colonum, Leptochloa Chinensis; Sedges-Cyperus Difformis; Broad leaf weeds- Eclipta alba, Sphenoclea Zeylanica, Ludwigia parviflora and Ammania baccifera.

Dated this 29th day of November, 2023.