The present invention relates to synergistic granular herbicidal composition for weed control in paddy crop. More particularly, the present invention relates to a storage stable synergistic granular herbicidal composition comprising (A) Penoxsulam or its agrochemically acceptable salts, derivatives in the range of 0.01 to 0.99% by weight of the composition; and (B) Pyrazosulfuron ethyl or its agrochemically acceptable salts, derivatives in the range of 0.01 to 0.99% by weight of the composition and (C) Bispyribac sodium or its agrochemically acceptable salts, derivatives in the range of 0.01 to 0.99% by weight of the composition. The present invention also relates to process for preparing such synergistic granular herbicidal composition for weed control in paddy crop.

BACKGROUND OF THE INVENTION

Weeds are undesirable plants that can severely damage yield in crops. Farmers usually control these plants at the pre-plant stage as well as after sowing. The weeds can reduce field crop yields by competing for water, sunlight and nutrients. Profitable crop production depends on effective weed control. Herbicides are pesticides useful for killing or controlling unwanted plants/weeds. The agriculture industry uses a wide range of herbicides, primarily to control undesired growth of weeds which interfere with growth, development, yield and quality of agricultural crops. More so, they are used to provide an optimum environment for growth and propagation of plant varieties. Modern herbicides are used to either control or suppress these undesirable plants so as to allow sown crops a greater share of nutrient.

Weeds are endemic in crops and a constant problem in crop production because of their dynamic nature. Despite modern control practices aimed at weed elimination, weed continues to be a ubiquitous and recurrent threat for crop production due to its ability to shift in response to management practices and environmental conditions. Because of the diversity and plasticity of weed communities, weed management should include diverse approaches and to be viewed as a continuous process. Physical, cultural, and biological weed management was the only weed control strategy till 1940s. Since the introduction of herbicides, their amazing performance led to the belief that herbicide would solve the weed problem to large extent. But concern over the escalating problems of herbicide persistence and resistance in weeds and herbicide toxicity to crop has reinforced the need for an ideal composition comprising herbicidal combination for comprehensive and one-shot weed management solution. Herbicides are often blamed for environmental pollution and impoverishment of the natural flora and fauna in agro ecosystem. Long term efficacy and sustainability issues are also the driving forces behind the reconsideration of an ideal herbicidal composition dependent weed management.

Amongst the most important crops grown across India and major parts of the world, is rice/paddy. The world’s rice demand is projected to increase by 25% from 2001 to 2025 to keep pace with population growth. Meeting this ever-increasing rice demand in a sustainable way with shrinking resources therefore presents a great challenge. Part of this resource shortage comes from less available water for irrigation and labor force urbanization in developing countries that also happen to be major rice producers. Further, weeds are a major source of yield reduction in rice production. The worldwide estimated loss in rice yield from weeds is around 10% of the total production. The hot and wet rice cultivation environment lends itself especially well to weed proliferation. Weed factors that affect rice yield include weed species, weed density, and weed competition timing. Weed competition timing refers to the time window during which a weed species will have its maximum impact on crop yield due to its particular growth characteristics. In the absence of an effective weed control program, weeds will outgrow rice.

The main challenge to controlling all major weeds with a one-shot application is the aforementioned weed competition timing. For example, Echinochloa crus-galli, which could cause 70% of rice yield loss, needs to be controlled in the rice early season while Heteranthera limosa, 21% of yield loss, needs to be eliminated in the rice middle season. Combined with an herbicide’s natural post-application tendency to quickly lose its activity owing to binding to the soil and/or degradation processes, it becomes hard for a single/solo herbicide application to account for all major weed varieties during the entirety of a rice cycle which generally spans 110-160 days. Thus, the need arises to develop and formulate a synergistic composition comprising two or more than two herbicides that can control all major rice weeds in both pre-emergence and post emergence stage, while not harmful to paddy rice.

Most important factor, which requires consideration while for such synergistic herbicidal compositions which have post-emergence and pre-emergence application, is that application of such herbicidal compositions ought to be user friendly, convenient and cost effective, while effectively control major varieties of weeds affecting paddy. The technique of broadcasting while application of such herbicidal composition is required to be followed for effective control coverage of weeds spanning large areas of water in which paddy is sown. Further, conventional herbicidal compositions formulated as wettable powder or water dispersible granules require mixing & dilution with water before application on the weeds. Thus, the need arises to arrive at synergistic herbicidal formulations in granular form, which are user friendly to the farmers, cost effective and saves time while effectively controlling broad spectrum of weeds affecting paddy spread across large areas. Granular formulation also eliminates the risk of inhalation or dermal toxicity.

A majority of the commercially available herbicides are selective in their action. A common problem with selective herbicides is its weed control spectrum, meaning the range of weed species effectively controlled by the herbicide, does not cover the full diversity of weeds affecting paddy and are not broad spectrum in nature. It is therefore, a practice to apply two or more herbicides simultaneously in order to achieve maximum spectrum of control. But it requires a lot of human ingenuity and rigorous efforts to identify specific formulation/composition having compatibility between the active ingredients and the specific ratios/weight percentage in which these components/herbicides must be mixed so as to obtain the maximum desired results.

In response to aforesaid problems, rice farming has been challenged to adopt a weed management strategy more respectful for environment. Weed management continues to be a huge challenge in aerobic rice which is highly vulnerable to weed infestation because of dry ploughing and aerobic soil conditions but it is never the less under upland transplanted conditions as well. Proper weed management is considered to be one of the most important prerequisites to ensure satisfactory yield of rice. High weed pressure in direct seeded rice lowers the economic return, and in extreme cases rice cultivation results in a losing concern. This demands reappearance of physical, cultural, and biological weed management combined with judicious application of herbicides based on a thorough understanding in the crop-weed ecology, known as comprehensive weed management (CWM). The CWM is a component of integrated pest management which involves the integration of effective, environmentally safe, and socially acceptable control tactics that reduce weed interference below the economic injury level. The CWM has got the potential to reduce herbicide use and to provide a robust and sustainable weed management of various types of weeds in rice crop. The ultimate challenge towards developing an effective CWM is to create a cropping system unfavourable for weeds and favourable for crop with proper herbicide treatment to control/supress all the different types of weeds affecting paddy.

Although weed management is herbicide dominated in many rice belts, there are strong indications that it will change in future. Because farmers are now very much concerned about the advent of herbicide resistance and unwarranted environmental hazard, and therefore are becoming increasingly interested in one-shot weed management approach, many farmers are using CWM approach for controlling weeds by mixing two or more herbicides as tank mix, which is unscientific and may do harm to crop rather than doing any good to the targeted crop also to some extent are hard to measure. None of the control measures in single can provide acceptable levels of weed control, and therefore, various components are to be integrated in a logical premix herbicides combinations, which are a new trend. But all those tools may not work in every situation or with every weed/crop species. Therefore, before comprehensive weed management, various combination of herbicides need to be evaluated for their efficacy.

Penoxsulam is a triazolopyrimidine sulfonamide herbicide, which is a post-germination herbicide having a broad spectrum used in paddy field. Penoxsulam belongs to an herbicide group called ALS (acetolactate synthase) inhibitors. It can control and kill Echinochloa crusgalli and annual Cyperus weeds effectively, and it also effective against a variety of leafy weeds. Penoxsulam has the broadest herbicide controlling spectrum among the herbicides used in paddy field, it is characterized by a long lasting period and a soil activity against Echinochloa crusgalli and a lot of leafy weeds and Cyperus weeds. However, as Penoxsulam is a strong acetolactate synthase inhibitor, its herbicidal effect shows slowly, and it takes time for the weeds to die gradually. In addition, Penoxsulam exhibits poor effect against certain leafy weeds and resistant Echinochloa crusgalli.
Penoxsulam is chemically known as (2-(2,2-difluoroethoxy)-N-(5,8-dimethoxy-[1,2,4]triazolo[1,5-c]pyrimidin-2-yl)-6-(trifluoromethyl)benzenesulfonamide and has the following structure:

Penoxsulam is designed for post-emergence control of annual grasses, sedges, and broadleaf weeds in rice culture. Penoxsulam herbicide is to be used as a foliar spray on dry- seeded rice crops, or as either a foliar spray or a granular formulation on water-seeded rice crops in order to control broadleaf weeds, aquatic plants, and certain grasses.
Pyrazosulfuron ethyl is a pyrimidinylsulfonylurea herbicide having IUPAC name ethyl 5-[(4,6-dimethoxypyrimidin-2-ylcarbamoyl)sulfamoyl]-1-methylpyrazole-4-carboxylate and has the following structure:

Pyrazosulfuron ethyl is a high-efficiency sulfonylurea selective paddy field herbicide. It acts by inhibiting acetolactate synthase. Pyrazosulfuron ethyl can be quickly diffused in water, and being a selective systemic herbicide, it is absorbed by roots and/or leaves and translocated to the meristem. Thus, Pyrazosulfuron ethyl acts by inhibiting biosynthesis of the essential amino acids valine and isoleucine, hence stopping cell division and plant growth. It is safe to rice and has wide spectrum and good control effect on broadleaf weeds, cyperaceae weeds, barnyard grass and the like. Pyrazosulfuron ethyl is used to control annual and perennial broad-leaved weeds and sedges, pre- or post-emergence, wet sown and transplanted rice crops. Pyrazosulfuron ethyl provides effective control against weed species like Cyperus Iria, Cyperus difformis, Fimbristylis miliacea, Monochoria vaginalis, Ludwigia parviflora etc.
Bispyribac Sodium is chemically known as sodium 2,6-bis[(4,6-dimethoxypyrimidin-2-yl)oxy]benzoate and has the following structure:

Bispyribac sodium is a broad spectrum, selective, systemic and post-emergence herbicide. Bispyribac sodium acts by inhibition of the plant enzyme acetolactate synthetase (ALS). It 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 effective against weed species including Echinochloa crusgalli Echinochloa colonum, Ischaemum rugosum Cyperus difformis, Cyperus iria, Fimbristylis miliacea , Eclipta alba , Ludwigia parviflora, Monochoria vaginalis, Alternantheraphiloxeroides Sphenoclcea zeylenica etc.
Combinations of herbicides are used to control a broader range of weeds. However, the combination of herbicides may not always result in the desired effect. Combination of herbicides may lead to an additive effect or an antagonistic effect. It may also result in phytotoxicity to the crops making it an undesirable combination. Agronomists must therefore, carefully select the herbicides that can be combined to offer a synergistic effect that would control weeds while having no phytotoxic effect on the crop, and reduce the chances of development of herbicide resistant weeds. Thus, there still remains a need for improved formulation of herbicidal combinations that can effectively control weeds thereby improving yield and plant health, with reduced phytotoxicity.
Accordingly, there is a need in the art to provide synergistic herbicidal composition of combination having two or more active ingredients with different physical and chemical properties, which are environmentally safe, easy and effective with enhanced efficacy and stable product during storage.
Another common problem with many commercially available herbicides is the narrow window of application. Most of them provide either a pre-emergence or a post-emergence weed control. An effective weed control can be achieved by usage of herbicides appropriately, which can be applied as an early post emergence to late post emergence (3-7/8 leaf stage of weeds) as one shot application without adversely affecting desirable plants and which reduces the amount of chemical herbicidal agent necessary to obtain the acceptable weed control. The activity of herbicides can be enhanced in various ways to achieve the maximum benefit. One of the ways is to use combinations. There is always a need in the art for improved herbicidal combinations with enhanced weed control efficacy, which are safe to crops and have no adverse effect on germination or growth of succeeding crops. Thus, there arises a need in the art to combine herbicides with varied modes of action, which allows for broader spectrum of control, targeted effect with reduced or no phytotoxicity in one shot application and good resistance management apart from good residual effect on succeeding crops using lower application rates.
Conventionally, herbicides are used in their salt forms. The salts are usually formulated as aqueous based formulations. However, such aqueous formulations are suffering from several drawbacks. Thus, a need remains in the art to arrive at synergistic herbicidal composition with better dispersibility and storage stability.
Certain patent applications disclose combinations of herbicides, but their compositions do not solve the technical problems existing in the art mentioned herein above. For instance:
CN102165956 discloses a kind of herbicidal composition containing Penoxsulam and Bispyribac-sodium. This formulation is suitable for preventing and controlling annual weeds in paddy fields. The total weight of the Bispyribac-sodium and Penoxsulam accounts for 1-40 percent of the weight of the pesticide composite in the disclosed formulation. However, this patent application does not disclose a storage stable synergistic granular formulation of Penoxsulam, Bispyribac-sodium and Pyrazosulfuron-ethyl in low dosage loading of actives thereby showing synergism.
Reference is made to CN103210933, wherein it discloses microcapsule suspension containing Bispyribac-sodium and Penoxsulam where Bispyribac-sodium and Penoxsulam is present in the range of 1-30% for controlling annual weeds in paddy fields. However, this patent application does not indicate any particular preference for a preferred storage stable synergistic granular formulation comprising Penoxsulam, Bispyribac-sodium and Pyrazosulfuron-ethyl in low dosage loading of actives thereby showing synergism.
The present invention resides in the synergistic effect of Penoxsulam, Bispyribac Sodium and Pyrazosulfuron ethyl in bioactive amounts. When applied in combination in specific range of weight percentage and as specific formulation, their herbicidal potency displays the synergistic effect.

Further, there arises need in the art to arrive at synergistic granular herbicidal composition comprising Penoxsulam, Bispyribac Sodium and Pyrazosulfuron ethyl whereby there is a gradual release of the active ingredient into the water and the surface layer of the soil in the paddy field, maintaining the efficacy for a long period of time, and reducing the phytotoxicity in the treatment immediately after transplanting the rice. By dropping such a practical granule for weed control in flooded paddy fields, the effect of the active ingredients is exhibited most efficiently and the effect is maintained for a long time, and the effect is great.

When applied to a paddy field, the herbicidal composition for paddy fields disintegrates in water and spreads to release herbicide components and disperse to exhibit an effective and synergistic effect. Granules are widely used because herbicides can be applied more labour-saving than powders and liquids.

Additionally, herbicidal compositions formulated as emulsions and/or wettable powders need to be diluted with a large amount of water and dispersing agents are also used. Further, conventionally used emulsions and wettable powders of the type diluted and sprayed with a large amount of water need to spray the active diluted with a large amount of water of 50 to 100 l per 10 acres. Thus, a great deal of labor is required for the spraying. For this reason, there are very few opportunities to be applied as compared with the granules and the seeding before rice transplantation.

On the other hand, granules are most frequently used because they are relatively easy to spray. This granule is usually mixed and ground with a fine powder carrier such as bentonite, talc, clay, etc., and then granulated, or a method such as adsorbing the herbicidal active compound onto a fine powder carrier previously formed into granules is used. Although formulated, the granules thus produced have a problem that the herbicidally active ingredient is not effectively used because the herbicidally active ingredient is generally firmly adhered to the carrier. Therefore, when spraying granules, in order to obtain the same herbicidal effect as when the emulsion or wettable powder is diluted with a large amount of water and sprayed, for example, the compounding amount of the herbicidally active compound in the granules is adjusted. It is necessary to increase the amount, but this increases the cost of the preparation and is not preferable from the viewpoint of environmental pollution. Thus, the inventors of the present invention have arrived as a suitable synergistic granular herbicidal formulation which overcomes the above mentioned drawbacks existing in the art and offers significant advantages over the liquid formulations such as ease of handling, ease of use, reduced work exposure, reduced toxicity, reduced spillage and waste disposal and less field drift.

Moreover, it has been observed by the present inventors that Penoxsulam, Pyrazosulfuron ethyl and Bispyribac sodium are rendered more vulnerable to degradation when presented in a liquid formulation. Thus, there exists a need in the art for a storage stable granular herbicidal composition comprising Penoxsulam, Pyrazosulfuron ethyl and Bispyribac Sodium.

OBJECTS AND ADVANTAGES OF THE INVENTION
It is an object of the present invention to provide a novel and effective synergistic granular herbicidal composition which demonstrates high weed control efficacy.
It is an object of the present invention to provide a novel and effective synergistic granular herbicidal composition which demonstrates high weed control efficacy in respect of paddy.
It is another object of the present invention to provide a novel and effective synergistic granular herbicidal composition as one shot application for controlling harmful weeds in plants including grassy weeds, broad leaved weeds and sedges.
It is another object of the present invention to provide a novel and effective synergistic granular herbicidal composition which can be easily formulated and sprayed.
It is another object of the present invention to provide a synergistic granular herbicidal composition which can be quickly absorbed by the roots of the growing weeds in paddy fields.
It is another object of the present invention to provide a novel and effective synergistic granular herbicidal composition which is ideal for weed resistance management and provides enhanced weed control efficacy.
It is another object of the present invention to provide a novel and effective synergistic herbicidal granular composition which provides a better control of weeds at lower use rates, and excellent residual control.
It is another object of the present invention to provide a novel and effective synergistic granular herbicidal composition which provides broader and more complete spectrum of weed control.
Thus, an object of the present invention is to provide a novel and effective synergistic granular herbicidal composition and a method of controlling pre-emergence, early post emergence to late post emergence (3-7/8 leaf stage of weeds) weeds.
It is another object of the present invention to provide a novel and effective synergistic granular herbicidal composition for improved & faster control of broad-leafed, sedges and grassy weeds without adversely affecting desirable plants.
It is another object of the present invention to provide a novel and effective synergistic granular herbicidal composition which reduces the amount of herbicidal agent necessary to obtain the acceptable weed control.
It is another object of the present invention to provide a novel and effective synergistic granular herbicidal composition showing improved resistance management as a result of broad spectrum activity of the combination of herbicides having same (ALS inhibition) modes of action but from different chemistries.
It is another object of the present invention to provide a novel and effective synergistic granular herbicidal composition which provides excellent crop safety in terms of no phytotoxicity and no adverse effect on germination or growth of succeeding crops due to reduced amount of dosage.
It is another object of the present invention to provide a novel and effective synergistic granular herbicidal composition which is effective against hard to kill and resistant weeds.
It is another object of the present invention to provide a novel and effective synergistic granular herbicidal composition which has increased shelf life and stability.
It is another object of the present invention to provide a novel process for preparing a granular herbicidal composition comprising synergistic combination of herbicides, mentioned above.
It is another object of the present invention to provide a novel and effective granular herbicidal composition which is environmentally safe, possesses broad spectrum bio-efficacy and is non- toxic in terms of phytotoxicity.
It is another object of the present invention to provide a novel and effective granular herbicidal composition which is safe to operate in the paddy filed and is non-toxic being environment friendly.
It is another object of the present invention to provide a novel and effective synergistic granular herbicidal composition which has enhanced efficacy and penetration capacity.

It is an object of the present invention to provide a novel and effective synergistic granular herbicidal composition which demonstrates a high controlling effect with reduced environmental load and maximum benefit: cost ratio.
Another object of the present invention is to provide a synergistic granular herbicidal composition useful for the synergistic herbicidal control and enhanced crop protection.
It is another object of the present invention to provide a novel and effective synergistic granular herbicidal composition which delays the dominance of the resistant strain of weeds.
Yet another object of the present invention is to provide a synergistic granular herbicidal composition showing better dispersibility.
Yet another object of the present invention is to reduce resistance development in weeds in so far as weed control is concerned.
Yet another object of the present invention is to provide a method of improving plant health and increasing crop yield by using herbicidal composition comprising combination of Penoxsulam or its agrochemically acceptable salts, derivatives and (B) Pyrazosulfuron ethyl or its agrochemically acceptable salts, derivatives and (C) Bispyribac sodium or its agrochemically acceptable salts, derivatives.

Yet another object of the present invention is to provide a synergistic granular herbicidal composition with a particle size of the range 5-45 microns.
Yet another object of the present invention is to provide a synergistic granular herbicidal composition used as one-shot application composition and minimises occupational exposure and hazards.
Still another object of the present invention is to provide a synergistic granular herbicidal composition which offers decrease in the cost of application, saves fuel cost, labour cost and saves applicator's precious time and is economical.
Some or all these and other objects of the invention can be achieved by way of the invention described hereinafter.

SUMMARY OF THE INVENTION
In one embodiment of the present invention, the synergistic granular herbicidal composition comprises of:
(A) Penoxsulam or its agrochemically acceptable salts, derivatives in the range of 0.01 to 0.99% by weight of the composition; and
(B) Pyrazosulfuron ethyl or its agrochemically acceptable salts, derivatives in the range of 0.01 to 0.99% by weight of the composition and
(C) Bispyribac sodium or its agrochemically acceptable salts, derivatives in the range of 0.01 to 0.99% by weight of the composition.
In one other aspect/embodiment of the present invention, the synergistic granular herbicidal composition comprises of:
(A) Penoxsulam or its agrochemically acceptable salts, derivatives in the range of 0.01 to 0.99% by weight of the composition; and
(B) Pyrazosulfuron ethyl or its agrochemically acceptable salts, derivatives in the range of 0.01 to 0.99% by weight of the composition and
(C) Bispyribac sodium or its agrochemically acceptable salts, derivatives in the range of 0.01 to 0.99% by weight of the composition.
Wherein the particle size of the composition is 5 to 45 microns.
In one other aspect/embodiment of the present invention, the synergistic granular herbicidal composition comprises of:
(A) Penoxsulam or its agrochemically acceptable salts, derivatives in the range of 0.01 to 0.99% by weight of the composition; and
(B) Pyrazosulfuron ethyl or its agrochemically acceptable salts, derivatives in the range of 0.01 to 0.99% by weight of the composition; and
(C) Bispyribac sodium or its agrochemically acceptable salts, derivatives in the range of 0.01 to 0.99% by weight of the composition; and
(D) one or more agrochemically acceptable excipients

In another embodiment of the present invention, the synergistic granular herbicidal composition comprises of:
(A) Penoxsulam or its agrochemically acceptable salts, derivatives in the range of 0.01 to 0.99% by weight of the composition; and
(B) Pyrazosulfuron ethyl or its agrochemically acceptable salts, derivatives in the range of 0.01 to 0.99% by weight of the composition; and
(C) Bispyribac sodium or its agrochemically acceptable salts, derivatives in the range of 0.01 to 0.99% by weight of the composition; and
(D) one or more agrochemically acceptable excipients
Wherein the particle size of the composition is 5 to 45 microns.

In another embodiment, the synergistic granular herbicidal composition comprises of:
(A) Penoxsulam or its agrochemically acceptable salts, derivatives in the range of 0.01 to 0.99% by weight of the composition; and
(B) Pyrazosulfuron ethyl or its agrochemically acceptable salts, derivatives in the range of 0.01 to 0.99% by weight of the composition; and
(C) Bispyribac sodium or its agrochemically acceptable salts, derivatives in the range of 0.01 to 0.99% by weight of the composition; and
(D) one or more agrochemically acceptable excipients selected from the group consisting of stabilizers, emetic agents, rain-fasteners, solubilizers, adjuvants, antifoaming agent, antifreezing agent, wetting agent, dispersing agent, dye (s), fillers, thickening agent, stabilizing agent, carriers, surface active compounds (surfactants and / or emulsifiers), antibacterial agents, protective colloids, adhesives, thixotropic agents, penetration agents, sequestering agents, quick coating agent or sticking agents/sticker, spreader, binders, anti-caking agents, adjuvants, emulsifiers, colouring pigments, dyes, preservatives, buffering agent, solvent or combination thereof.
In a preferred embodiment of present invention, the synergistic granular herbicidal composition comprises of:
(A) Penoxsulam or its agrochemically acceptable salts, derivatives in the range of 0.02 to 0.5% by weight of the composition; and
(B) Pyrazosulfuron ethyl or its agrochemically acceptable salts, derivatives in the range of 0.02 to 0.5% by weight of the composition; and
(C) Bispyribac sodium or its agrochemically acceptable salts, derivatives in the range of 0.02 to 0.5% by weight of the composition.
In a more preferred embodiment of present invention, the synergistic granular herbicidal composition comprises of:
(A) Penoxsulam or its agrochemically acceptable salts, derivatives as 0.25% by weight of the composition; and
(B) Pyrazosulfuron ethyl or its agrochemically acceptable salts, derivatives as 0.20% by weight of the composition; and
(C) Bispyribac sodium or its agrochemically acceptable salts, derivatives as 0.25% by weight of the composition.
In another embodiment, the present invention provides a method of controlling broad spectrum of weeds affecting paddy by applying a composition of the present invention.
In another preferred embodiment, the present invention provides a process of preparing the synergistic granular herbicidal composition comprising of (A) Penoxsulam or its agrochemically acceptable salts, derivatives in the range of 0.02 to 0.5% by weight of the composition; and (B) Pyrazosulfuron ethyl or its agrochemically acceptable salts, derivatives in the range of 0.02 to 0.5% by weight of the composition; and (C) Bispyribac sodium or its agrochemically acceptable salts, derivatives in the range of 0.02 to 0.5% by weight of the composition.
In one embodiment of the present invention, the present herbicidal composition controls various weeds in field crops, turf grass, horticulture & forestry, etc.
In one embodiment of the present invention, the present herbicidal composition is storage stable and has enhanced shelf life.
In one another embodiment of the present invention, the present herbicidal composition has better dispersibility and ease in application.
In another embodiment, the present invention provides a process for preparing synergistic granular herbicidal composition comprising the steps of:
a. blending all the active ingredients with wetting agent, dispersing agent, suspending agent and filler along with other excipients to a homogenous mixture;
b. grinding the blended mixture obtained in step a) through Jet mill/ air classifier mills;
c. finely grinded material obtained in step b) is blended in post blended to obtain homogenous material to obtain particle size in the range of 5-45 microns;
d. homogenous material of step c) is unloaded into 25 kg. HDPE bag with LDPE liner inside;
e. Charge the required quantity of sand in granulator, to which is added DM water, sticking agent and remaining excipients till it become homogeneous;
f. Adding finely grinded material obtained in step e) to be completely coated on sand.
In one another embodiment of the present invention, the present herbicidal composition can be applied to a plant/crop without any on-farm dilution.
In further embodiment of the present invention, synergistic herbicidal granular composition of the present invention further comprises agriculturally acceptable excipients selected from the group consisting of stabilizers, emetic agents, rain-fasteners, solubilizers, adjuvants, antifoaming agent, wetting agent, dispersing agent, dye (s), fillers, carriers, surface active compounds (surfactants and / or emulsifiers) and optionally solid and/ or liquid auxiliaries. Additional components may also be included, e.g., protective colloids, adhesives, thickeners, thixotropic agents, penetration agents, stabilisers, sequestering agents. More generally, the active materials can be combined with any solid or liquid additive/excipient, which complies with usual formulation techniques.
In further embodiment of the present invention, dispersing agent is selected from and not limited to group comprising of Sodium ligno sulphate, Calcium ligno sulphate, Polyarylphenyl ether phosphate, tristyryl phenol ethylated , Acrylic Copolymer, Ethoxylated Tristryl phenol Sulphate, Naphthalene sulfonic acid, sodium salt condensate with formaldehyde, Ethoxylated oleyl cetyl alcohol, Polyalkelene glycol ether, Ethoxylated Fatty alcohol and/or mixtures thereof.
The dispersing agent is further selected from and not limited to group comprising of sodium lignosulphonates, Sodium lauryl sulphate, sodium naphthalene sulphonate formaldehyde condensates, Sodium polyalkylnaphthalene sulphonate (Dispersal BB4), sodium polycarboxylate (Geropon T 36), sodium methyl oleoyltaurate (Geropon T 77), phenol sulfonic acid-formaldehyde-polycondensation as sodium salt (Tamol FBPP), sodium salt of methyl naphthalene sulfonate (Supragil MNS 90), phenol sulfonic acid-formaldehyde-polycondensation as sodium salt (Dispersal PSRl 9), calcium dodecylbenzene sulfonate (Rhodocal 60 BR), polyalkoxylated butyl ether (Ethylan NS 500 LQ), phenol sulfonic acid-formaldehyde (Tamol DN), tristyrylphenol ethoxylate phosphate esters, aliphatic alcohol ethoxylates, alky ethoxylates; EO-PO block copolymers, and graft copolymers, Acrylate copolymer (Agrilan 789), polycarboxylates, alkyl naphthalene sulfonates (such as Morwet IP, Morwet EFW), sodium salt of naphthalene sulfonate condensate (Morwet D-425), phenol sulphonic acid condensates, alkyl sulfonates, alkenyl sylfonates, mixture of alkyl sulfonates and alkenyl sylfonates (Lissapol D), alkyl suflosuccinates (Geropon), L-Wet, methyl oleyltaurates and poly vinyl alcohols.
The dispersing agent is present in the composition in a range of about 0.5-10% of the total weight of the composition.
In further embodiment of the present invention, wetting agent is selected from and not limited to the group consisting of non-ionic surfactants, anionic surfactant and a mixture of anionic and non-ionic surfactant and polymeric surfactant. The wetting agent used in the present composition is selected from and not limited to Tristyrylphenol ethoxylate non-ionic emulsifier, mixture of non-ionic surfactants & alkoxylated alcohol/block copolymer and/or mixtures thereof.
The wetting agent is present in the composition in a range of about 0.5-10% of the total weight of the composition.
In further embodiment of the present invention, antifoaming agent is selected from and not limited to group comprising of Siloxane polyalkyleneoxide, polydimethyl siloxane, silicon based agents, absorbed polydimethyl siloxane, stearates, silicones (SILFOAM®, SILFAR®, PULPSIL ® and WACKER® AK) and ethoxylates and mixtures thereof.
The antifoaming agent is present in the composition in a range of about 0.01-1% of the total weight of the composition.
In further embodiment of the present invention, anti-freezing agent is selected from and not limited to group comprising of Glycol, Propylene Glycol, Mono ethylene glycol, Glycerin, Diethylene glycol and mixtures thereof.
The anti-freezing agent is present in the composition in a range of about 0.1-10% of the total weight of the composition.
An adjuvant used in the present invention is any material that is added to an agrochemical formulation to enhance or modify the performance of the formulation. An adjuvant used in the present invention to make it safer to ecological environmental, having low toxicity and having no phytotoxicity effects on any part of the plant.
In further embodiment of the present invention, adjuvants are selected from and not limited to group comprising of Silicone Ethoxylated Oil, Polyvinyl Pyrrolidone, Poly vinyl Alcohol, blend of poly terpene resin and mixtures thereof.
The adjuvants are present in the composition in a range of about 0.1-10% of the total weight of the composition.
In further embodiment of the present invention, filler is selected from and not limited to group comprising of Silicon Dioxide, China –Clay, Sand, Kaolin, Talc, starch, Urea formaldehyde resin and mixtures thereof.
The filler is present in the composition in a range of about 0.1-20% of the total weight of the composition.
In another embodiment of present invention, the base used for preparation of preferred granular composition of present invention is sand.
In further embodiment of the present invention, anti-bacterial agent is selected from and not limited to group comprising of Benzisothiazolin-3-one, Formaldehyde/Sodium benzoate/Sodium o-phenyl phenate, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one and mixtures thereof.
The anti-bacterial agent is present in the composition in a range of about 0.01-1% of the total weight of the composition.
In further embodiment of the present invention, thickening and stabilising agent is selected from and not limited to group comprising of Polysaccharides, carboxymethyl cellulose, Bentonite Clay, Aluminum Magnesium Silicate and mixtures thereof.
The thickening and stabilising agent used is present in the composition in a range of about 0.01-3% of the total weight of the composition.
The granular herbicidal composition of the present invention is found to be effective in controlling the growth of undesirable vegetation in Rice/paddy including all varieties of paddy of transplanted & direct seeded cultures.
The synergistic granular herbicidal composition of the present invention is effective against weed species including but not limited to Echinochloa colona, Echinochloa crus-galli, Chloris barbata, Panicum sp, Cynodon dactylon, Ageratum conyzoides, Ammania baccifera, Asteracantha longifolia, Centella asiatica, Commelina benghalensis, Cyanotis axillaris, Eclipta prostrata, Marselia quadrifolia, Monochoria vaginalis, Nastridium indicum, Phyla nodiflora, Phyllanthes niruri, Rotala densiflora, Ruellia tuberose, Sonchus oleraceus, Sphaeranthus indicus, Cyperus difformis, Spilanthes iabadicensis, Cyperus iria, Fimbristylis milliacea.

DETAILED DESCRIPTION OF THE INVENTION
Discussed below are some representative embodiments of the present invention. The invention in its broader aspects is not limited to the specific details and representative methods. The illustrative examples are described in this section in connection with the embodiments and methods provided.
All technical and scientific terms used herein have the same meanings as commonly understood by someone ordinarily skilled in the art to which the present subject matter belongs.
It is to be noted that, as used in the specification, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to a composition containing “a compound” includes a mixture of two or more compounds. It should also be noted that the term “or” is generally employed in its sense including “and/or” unless the content clearly dictates otherwise.
The expression of various quantities in terms of “% w/w” or “%” means the percentage by weight, relative to the weight of the total composition unless otherwise specified.
The term "comprising", which is synonymous with "including", "containing", or "characterized by" here is defined as being inclusive or open-ended, and does not exclude additional, unrecited elements or method steps, unless the context clearly requires otherwise. The term “formulation” and “composition” as used herein conveys the same meaning and can be used interchangeably.
The term “derivatives” and “salts” as used in the present disclosure and claims, mean to include all possible agrochemically active salts and derivatives of the active ingredients/herbicides used in the composition of present invention.
The term “control” as used in the present disclosure and claims, means to prevent the appearance of undesired vegetation or to reduce its growth or vigor.
The term “active ingredient” (a.i.) or “active agent” used herein refers to that component of the composition responsible for control and killing of weeds.
The terms “plants” and “vegetation” include, but are not limited to, germinant seeds, emerging seedlings, plants emerging from vegetative propagules, and established vegetation.
The term “locus” as used herein shall denote the vicinity of a desired crop in which weed control, typically selective weed control, of weeds 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.
The term “non-crop” areas shall include airport, railway stations, metro areas, between trees, horticulture areas, industrial areas, etc
The term “synergistic”, as used herein, refers to the combined action of two or more active agents blended together and administered conjointly that is greater than the sum of their individual effects.
“Bioactive amounts” as mentioned herein means that amount which, when applied for treatment of crops, is sufficient to give effect in such treatment.
The term “herbicide” is used herein to mean an active ingredient that kills, controls or otherwise adversely modifies the growth of plants. An herbicidally effective or vegetation controlling amount is an amount of active ingredient which causes a “herbicidal effect,” i.e., an adversely modifying effect and includes deviations from natural development, killing, regulation, desiccation, retardation, and the like.
The term "health of a plant" or "plant health" is defined as a condition of the plant and/or its products. As a result of the improved health; yield, plant vigour, quality and tolerance to abiotic or biotic stress is increased. It is noteworthy that the health of a plant when applying the composition according to the present invention, is increased independently of the pesticidal properties of the active ingredients used; because the increase in health is not based upon the reduced pest pressure but instead on complex physiological and metabolic reactions which result for example in an activation of the plant's own natural defence system. As a result, the health of a plant is increased even in the absence of pest pressure.
According to the present invention, "increased yield" of a plant, in particular of an agricultural, silvicultural and/or horticultural plant means that the yield of a product of the respective plant is increased by a measurable amount over the yield of the same product of the plant produced under the same conditions, but without the application of the combination according to the invention.
Increased yield can be characterized, among others, by the following improved properties of the plant: increased plant weight, increased plant height, increased biomass such as higher overall fresh weight (FW), increased number of flowers per plant, higher grain yield, more tillers or side shoots (branches), larger leaves, increased shoot growth, increased protein content, increased oil content, increased starch content, increased pigment content, increased leaf are index.
The term “benefit: cost” refers to a ratio used in a cost-benefit analysis to summarize the overall relationship between the relative costs and benefits of a proposed composition. If a treatment has a benefit-cost ratio greater than 1.0, the treatment is expected to deliver a positive and better outcome.
A further indicator for the condition of the plant is the plant vigour. The plant vigour manifests in several aspects such as the general visual appearance. Improved plant vigour can be characterized, among others, by the following improved properties of the plant: improved vitality of the plant, improved plant growth, improved plant development, improved visual appearance, improved plant stand (less plant verse/lodging), improved emergence, enhanced root growth and/or more developed root system, enhanced nodulation, in particular rhizobial nodulation, bigger leaf blade, bigger size, increased plant weight, increased plant height, increased tiller number, increased number of side shoots, increased number of flowers per plant, increased shoot growth, increased root growth (extensive root system), increased yield when grown on poor soils or unfavourable climate, enhanced photosynthetic activity (e.g. based on increased stomatal conductance and/or increased CO2 assimilation rate), increased stomatal conductance, increased CO2 assimilation rate, enhanced pigment content (e.g. chlorophyll content), earlier flowering, earlier fruiting, earlier and improved germination, earlier grain maturity, improved self-defence mechanisms, improved stress tolerance and resistance of the plants against biotic and abiotic stress factors such as fungi, bacteria, viruses, insects, heat stress, cold stress, drought stress, UV stress and/or salt stress, less non-productive tillers, less dead basal leaves, less input needed (such as fertilizers or water), greener leaves, complete maturation under shortened vegetation periods, less fertilizers needed, less seeds needed, easier harvesting, faster and more uniform ripening, longer shelf-life, longer panicles, delay of senescence, stronger and/or more productive tillers, better extractability of ingredients, improved quality of seeds (for being seeded in the following seasons for seed production), better nitrogen uptake, improved reproduction, reduced production of ethylene and/or the inhibition of its reception by the plant.
In another especially preferred embodiment of the invention, the plant vigour of the treated plant is increased. In another preferred embodiment of the invention, the plant vigour of the plants treated according to the composition of the present invention is increased synergistically.
The improvement of the plant vigour according to the present invention particularly means that the improvement of any one or several or all of the above mentioned plant characteristics are improved.
Another indicator for the condition of the plant is the “quality” of a plant and/or its products.
In an especially preferred embodiment of the invention, the quality of the treated plant is increased.
According to the present invention, enhanced quality means that certain plant characteristics such as the content or composition of certain ingredients are increased or improved by a measurable or noticeable amount over the same factor of the plant produced under the same conditions. Enhanced quality can be characterized, among others, by following improved properties of the plant or its product: increased nutrient content, increased protein content, increased content of fatty acids, increased metabolite content, increased carotenoid content, increased sugar content, increased amount of essential amino acids, improved nutrient composition, improved protein composition, improved composition of fatty acids, improved metabolite composition, improved carotenoid composition, improved sugar composition, improved amino acids composition, improved or optimal fruit colour, improved leaf colour, higher storage capacity, higher processability of the harvested products.
When using the composition according to the invention, the application rate can be varied within a relatively wide range, depending on the kind of paddy cultivation- nursery, transplanted or DSR. Dose per hectare may range from 2000 g to 10,000 g.
In accordance with an embodiment of the invention, there is provided a granular herbicidal composition for weed control comprising active ingredients present in the weight percentage range as given below:

Penoxsulam
or its agrochemically acceptable salts, derivatives Pyrazosulfuron ethyl
or its agrochemically acceptable salts, derivatives
Bispyribac sodium
or its agrochemically acceptable salts, derivatives

0.01 to 0.99% 0.01 to 0.99% 0.01 to 0.99%

In another embodiment, the present invention provides a process for preparing synergistic granular herbicidal composition comprising the steps of:
a. blending all the active ingredients with wetting agent, dispersing agent, suspending agent and filler along with other excipients to a homogenous mixture;
b. grinding the blended mixture obtained in step a) through Jet mill/ air classifier mills;
c. finely grinded material obtained in step b) is blended in post blended to obtain homogenous material to obtain particle size in the range of 5-45 microns;
d. homogenous material of step c) is unloaded into 25 kg. HDPE bag with LDPE liner inside;
e. Charge the required quantity of sand in granulator, to which is added DM water, sticking agent and remaining excipients till it become homogeneous;
f. Adding finely grinded material obtained in step e) to be completely coated on sand.
In yet another embodiment of the present invention, there is higher benefit: cost ratio.
In one embodiment, the compositions according to the present invention acts synergistically to control broad spectrum of weeds in paddy.
In an especially preferred embodiment of the invention, the yield of the treated plant and crop is increased.
In another preferred embodiment of the invention, the yield of the plants (paddy) treated according to the method of the invention, is increased synergistically.
In order that the present invention may be more readily understood, reference will now be made, by way of example, to the following description. It will be understood that the specification and examples are illustrative but not limitative of the present invention and that other embodiments within the spirit and scope of the invention will suggest themselves to those skilled in the art. Other embodiments can be practiced that are also within the scope of the present invention. The following illustrations of examples are intended to illustrate a stable synergistic granular herbicidal composition, but in no way limit the scope of the present invention.
It is to be understood that the present invention is susceptible to modifications, changes and adaptations by those skilled in the art. Such modifications, changes, adaptations are intended to be within the scope of the present invention.
The invention is illustrated by the following example below and is not limited thereto.
Granular composition (GR) of Penoxsulam, Pyrazosulfuron ethyl and Bispyribac sodium according to the present invention was prepared as follows:
GR formulation
Sr. No. Component Composition
1 2 3 4 5
1 Bispyribac Sodium Technical 0.01 0.99 0.25 0.5 0.1
2 Pyrazosulfuron ethyl Technical 0.01 0.99 0.2 0.3 0.3
3 Penoxsulam Technical 0.01 0.99 0.25 0.2 0.6
4 Sodium Polycarboxylate 3.00 3.00 3.00 3.00 3.00
5 Sodium Lauryl Sulfate 4.00 4.00 4.00 4.00 4.00
6 Pigment blue 0.10 0.10 0.10 0.10 0.10
7 China Clay 5.00 5.00 5.00 5.00 5.00
8 DM water 1.00 2.00 1.00 2.00 1.00
11 Sand QS to Make 100 QS to Make 100 QS to Make 100 QS to Make 100 QS to Make 100

Example 1:
Sr. No. Recipe % w/w
1 Bispyribac Sodium Technical 0.01-0.99%
2 Pyrazosulfuron ethyl Technical 0.01-0.99%
3 Penoxsulam Technical 0.01-0.99%
4 Dispersing Agent- Polyarylphenyl ether phosphate, tristyryl phenol ethylated /Acrylic
Copolymer/ Ethoxylated Tristryl phenol Sulphate,Naphthalene sulfonic acid,sodium salt condensate with formaldehyde,Ethoxylated oleyl cetyl alcohol, Polyalkelene glycol ether,Ethoxylated Fatty alcohol 0.5-10%
5 Wetting Agent- Tristyrylphenol ethoxylate non-ionic
emulsifier/ Mixture of non-ionic surfactants
& Alkoxylated Alcohol/Block copolymer 0.5-10%
6 Antifoaming Agent-Siloxane polyalkyleneoxide 0.01-1%
7 Antifreezing Agent- Glycol,Propylene Glycol, Mono ethylene glycol,Glycerin,Diethylene glycol 0.1-10%
8 Adjuvants- Silicone Ethoxylated Oil, Polyvinyl Pyrrolidon,Poly vinyl Alcohol,Blend of poly terpene resin 0.1-10%
9 Filler- Silicon Dioxide/China -
Clay/Kaolin/Talc/starch /Urea formaldehyde resin 0.1-20%
10 Anti-bacterial – Benzisothiazolin-3-one / Formaldehyde/Sodium benzoate/Sodium o-phenylphenate, 5-chloro-2-methyl-4-isothiazolin-3-one & 2-
methyl-4-isothiazolin-3-onee 0.01-1%
11 Polysaccharides/carboxymethyl cellulose/Bentonite Clay /Aluminum Magnesium Silicate 0.01-3%
12 Sand Q.s to make 100
Total 100

Example 2: Granular composition (GR) of Penoxsulam, Pyrazosulfuron ethyl and Bispyribac sodium
Sr. No. Recipe % w/w
1 Bispyribac Sodium Technical 0.99%
2 Pyrazosulfuron ethyl Technical 0.01%
3 Penoxsulam Technical 0.02%
4 Dispersing Agent- Calcium Ligno sulphate/Sodium ligno sulphate 3%
5 Pigment Blue 0.20%
6 Filler- Urea formaldehyde resin 1%
7 Adjuvants-Polyvinyl pyrrolidone 0.1%
8 DM water 1%
9 Sand Q.s to make 100
Total 100

Process:
a. blending all the active ingredients with wetting agent, dispersing agent, suspending agent and filler along with other excipients to a homogenous mixture;
b. grinding the blended mixture obtained in step a) through Jet mill/ air classifier mills;
c. finely grinded material obtained in step b) is blended in post blended to obtain homogenous material to obtain particle size in the range of 5-45 microns;
d. homogenous material of step c) is unloaded into 25 kg. HDPE bag with LDPE liner inside;
e. Charge the required quantity of sand in granulator, to which is added DM water, sticking agent and remaining excipients till it become homogeneous;
f. Adding finely grinded material obtained in step e) to be completely coated on sand to obtain the granular herbicidal composition of present invention.
Biological Examples:
Bio-efficacy studies
The presence of a synergistic effect between three active ingredients is established with the aid of the Colby equation (se S. R. Colby, "Calculating Synergistic and Antagonistic Responses of Herbicide Combinations', Weeds,1967,15,20-22). The action expected for a given combination of three active components can be calculated as follows:

Using the method of Colby, the presence of a synergistic interaction between three active ingredients is established by first calculating the predicted activity, p, of the composition based on activities of the three components applied alone. If 'p' is lower than the experimentally established efficacy, Synergism has occurred. In the equation above, A is the pesticidal (herbicidal) activity in percentage control of one component applied alone at rate x. The term B is the pesticidal (herbicidal) activity in percentage control of the second component applied at rate 'y' & similarly C is the corresponding value for the third component applied at rate z. The equation estimates p, the pesticidal(herbicidal)activity of the combination of A at rate X with B at rate y & C at rate z if their effects are strictly additive then no interaction has occurred.
In rice, many studies have been conducted on comprehensive weed management (CWM), most of which have looked at one or two of those components in isolation. Since the concept of CWM issue is yet to be addressed properly considering the diverse weed management approaches. Therefore, for designing a sustainable weed management strategy for rice, it is a prerequisite to assess the simultaneous effect of different herbicidal combinations with timely herbicide application. The present study was, therefore, conducted to find out suitable herbicidal combination as composition to give one shot treatment to control or supress the weed flora complex in rice crop and compared with manual weeding under transplanted rice variety CSR 30
Materials and Methods
Experimental Site and Soil: The field trials were conducted in main season 2020/2021 (May–October) at farm situated in Gharaunda, district Karnal in Haryana, (29.5397° N, 76.9731°'E). The experimental soil (medium alluvial) was clay loam in texture (26.77% sand, 21.30% silt, and 51.93% clay) and acidic in reaction (pH 5.6) with 1.42?g?cc-1 bulk density, 1.77% organic carbon, and 17.24?me 100?g-1 soil CEC. Soil contained 0.38% total N, 21.5?ppm available P, 139?ppm available K, 803?ppm?Ca, and 159?ppm?Mg. At field capacity, soil water retention was 55.69% (wet basis) and 39.35% (dry basis). The local climate was hot humid sub-tropic with ample rainfall. During the experimental period, average maximum and minimum temperatures, relative humidity ranged from 31.7 to 45.0°C and 22.9 to 34.4°C, 43.5 to 54.7%, respectively.
Plant Material: rice variety CSR 30 was used as the plant material in the present study. This variety is sourced from Pusa research centre.

Experimental Treatments and Design:
The experiment was laid out in a randomized complete block design with three replications. Thirty two different combinations of herbicides and manual weeding were evaluated for their efficacy in controlling weeds in transplanted rice crop; season-long weed-free check and season-long weedy check were also included in the trial. Herbicides included, in various combinations (Cyhalofop-butyl, Penoxsulam, Bispyribac-sodium, Pyrazosulfuron ethyl), some of them were available as commercial products. Herbicides used in this experiment were selected based on their performances in the earlier studies to enhance the spectrum of weed control. Season-long weed-free plots were maintained through manual weeding as and when necessary. In weedy checks, no weeding operations were done.
Crop Husbandry:
The soil was ploughed, harrowed flooded with water and puddled during preparation. 25 days old Rice seedlings were transplanted in the weed puddled filed at > 100% moisture capacity with spacing of 25?cm X 15?cm . Each plot, of size 5?m long and 4?m wide, was fertilized with single super phosphate (SSP) and muriate of potash (MP) at the rate of 100?kg?P/ha and 100?kg?K/ha, respectively, during final land preparation; urea was top dressed thrice each at the rate of 50?kg?N/ha at 2, 4, and 6 weeks after transplanting. Soil was maintained under saturated anaerobic conditions with intermittent aerobic conditions for very short period. The trial was primarily irrigated with canal water, but supplemental with ground water irrigation (tubewell) was given whenever necessary to maintain water level of 1.5 to 2.0 cm. Overflow canals were kept to facilitate drainage following heavy rainfall to avoid ponding. Different intercultural operations and plant protection measures were taken following standard practices.
Weed Measurements:
A 25?cm × 25?cm quadrate was randomly placed lengthwise at four spots in each plot for recording of weed data at 15, 30, and 45 days after transplanting (DAT). Weeds were clipped to ground level, identified and counted by species, and separately oven dried at 70°C for 72?h. Weed density (WD) and weed dry weight (WDW) were expressed as no./m2 and g/m2, respectively. Dominant weed species were identified using the summed dominance ratio (SDR) computed.
Rice Measurements:
At maturity, yield attributes were recorded from ten randomly selected hills. All the panicles of sample hills were counted and converted to panicles/m2. Sample panicles were hand threshed; filled grains were separated from unfilled grains and counted to calculate filled grains/panicle. Central 3?m2 area of each plot was hand harvested to record grain yield (t/ha) and thousand-seed weight (g). Grain yield and thousand-seed weight were adjusted to 14% moisture content. Percent relative yield loss (RYL) due to weeds was calculated as [100 × (weed-free yield - weedy yield)/weed-free yield]. Crop phytotoxicity rating of different herbicides was assessed visually at 7, 14, and 21 days after application (DAA) of herbicide using a scale of 1 to 10.
Economic Measurements:
Economic analysis was performed following the procedure by Hussain et al. Two manual weedings were considered sufficient to keep the plots weed-free throughout. Laborers required for one round weeding and one round herbicide spraying per hectare were 30 and 2, respectively. The cost for laborer was Rs 500/laborer/day. The cost of each herbicide was estimated based on their local market price. Price of paddy was collected from minimum support price (MSP) for calculating the gross return. The net benefit per hectare for each treatment was calculated by deducting the weed management cost from the gross return.
Weed composition in the selected experimental field was 52% grassy weeds, 27% broad leaved weeds (BLW) and rest 31% were sedges.
It was found that ternary herbicidal composition of present invention as ready mix showed superior control over all the three types of weed flora as supported in better weed control efficacy (WCE) with proven synergy as supported with application of Colby equation.
The following treatment options were used in the field studies described above:
Table 1
S. No. Penoxsulam Pyrazosulfuron Ethyl Bispyribac Sodium Formulation ml-g/ha
T1 15.00 0.00 0.00 562
T2 18.75 0.00 0.00 702
T3 22.50 0.00 0.00 843
T4 25.00 0.00 0.00 936
T5 0.00 12.00 0.00 120
T6 0.00 15.00 0.00 150
T7 0.00 18.00 0.00 180.0
T8 0.00 20.00 0.00 200
T9 0.00 0.00 15.00 150
T10 0.00 0.00 18.75 188
T11 0.00 0.00 22.50 225
T12 0.00 0.00 25.00 250
T13 15.00 12.00 15.00 6000 g of Ready mix of Penoxsulam 0.25% + Pyrazosulfuron ethyl 0.20% + Bispyribac sodium 0.25%- GR
T14. 15.00 12.00 15.00 Tank mix of 562ml Penoxsulam 2.67% OD + 120g of Pyrazosulfuron 10%WP + 150ml Bispyribac sodium 10%EC
T15 15.00 15.00 18.75 Tank mix of 562ml Penoxsulam 2.67% OD + 150g of Pyrazosulfuron 10%WP + 188ml Bispyribac sodium 10%EC
T16 15.00 18.00 22.50 Tank mix of 562ml Penoxsulam 2.67% OD + 180g of Pyrazosulfuron 10%WP + 225ml Bispyribac sodium 10%EC
T17 15.00 20.00 25.00 Tank mix of 562ml Penoxsulam 2.67% OD + 200g of Pyrazosulfuron 10%WP + 250ml Bispyribac sodium 10%EC
T18 18.75 12.00 15.00 Tank mix of 702ml Penoxsulam 2.67% OD + 120g of Pyrazosulfuron 10%WP + 150ml Bispyribac sodium 10%EC
T19 18.75 15.00 18.75 7500 g of Ready mix of Penoxsulam 0.25% + Pyrazosulfuron ethyl 0.20% + Bispyribac sodium 0.25%- GR
T20 18.75 15.00 18.75 Tank mix of 702ml Penoxsulam 2.67% OD + 150g of Pyrazosulfuron 10%WP + 188 ml Bispyribac sodium 10%EC
T21 18.75 18.00 22.50 Tank mix of 702ml Penoxsulam 2.67% OD + 180g of Pyrazosulfuron 10%WP + 225ml Bispyribac sodium 10%EC
T22 18.75 20.00 25.00 Tank mix of 702ml Penoxsulam 2.67% OD + 200g of Pyrazosulfuron 10%WP + 250ml Bispyribac sodium 10%EC
T23 22.50 12.00 15.00 Tank mix of 843ml Penoxsulam 2.67% OD + 120g of Pyrazosulfuron 10%WP + 150ml Bispyribac sodium 10%EC
T24 22.50 15.00 18.75 Tank mix of 843ml Penoxsulam 2.67% OD + 150g of Pyrazosulfuron 10%WP + 188ml Bispyribac sodium 10%EC
T25 22.50 18.00 22.50 9000 g of Ready mix of Penoxsulam 0.25% + Pyrazosulfuron ethyl 0.20% + Bispyribac sodium 0.25%- GR
T26 22.50 18.00 22.50 Tank mix of 843ml Penoxsulam 2.67% OD + 180g of Pyrazosulfuron 10%WP + 225 ml Bispyribac sodium 10%EC
T27 22.50 20.00 25.00 Tank mix of 843ml Penoxsulam 2.67% OD + 200g of Pyrazosulfuron 10%WP + 250ml Bispyribac sodium 10%EC
T28 25.00 12.00 15.00 Tank mix of 936ml Penoxsulam 2.67% OD + 120g of Pyrazosulfuron 10%WP + 150ml Bispyribac sodium 10%EC
T29 25.00 15.00 18.75 Tank mix of 936ml Penoxsulam 2.67% OD + 150g of Pyrazosulfuron 10%WP + 188ml Bispyribac sodium 10%EC
T30 25.00 18.00 22.50 Tank mix of 936ml Penoxsulam 2.67% OD + 180 g of Pyrazosulfuron 10%WP + 225ml Bispyribac sodium 10%EC
T31 25.00 20.00 25.00 Tank mix of 936ml Penoxsulam 2.67% OD + 200g of Pyrazosulfuron 10%WP + 250 ml Bispyribac sodium 10%EC
T32 25.00 20.00 25.00 10000 g of Ready mix of Penoxsulam 0.25% + Pyrazosulfuron ethyl 0.20% + Bispyribac sodium 0.25%- GR
T33 Bispyribac sodium 20% + Pyrazosulfron15%-WDG @ (20 + 15 g/ha) Commercial formulation @ 100g

T34 Penoxsulam 1.02% + Cyhalofop butyl 5.1%-OD @ 120g a.i./ha Commercial formulation @2000ml

T35 Handweeding @ 20 & 40 DAS Two hand weedings

T36 WEED CHECK Control plot

Synergistic effect of herbicidal composition comprising Penoxsulam, Pyrazosulfuron ethyl & Bispyribac sodium in Paddy
Table 2:
Treatments g a.i/ha Weeds count/sq cm at 45 DAA
S. No. Penoxsulam Pyrazosulfuron Ethyl Bispyribac Sodium Grasses BLW Sedges Total
T1 15.00 0.00 0.00 9.00 7.33 6.00 22.33
T2 18.75 0.00 0.00 7.66 6.50 6.00 20.16
T3 22.50 0.00 0.00 6.25 6.50 5.50 18.25
T4 25.00 0.00 0.00 5.00 6.00 4.50 15.50
T5 0.00 12.00 0.00 20.00 5.66 7.67 33.33
T6 0.00 15.00 0.00 19.00 5.00 7.00 31.00
T7 0.00 18.00 0.00 19.00 4.33 6.50 29.83
T8 0.00 20.00 0.00 17.66 4.00 6.25 27.91
T9 0.00 0.00 15.00 11.00 9.50 8.33 28.83
T10 0.00 0.00 18.75 9.66 8.66 7.00 25.32
T11 0.00 0.00 22.50 8.00 8.00 6.67 22.67
T12 0.00 0.00 25.00 7.50 8.00 6.50 22.00
T13 15.00 12.00 15.00 4.50 3.50 3.00 9.50
T14. 15.00 12.00 15.00 7.00 6.00 5.00 18.00
T15 15.00 15.00 18.75 6.00 4.66 5.00 15.66
T16 15.00 18.00 22.50 5.66 4.00 4.66 14.32
T17 15.00 20.00 25.00 5.25 4.00 4.50 13.75
T18 18.75 12.00 15.00 3.50 5.00 4.00 13.00
T19 18.75 15.00 18.75 1.75 2.00 2.00 6.75
T20 18.75 15.00 18.75 2.50 3.00 3.00 8.50
T21 18.75 18.00 22.50 1.50 2.50 3.00 7.00
T22 18.75 20.00 25.00 1.50 2.00 2.00 5.50
T23 22.50 12.00 15.00 2.00 3.00 2.67 7.67
T24 22.50 15.00 18.75 2.00 1.67 2.00 5.67
T25 22.50 18.00 22.50 1.25 1.50 1.50 5.00
T26 22.50 18.00 22.50 2.33 2.00 2.00 6.33
T27 22.50 20.00 25.00 1.75 1.25 1.50 4.50
T28 25.00 12.00 15.00 2.00 2.50 2.00 6.50
T29 25.00 15.00 18.75 2.00 1.75 1.50 5.25
T30 25.00 18.00 22.50 1.50 1.50 1.50 4.50
T31 25.00 20.00 25.00 1.00 0.66 1.50 3.16
T32 25.00 20.00 25.00 0.67 1.00 1.50 3.33
T33 Bispyribac sodium 20% + Pyrazosulfron15%-WDG @ (20 + 15 g/ha) 10.00 5.00 6.00 21.00
T34 Penoxsulam 1.02% + Cyhalofop butyl 5.1%-OD @ 120g a.i./ha 6.00 8.00 6.00 20.00
T35 Handweeding @ 20 & 40 DAS 0.75 1.25 1.00 3.00
T36 WEED CHECK 24.50 12.66 10.33 47.49
DAA: Days after Application
BLW: Broad leaf weeds

Table 3:
Treatments g a.i/ha Weed Control Efficiency (Total Weeds)
S. No.
Penoxsulam
Pyrazosulfuron Ethyl
Bispyribac Sodium Observed WCE% Expected WCE% Difference
T1 15.00 0.00 0.00 52.98 - -
T2 18.75 0.00 0.00 57.55 - -
T3 22.50 0.00 0.00 61.57 - -
T4 25.00 0.00 0.00 67.36 - -
T5 0.00 12.00 0.00 29.82 - -
T6 0.00 15.00 0.00 34.72 - -
T7 0.00 18.00 0.00 37.19 - -
T8 0.00 20.00 0.00 41.23 - -
T9 0.00 0.00 15.00 39.29 - -
T10 0.00 0.00 18.75 46.68 - -
T11 0.00 0.00 22.50 52.26 - -
T12 0.00 0.00 25.00 53.67 - -
T13 15.00 12.00 15.00 80.00 79.97 0.03
T14 15.00 12.00 15.00 62.10 79.97 -17.87
T15 15.00 15.00 18.75 67.02 83.64 -16.61
T16 15.00 18.00 22.50 69.85 85.90 -16.05
T17 15.00 20.00 25.00 71.05 87.20 -16.15
T18 18.75 12.00 15.00 72.63 81.91 -9.29
T19 18.75 15.00 18.75 85.79 85.23 0.56
T20 18.75 15.00 18.75 82.10 85.23 -3.12
T21 18.75 18.00 22.50 85.26 87.27 -2.01
T22 18.75 20.00 25.00 88.42 88.44 -0.02
T23 22.50 12.00 15.00 83.85 83.63 0.22
T24 22.50 15.00 18.75 88.06 86.63 1.44
T25 22.50 18.00 22.50 89.47 88.48 0.99
T26 22.50 18.00 22.50 86.67 88.48 -1.81
T27 22.50 20.00 25.00 90.52 89.54 0.99
T28 25.00 12.00 15.00 86.31 86.09 0.22
T29 25.00 15.00 18.75 88.95 88.64 0.30
T30 25.00 18.00 22.50 90.52 90.21 0.31
T31 25.00 20.00 25.00 93.35 91.11 2.23
T32 25.00 20.00 25.00 92.99 91.11 1.87
T33 Bispyribac sodium 20% + Pyrazosulfron15%-WDG @ (20 + 15 g/ha) 55.78 - -
T34 Penoxsulam 1.02% + Cyhalofop butyl 5.1%-OD @ 120g a.i./ha 57.89 - -
T35 Handweeding @ 20 & 40 DAS 93.68 - -
T36 WEED CHECK 0.00 - -

It can be observed from Table 2 and 3 that the compositions of the present invention showed synergistic effect and increased weed control efficiency-which was found to be more than 75% as compared to commercially available binary combinations as post-emergent treatments and solo treatments. Also when Coly equation was applied there was found synergy in these three herbicides resulting in a synergetic herbicidal composition

Synergistic effect of herbicidal composition comprising Penoxsulam, Pyrazosulfuron ethyl & Bispyribac sodium against grassy weeds in Paddy
Table 4:

Treatments g a.i/ha Grass weeds count Weed Control Efficiency
(Grasses weeds)
S. No. Penoxsulam Pyrazosulfuron Ethyl Bispyribac Sodium Number/Sq mt. Observed WCE% Expected WCE% Difference
T1 15.00 0.00 0.00 9.00 63.27 - -
T2 18.75 0.00 0.00 7.66 68.73 - -
T3 22.50 0.00 0.00 6.25 74.49 - -
T4 25.00 0.00 0.00 5.00 79.59 - -
T5 0.00 12.00 0.00 20.00 18.37 - -
T6 0.00 15.00 0.00 19.00 22.45 - -
T7 0.00 18.00 0.00 19.00 22.45 - -
T8 0.00 20.00 0.00 17.66 27.91 - -
T9 0.00 0.00 15.00 11.00 55.10 - -
T10 0.00 0.00 18.75 9.66 60.57 - -
T11 0.00 0.00 22.50 8.00 67.35 - -
T12 0.00 0.00 25.00 7.50 69.38 - -
T13 15.00 12.00 15.00 4.50 81.63 86.54 -4.90
T14 15.00 12.00 15.00 7.00 71.43 86.54 -15.11
T15 15.00 15.00 18.75 6.00 75.51 88.77 -13.26
T16 15.00 18.00 22.50 5.66 76.90 90.70 -13.80
T17 15.00 20.00 25.00 5.25 78.57 91.89 -13.32
T18 18.75 12.00 15.00 3.50 85.71 88.54 -2.83
T19 18.75 15.00 18.75 1.75 92.85 90.44 2.41
T20 18.75 15.00 18.75 2.50 89.79 90.44 -0.65
T21 18.75 18.00 22.50 1.50 93.88 92.08 1.79
T22 18.75 20.00 25.00 1.50 93.88 93.10 0.78
T23 22.50 12.00 15.00 2.00 91.84 90.65 1.19
T24 22.50 15.00 18.75 2.00 91.83 92.20 -0.37
T25 22.50 18.00 22.50 1.25 94.90 93.54 1.36
T26 22.50 18.00 22.50 2.33 90.49 93.54 -3.05
T27 22.50 20.00 25.00 1.75 92.86 94.37 -1.51
T28 25.00 12.00 15.00 2.00 91.84 92.52 -0.68
T29 25.00 15.00 18.75 2.00 91.84 93.76 -1.92
T30 25.00 18.00 22.50 1.50 93.88 94.83 -0.95
T31 25.00 20.00 25.00 1.00 95.91 95.49 0.42
T32 25.00 20.00 25.00 0.67 97.27 95.49 1.77
T33 Bispyribac sodium 20% + Pyrazosulfron15%-WDG @ (20 + 15 g/ha) 10.00 59.18 - -
T34 Penoxsulam 1.02% + Cyhalofop butyl 5.1%-OD @ 120g a.i./ha 6.00 75.51 - -
T35 Hand weeding 20& 40 DAS 0.75 96.94 - -
T36 Weed Check 24.50 0.00 - -

As the maximum weed pressure in rice crop appears to be grassy weeds, therefore separate weed types data was collected and after analysing the same it is inferred from Table 4 that the ternary compositions as per the present invention show better weed control efficiency (as compared to commercially available binary herbicidal combination treatment and solo herbicidal treatments) due to synergistic effect against the grassy weeds as well.

Synergistic effect of herbicidal composition comprising Penoxsulam, Pyrazosulfuron ethyl & Bispyribac sodium in reducing weed bio-mass & increasing the Weed control Index (WCI)

Weed control index (WCI)

To compare the different treatments of weed control on the basis of dry weight, weed control index (WCI) was calculated as follows (Mani et al., 1973 and Das, 2008). It indicates the percent reduction in the dry weight in treated plots compared to weedy plots.

DWC – DWT
(WCI), % = -------------------------------- × 100
DWC

Where,
WCI = Weed control Index
DWC = Dry weight of weeds in control plots
DWT = Dry weight of weeds in treated plots
Table 5:
Treatments g a.i./ha Weed Bio-mass Weed Control Index.
(Total weeds)
S. No. Penoxsulam Pyrazosulfuron Ethyl Bispyribac Sodium g/ sqm Observed
WCI% Expected WCI% Difference
T1 15.00 0.00 0.00 15.00 60.00 - -
T2 18.75 0.00 0.00 12.66 66.24 - -
T3 22.50 0.00 0.00 11.00 70.67 - -
T4 25.00 0.00 0.00 10.75 71.33 - -
T5 0.00 12.00 0.00 19.00 49.33 - -
T6 0.00 15.00 0.00 18.25 51.33 - -
T7 0.00 18.00 0.00 13.00 65.33 - -
T8 0.00 20.00 0.00 12.60 66.40 - -
T9 0.00 0.00 15.00 16.00 57.33 - -
T10 0.00 0.00 18.75 14.00 62.67 - -
T11 0.00 0.00 22.50 12.00 68.00 - -
T12 0.00 0.00 25.00 12.00 68.00 - -
T13 15.00 12.00 15.00 10.00 73.33 91.35 -18.02
T14 15.00 12.00 15.00 12.00 68.00 91.35 -23.35
T15 15.00 15.00 18.75 10.00 73.33 92.73 -19.40
T16 15.00 18.00 22.50 6.50 82.67 95.56 -12.90
T17 15.00 20.00 25.00 6.00 84.00 95.70 -11.70
T18 18.75 12.00 15.00 4.30 88.53 92.70 -4.17
T19 18.75 15.00 18.75 2.00 94.67 93.87 0.80
T20 18.75 15.00 18.75 3.50 90.67 93.87 -3.20
T21 18.75 18.00 22.50 1.00 97.33 96.25 1.08
T22 18.75 20.00 25.00 1.00 97.33 96.37 0.96
T23 22.50 12.00 15.00 1.00 97.33 93.66 3.67
T24 22.50 15.00 18.75 1.50 96.00 94.67 1.33
T25 22.50 18.00 22.50 1.00 97.33 96.75 0.59
T26 22.50 18.00 22.50 1.33 96.45 96.75 -0.29
T27 22.50 20.00 25.00 1.00 97.33 96.85 0.49
T28 25.00 12.00 15.00 1.00 97.33 96.74 0.59
T29 25.00 15.00 18.75 1.00 97.33 97.15 0.19
T30 25.00 18.00 22.50 0.50 98.67 98.41 0.26
T31 25.00 20.00 25.00 0.50 98.67 98.53 0.13
T32 25.00 20.00 25.00 0.00 100.00 98.53 1.47
T33 Bispyribac sodium 20% + Pyrazosulfron15%-WDG @ (20 + 15 g/ha) 9.67 74.21 - -
T34 Penoxsulam 1.02% + Cyhalofop butyl 5.1%-OD @ 120g a.i./ha 7.50 80.00 - -
T35 Handweeding @ 20 & 40 DAS 1.50 96.00 - -
T36 WEED CHECK 37.50 - - -

From Table 45 it is evident that weed bio-mass was drastically reduced in all the herbicidal treatments, at normal to high doses of ternary herbicidal composition of present invention. Also treatments of ternary herbicidal composition of present invention exhibited synergistic effect in reducing the weed bio mass.

Synergistic effect of herbicidal composition comprising Penoxsulam, Pyrazosulfuron ethyl & Bispyribac sodium on yield attributes and Harvest Index in relation to paddy
Table 6:

Treatments g a.i/ha Yield Index
S. No. Penoxsulam
Pyrazosulfuron Ethyl Bispyribac Sodium Paddy Yield
mt/ha %increase in yield over control Expected % increase in yield as per Colby equation Difference
T1 15.00 0.00 0.00 2.89 22.98 - -
T2 18.75 0.00 0.00 2.99 27.23 - -
T3 22.50 0.00 0.00 3.23 37.45 - -
T4 25.00 0.00 0.00 3.34 42.13 - -
T5 0.00 12.00 0.00 2.50 6.38 - -
T6 0.00 15.00 0.00 2.58 9.79 - -
T7 0.00 18.00 0.00 2.62 11.49 - -
T8 0.00 20.00 0.00 2.70 14.89 - -
T9 0.00 0.00 15.00 2.70 14.89 - -
T10 0.00 0.00 18.75 2.75 17.02 - -
T11 0.00 0.00 22.50 2.98 26.81 - -
T12 0.00 0.00 25.00 3.10 31.91 - -
T13 15.00 12.00 15.00 3.66 55.74 38.63 17.11
T14 15.00 12.00 15.00 3.51 49.36 38.63 10.73
T15 15.00 15.00 18.75 3.72 58.30 42.34 15.95
T16 15.00 18.00 22.50 3.82 62.55 50.10 12.45
T17 15.00 20.00 25.00 3.88 64.94 55.37 9.57
T18 18.75 12.00 15.00 3.86 64.26 42.02 22.23
T19 18.75 15.00 18.75 4.15 76.60 45.53 31.07
T20 18.75 15.00 18.75 4.00 70.21 45.53 24.68
T21 18.75 18.00 22.50 4.21 79.06 52.86 26.20
T22 18.75 20.00 25.00 4.19 78.30 57.84 20.46
T23 22.50 12.00 15.00 3.92 66.81 50.16 16.65
T24 22.50 15.00 18.75 3.98 69.36 53.17 16.19
T25 22.50 18.00 22.50 4.07 73.11 59.48 13.63
T26 22.50 18.00 22.50 4.04 71.91 59.48 12.44
T27 22.50 20.00 25.00 4.10 74.47 63.75 10.71
T28 25.00 12.00 15.00 4.12 75.32 53.89 21.43
T29 25.00 15.00 18.75 4.22 79.57 56.68 22.90
T30 25.00 18.00 22.50 4.30 82.98 62.51 20.47
T31 25.00 20.00 25.00 4.30 82.98 66.47 16.51
T32 25.00 20.00 25.00 4.33 84.26 66.47 17.79
T33 Bispyribac sodium 20% + Pyrazosulfron15%-WDG @ (20 + 15 g/ha) 3.67 56.17 - -
T34 Penoxsulam 1.02% + Cyhalofop butyl 5.1%-OD @ 120g a.i./ha 3.82 62.55 - -
T35 Hand weeding @ 20 & 40 DAS 4.24 80.43 - -
T36 WEED CHECK 2.35 0.00 - -
Table 7:
Treatments g a.i/ha Herbicides Efficiency Index
S. No. Penoxsulam
Pyrazosulfuron Ethyl Bispyribac Sodium No. of tillers per sq m. %increase in tillers over control Expected % increase in pods number over untreated Difference
T1 15.00 0.00 0.00 222.00 79.03 - -
T2 18.75 0.00 0.00 232.00 87.10 - -
T3 22.50 0.00 0.00 233.00 87.90 - -
T4 25.00 0.00 0.00 236.00 90.32 - -
T5 0.00 12.00 0.00 143.00 15.32 - -
T6 0.00 15.00 0.00 146.00 17.74 - -
T7 0.00 18.00 0.00 148.00 19.35 - -
T8 0.00 20.00 0.00 154.00 24.19 - -
T9 0.00 0.00 15.00 214.00 72.58 - -
T10 0.00 0.00 18.75 220.00 77.42 - -
T11 0.00 0.00 22.50 220.00 77.42 - -
T12 0.00 0.00 25.00 224.00 80.65 - -
T13 15.00 12.00 15.00 230.00 85.48 95.13 -9.65
T14 15.00 12.00 15.00 228.00 83.87 95.13 -11.26
T15 15.00 15.00 18.75 237.00 91.13 96.11 -4.98
T16 15.00 18.00 22.50 238.00 91.94 96.18 -4.25
T17 15.00 20.00 25.00 245.00 97.58 96.92 0.66
T18 18.75 12.00 15.00 250.00 101.61 97.00 4.61
T19 18.75 15.00 18.75 265.00 113.71 97.60 16.11
T20 18.75 15.00 18.75 260.00 109.68 97.60 12.07
T21 18.75 18.00 22.50 268.00 116.13 97.65 18.48
T22 18.75 20.00 25.00 270.00 117.74 98.11 19.64
T23 22.50 12.00 15.00 255.00 105.65 97.19 8.45
T24 22.50 15.00 18.75 265.00 113.71 97.75 15.96
T25 22.50 18.00 22.50 270.00 117.74 97.80 19.94
T26 22.50 18.00 22.50 267.00 115.32 97.80 17.53
T27 22.50 20.00 25.00 270.00 117.74 98.23 19.52
T28 25.00 12.00 15.00 270.00 117.74 97.75 19.99
T29 25.00 15.00 18.75 276.00 122.58 98.20 24.38
T30 25.00 18.00 22.50 280.00 125.81 98.24 27.57
T31 25.00 20.00 25.00 280.00 125.81 98.58 27.23
T32 25.00 20.00 25.00 282.00 127.42 98.58 28.84
T33 Bispyribac sodium 20% + Pyrazosulfron15%-WDG @ (20 + 15 g/ha) 194.00 56.45 - -
T34 Penoxsulam 1.02% + Cyhalofop butyl 5.1%-OD @ 120g a.i./ha 203.00 63.71 - -
T35 Hand weeding @ 20 & 40 DAS 286.00 130.65 - -
T36 WEED CHECK 124.00 0.00 - -
It is evident from table 6 and 7 that in respect of treatment with ternary herbicidal composition of present invention, yield increase of > 80% was observed as compared to control plot’s yield. Similar trend was also reflected in the number of tillers per square meter area and found that in most cases, it was more than the double than the untreated control plot.

Impact on paddy yield and net returns in respect of treatment on paddy using herbicidal composition comprising Penoxsulam, Pyrazosulfuron ethyl & Bispyribac sodium
Table 8:
Treatments g a.i./ha Effect of treatments on yield
S. No. Penoxsulam Pyrazosulfuron ethyl Bispyribac sodium Paddy Yield
mt/ha
T1 15.00 0.00 0.00 2.89
T2 18.75 0.00 0.00 2.99
T3 22.50 0.00 0.00 3.23
T4 25.00 0.00 0.00 3.34
T5 0.00 12.00 0.00 2.50
T6 0.00 15.00 0.00 2.58
T7 0.00 18.00 0.00 2.62
T8 0.00 20.00 0.00 2.70
T9 0.00 0.00 15.00 2.70
T10 0.00 0.00 18.75 2.75
T11 0.00 0.00 22.50 2.98
T12 0.00 0.00 25.00 3.10
T13 15.00 12.00 15.00 3.66
T14 15.00 12.00 15.00 3.51
T15 15.00 15.00 18.75 3.72
T16 15.00 18.00 22.50 3.82
T17 15.00 20.00 25.00 3.88
T18 18.75 12.00 15.00 3.86
T19 18.75 15.00 18.75 4.15
T20 18.75 15.00 18.75 4.00
T21 18.75 18.00 22.50 4.21
T22 18.75 20.00 25.00 4.19
T23 22.50 12.00 15.00 3.92
T24 22.50 15.00 18.75 3.98
T25 22.50 18.00 22.50 4.07
T26 22.50 18.00 22.50 4.04
T27 22.50 20.00 25.00 4.10
T28 25.00 12.00 15.00 4.12
T29 25.00 15.00 18.75 4.22
T30 25.00 18.00 22.50 4.30
T31 25.00 20.00 25.00 4.30
T32 25.00 20.00 25.00 4.33
T33 Bispyribac sodium 20% + Pyrazosulfron15%-WDG @ (20 + 15 g/ha) 3.37
T34 Penoxsulam 1.02% + Cyhalofop butyl 5.1%-OD @ 120g a.i./ha (Rs 1400/lt) 3.82
T35 Handweeding @ 20 & 40 DAS 4.24
T36 WEED CHECK 2.35
Table 9:
Treatments g a.i./ha Effect of treatments on economics of paddy
S. No. Penoxsulam Pyrazosulfuron ethyl Bispyribac sodium Cost of Herbicide treatment (including spraying charges)
Rs/Ha Additional yield kg/ha Additional income based on MSP of Paddy @ Rs30/kg Benefit: Cost Ratio
T1 15.00 0.00 0.00 2390 540 16200 6.78
T2 18.75 0.00 0.00 2738 640 19200 7.01
T3 22.50 0.00 0.00 3086 880 26400 8.55
T4 25.00 0.00 0.00 3317 990 29700 8.95
T5 0.00 12.00 0.00 1258 150 4500 3.58
T6 0.00 15.00 0.00 1323 230 6900 5.22
T7 0.00 18.00 0.00 1387 270 8100 5.84
T8 0.00 20.00 0.00 1452 350 10500 7.23
T9 0.00 0.00 15.00 1390 350 10500 7.55
T10 0.00 0.00 18.75 1488 400 12000 8.06
T11 0.00 0.00 22.50 1585 630 18900 11.92
T12 0.00 0.00 25.00 1650 750 22500 13.64
T13 15.00 12.00 15.00 3038 1310 39300 12.94
T14 15.00 12.00 15.00 3038 1160 34800 11.45
T15 15.00 15.00 18.75 3201 1370 41100 12.84
T16 15.00 18.00 22.50 3362 1470 44100 13.12
T17 15.00 20.00 25.00 3492 1526 45780 13.11
T18 18.75 12.00 15.00 3386 1510 45300 13.38
T19 18.75 15.00 18.75 3549 1800 54000 15.22
T20 18.75 15.00 18.75 3549 1650 49500 13.95
T21 18.75 18.00 22.50 3710 1858 55740 15.02
T22 18.75 20.00 25.00 3840 1840 55200 14.38
T23 22.50 12.00 15.00 3734 1570 47100 12.61
T24 22.50 15.00 18.75 3897 1630 48900 12.55
T25 22.50 18.00 22.50 4058 1718 51540 12.70
T26 22.50 18.00 22.50 4058 1690 50700 12.49
T27 22.50 20.00 25.00 4188 1750 52500 12.54
T28 25.00 12.00 15.00 3965 1770 53100 13.39
T29 25.00 15.00 18.75 4128 1870 56100 13.59
T30 25.00 18.00 22.50 4289 1950 58500 13.64
T31 25.00 20.00 25.00 4419 1950 58500 13.24
T32 25.00 20.00 25.00 4419 1980 59400 13.44
T33 Bispyribac sodium 20% + Pyrazosulfron15%-WDG @ (20 + 15 g/ha) 2298 1020 30600 13.32
T34 Penoxsulam 1.02% + Cyhalofop butyl 5.1%-OD @ 120g a.i./ha (Rs 1400/lt) 3650 1470 44100 12.08
T35 Handweeding @ 20 & 40 DAS 15000 1890 56700 3.78
T36 WEED CHECK 0 0 - -
MSP: Minimum support price
It is evident from table 8 and 9, cost of cultivation of paddy was highest in hand weeding operations with much lower in ternary herbicidal composition of present invention. Further, net returns were also highest in respect of treatment with ternary herbicidal composition of present invention with healthy Benefit: Cost ratio of 15.22:1.
Phytotoxicity Studies:
Experimental Methodology: The Untreated check plot was sprayed with water alone. Observations on phytotoxicity viz., yellowing, stunting, epinasty and hyponasty was recorded at 7, 14 and 21 days after application of , by adopting 0-10 rating scale as below:
Table 10:
Rating % of phytotoxicity
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%
10 91-100%

Table 11:
Treatments g a.i./ha Mean of Cumulative Phytotoxicity (%) on 7, 14 & 21st Day after application (DAA)
S. No. Penoxsulam Pyrazosulfuron ethyl Bispyribac sodium Yellowing (%) Stunting % Epinasty % Hyponasty %
T1 15.00 0.00 0.00 0.00 0.00 0.00 0.00
T2 18.75 0.00 0.00 0.00 0.00 0.00 0.00
T3 22.50 0.00 0.00 0.00 0.00 0.00 0.00
T4 25.00 0.00 0.00 0.00 0.00 0.00 0.00
T5 0.00 12.00 0.00 0.00 0.00 0.00 0.00
T6 0.00 15.00 0.00 0.00 0.00 0.00 0.00
T7 0.00 18.00 0.00 0.00 0.00 0.00 0.00
T8 0.00 20.00 0.00 0.00 0.00 0.00 0.00
T9 0.00 0.00 15.00 0.00 0.00 0.00 0.00
T10 0.00 0.00 18.75 0.00 0.00 0.00 0.00
T11 0.00 0.00 22.50 0.00 0.00 0.00 0.00
T12 0.00 0.00 25.00 0.00 0.00 0.00 0.00
T13 15.00 12.00 15.00 0.00 0.00 0.00 0.00
T14 15.00 12.00 15.00 0.00 0.00 0.00 0.00
T15 15.00 15.00 18.75 0.00 0.00 0.00 0.00
T16 15.00 18.00 22.50 0.00 0.00 0.00 0.00
T17 15.00 20.00 25.00 0.00 0.00 0.00 0.00
T18 18.75 12.00 15.00 0.00 0.00 0.00 0.00
T19 18.75 15.00 18.75 0.00 0.00 0.00 0.00
T20 18.75 15.00 18.75 0.00 0.00 0.00 0.00
T21 18.75 18.00 22.50 0.00 0.00 0.00 0.00
T22 18.75 20.00 25.00 0.00 0.00 0.00 0.00
T23 22.50 12.00 15.00 0.00 0.00 0.00 0.00
T24 22.50 15.00 18.75 0.00 0.00 0.00 0.00
T25 22.50 18.00 22.50 0.00 0.00 0.00 0.00
T26 22.50 18.00 22.50 0.00 0.00 0.00 0.00
T27 22.50 20.00 25.00 0.00 0.00 0.00 0.00
T28 25.00 12.00 15.00 0.00 0.00 0.00 0.00
T29 25.00 15.00 18.75 0.00 0.00 0.00 0.00
T30 25.00 18.00 22.50 0.00 0.00 0.00 0.00
T31 25.00 20.00 25.00 0.00 0.00 0.00 0.00
T32 25.00 20.00 25.00 0.00 0.00 0.00 0.00
T33 Bispyribac sodium 20% + Pyrazosulfron15%-WDG @ (20 + 15 g/ha) 0.00 0.00 0.00 0.00
T34 Penoxsulam 1.02% + Cyhalofop butyl 5.1%-OD @ 120g a.i./ha 0.00 0.00 0.00 0.00
T35 Handweeding @ 20 & 40 DAS 0.00 0.00 0.00 0.00
T36 WEED CHECK (control plot) 0.00 0.00 0.00 0.00
It is evident from table 11 that ternary herbicidal composition of present invention did not cause any significant visible damage to the paddy crop in terms of loss of pigmentation, crop growth, crop vigour etc. even at the suggested higher dosages.

Residual effect of herbicidal composition comprising Penoxsulam, Pyrazosulfuron ethyl & Bispyribac sodium on the succeeding crop:
The impact of the above treatments on the succeeding crop of Bengal gram was also studied in the following season after the harvest of paddy crop, and germination and crop growth parameters were studied and evaluated. It was found that the germination of Bengal gram crop was unaffected in treated as compared to the control plots. The response even at the higher dose of ternary herbicidal composition of present invention was not found to be adversely affecting the germination of the succeeding crop. Growth parameters as well yield of succeeding crop of Bengal gram taken in the same sub plots of the experimental field shown no reduction in germination, nil phytotoxicity or injury to Bengal gram crop. In fact, the yield attributes confirmed that there is no residual impact of the ternary herbicidal composition of present invention on the succeeding crop. This shows the safety of the ternary herbicidal composition of present invention in the next season on sensitive crop like Bengal gram
Table 12:
Treatments g a.i./ha Residual effect on succeeding crop
S. No. Penoxsulam Pyrazosulfuron ethyl Bispyribac sodium Germination% of succeeding gram crop after 10 DAS in the earlier treated plots Mean of Cumulative Phytotoxicity (%) on 1, 5, 10th Day after sowing gram crop Yield of Bengal gram kg/ha
T1 15.00 0.00 0.00 86.50 NS 1920.00
T2 18.75 0.00 0.00 86.30 NS 1960.00
T3 22.50 0.00 0.00 87.50 NS 1960.00
T4 25.00 0.00 0.00 87.00 NS 2050.00
T5 0.00 12.00 0.00 85.00 NS 1870.00
T6 0.00 15.00 0.00 85.67 NS 1920.00
T7 0.00 18.00 0.00 86.00 NS 1890.00
T8 0.00 20.00 0.00 86.00 NS 1900.00
T9 0.00 0.00 15.00 86.30 NS 1890.00
T10 0.00 0.00 18.75 86.33 NS 1880.00
T11 0.00 0.00 22.50 86.00 NS 1910.00
T12 0.00 0.00 25.00 86.30 NS 1900.00
T13 15.00 12.00 15.00 85.67 NS 1840.00
T14 15.00 12.00 15.00 85.00 NS 1830.00
T15 15.00 15.00 18.75 86.00 NS 1900.00
T16 15.00 18.00 22.50 86.00 NS 1800.00
T17 15.00 20.00 25.00 86.00 NS 1910.00
T18 18.75 12.00 15.00 86.00 NS 1900.00
T19 18.75 15.00 18.75 88.66 NS 1875.00
T20 18.75 15.00 18.75 88.02 NS 1862.00
T21 18.75 18.00 22.50 88.00 NS 1900.00
T22 18.75 20.00 25.00 87.40 NS 1920.00
T23 22.50 12.00 15.00 88.00 NS 1920.00
T24 22.50 15.00 18.75 87.00 NS 1880.00
T25 22.50 18.00 22.50 87.20 NS 1900.00
T26 22.50 18.00 22.50 87.00 NS 1872.00
T27 22.50 20.00 25.00 87.66 NS 1930.00
T28 25.00 12.00 15.00 88.00 NS 1885.00
T29 25.00 15.00 18.75 87.26 NS 1890.00
T30 25.00 18.00 22.50 88.00 NS 1920.00
T31 25.00 20.00 25.00 87.90 NS 1908.00
T32 25.00 20.00 25.00 88.60 NS 1925.00
T33 Bispyribac sodium 20% + Pyrazosulfron15%-WDG @ (20 + 15 g/ha) 85.00 NS
1900.00
T34 Penoxsulam 1.02% + Cyhalofop butyl 5.1%-OD @ 120g a.i./ha 86.00 NS 1910.00
T35 Handweeding @ 20 & 40 DAS 87.00 -
1880.00
T36 WEED CHECK (control plot) 83.33 -
1920.00
NS: Not significant
From the foregoing, it will be observed that numerous modifications and variations can be effectuated without departing from the true spirit and scope of the novel concepts of the present invention. It is to be understood that no limitations with respect to the specific embodiments illustrated is intended or should be inferred. It should be understood that all such modifications and improvements have been deleted herein for the sake of conciseness and readability but are properly within the scope of the following claims.
Although the invention has been described above with reference to the disclosed embodiments, those skilled in the art will readily appreciate that the specific embodiments detailed are only illustrative of the invention.

WE CLAIM:

[CLAIM 1]. A synergistic granular herbicidal composition comprising:
a. Penoxsulam or its agrochemically acceptable salts, derivatives in the range of 0.01 to 0.99% by weight of the composition; and
b. Pyrazosulfuron ethyl or its agrochemically acceptable salts, derivatives in the range of 0.01 to 0.99% by weight of the composition; and
c. Bispyribac sodium or its agrochemically acceptable salts, derivatives in the range of 0.01 to 0.99% by weight of the composition.
[CLAIM 2]. The granular herbicidal composition as claimed in claim 1, further comprising one or more of agrochemically acceptable excipients.

[CLAIM 3]. The granular herbicidal composition as claimed in claim 2, wherein the agrochemically acceptable excipients are selected from the group comprising of stabilizers, emetic agents, rain-fasteners, solubilizers, adjuvants, antifoaming agent, anti-freezing agent, wetting agent, dispersing agent, dye (s), fillers, thickening agent, stabilizing agent, carriers, surface active compounds (surfactants and / or emulsifiers), antibacterial agents, protective colloids, adhesives, thixotropic agents, penetration agents, sequestering agents, quick coating agent or sticking agents/sticker, spreader, binders, anti-caking agents, adjuvants, emulsifiers, colouring pigments, dyes, preservatives, buffering agent, solvent or combination thereof.
[CLAIM 4]. The granular herbicidal composition as claimed in claim 3, wherein the dispersing agent is selected from the group comprising of Sodium ligno sulphate, Calcium ligno sulphate, Polyarylphenyl ether phosphate, tristyryl phenol ethylated , Acrylic Copolymer, Ethoxylated Tristryl phenol Sulphate, Naphthalene sulfonic acid, sodium salt condensate with formaldehyde, Ethoxylated oleyl cetyl alcohol, Polyalkelene glycol ether, Ethoxylated Fatty alcohol, Sodium lauryl sulphate, sodium naphthalene sulphonate formaldehyde condensates, Sodium polyalkylnaphthalene sulphonate (Dispersal BB4), sodium polycarboxylate (Geropon T 36), sodium methyl oleoyltaurate (Geropon T 77), phenol sulfonic acid-formaldehyde-polycondensation as sodium salt (Tamol FBPP), sodium salt of methyl naphthalene sulfonate (Supragil MNS 90), phenol sulfonic acid-formaldehyde-polycondensation as sodium salt (Dispersal PSRl 9), calcium dodecylbenzene sulfonate (Rhodocal 60 BR), polyalkoxylated butyl ether (Ethylan NS 500 LQ), phenol sulfonic acid-formaldehyde (Tamol DN), tristyrylphenol ethoxylate phosphate esters, aliphatic alcohol ethoxylates, alky ethoxylates; EO-PO block copolymers, and graft copolymers, Acrylate copolymer (Agrilan 789), polycarboxylates, alkyl naphthalene sulfonates (such as Morwet IP, Morwet EFW), sodium salt of naphthalene sulfonate condensate (Morwet D-425), phenol sulphonic acid condensates, alkyl sulfonates, alkenyl sylfonates, mixture of alkyl sulfonates and alkenyl sylfonates (Lissapol D), alkyl suflosuccinates (Geropon), L-Wet, methyl oleyltaurates and poly vinyl alcohols or mixtures thereof.
[CLAIM 5]. The granular herbicidal composition as claimed in claim 4, wherein the dispersing agent is present in a range of about 0.5-10% of the total weight of the composition.
[CLAIM 6]. The granular herbicidal composition as claimed in claim 3, wherein the wetting agent is selected from the group comprising of non-ionic surfactants, anionic surfactant and a mixture of anionic and non-ionic surfactant and polymeric surfactant.
[CLAIM 7]. The granular herbicidal composition as claimed in claim 6, wherein the wetting agent is selected from Tristyrylphenol ethoxylate, non-ionic emulsifier, mixture of non-ionic surfactants & alkoxylated alcohol/block copolymer or mixtures thereof.

[CLAIM 8]. The granular herbicidal composition as claimed in claim 7, wherein the wetting agent is present in a range of about 0.5-10% of the total weight of the composition.
[CLAIM 9]. The granular herbicidal composition as claimed in claim 3, wherein the antifoaming agent is selected from the group comprising of Siloxane polyalkyleneoxide, polydimethyl siloxane, silicon based agents, absorbed polydimethyl siloxane, stearates, silicones (SILFOAM®, SILFAR®, PULPSIL ® and WACKER® AK) and ethoxylates or mixtures thereof.
[CLAIM 10]. The granular herbicidal composition as claimed in claim 9, wherein the antifoaming agent is present in a range of about 0.01-1% of the total weight of the composition.
[CLAIM 11]. The granular herbicidal composition as claimed in claim 3, wherein the anti-freezing agent is selected from the group comprising of Glycol, Propylene Glycol, Mono ethylene glycol, Glycerin, Diethylene glycol or mixtures thereof.
[CLAIM 12]. The granular herbicidal composition as claimed in claim 11, wherein the anti-freezing agent is present in a range of about 0.1-10% of the total weight of the composition.
[CLAIM 13]. The granular herbicidal composition as claimed in claim 3, wherein the adjuvants are selected from the group comprising of Silicone Ethoxylated Oil, Polyvinyl Pyrrolidone, Poly vinyl Alcohol, blend of poly terpene resin or mixtures thereof.
[CLAIM 14]. The granular herbicidal composition as claimed in claim 13, wherein the adjuvants are present in a range of about 0.1-10% of the total weight of the composition.
[CLAIM 15]. The granular herbicidal composition as claimed in claim 3, wherein the filler is selected from the group comprising of Silicon Dioxide, China –Clay, Kaolin, sand, Talc, starch, Urea formaldehyde resin or mixtures thereof.
[CLAIM 16]. The granular herbicidal composition as claimed in claim 15, wherein the filler is present in a range of about 0.1-20% of the total weight of the composition.
[CLAIM 17]. The granular herbicidal composition as claimed in claim 3, wherein the anti-bacterial agent is selected from the group comprising of Benzisothiazolin-3-one, Formaldehyde/Sodium benzoate/Sodium o-phenyl phenate, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one or mixtures thereof.
[CLAIM 18]. The granular herbicidal composition as claimed in claim 17, wherein the anti-bacterial agent is present in a range of about 0.01-1% of the total weight of the composition.
[CLAIM 19]. The granular herbicidal composition as claimed in claim 3, wherein the thickening and stabilising agent is selected from the group comprising of Polysaccharides, carboxymethyl cellulose, Bentonite Clay, Aluminum Magnesium Silicate or mixtures thereof.
[CLAIM 20]. The granular herbicidal composition as claimed in claim 19, wherein thickening and stabilising agent is present in a range of about 0.01-3% of the total weight of the composition.
[CLAIM 21]. The granular herbicidal composition as claimed in claim 1 or 2, wherein the particle size of composition is in the range 5-45 microns.
[CLAIM 22]. The granular herbicidal composition as claimed in claim 1 or 2, wherein the composition is applied to directly to a plant/crop without any on-farm dilution.
[CLAIM 23] A process for preparing synergistic granular herbicidal composition comprising the steps of:
a. blending all the active ingredients with wetting agent, dispersing agent, suspending agent and filler along with other excipients to a homogenous mixture;
b. grinding the blended mixture obtained in step a) through Jet mill/ air classifier mills;
c. finely grinded material obtained in step b) is blended in post blended to obtain homogenous material to obtain particle size in the range of 5-45 microns;
d. homogenous material of step c) is unloaded into 25 kg. HDPE bag with LDPE liner inside;
e. Charge the required quantity of sand in granulator, to which is added DM water, sticking agent and remaining excipients till it become homogeneous;
f. Adding finely grinded material obtained in step e) to be completely coated on sand.
[CLAIM 24]. A kit-of-parts comprising a plurality of components, wherein said plurality of components comprises:
a. Penoxsulam or its agrochemically acceptable salts, derivatives in the range of 0.01 to 0.99% by weight of the composition; and
b. Pyrazosulfuron ethyl or its agrochemically acceptable salts, derivatives in the range of 0.01 to 0.99% by weight of the composition; and
c. Bispyribac sodium or its agrochemically acceptable salts, derivatives in the range of 0.01 to 0.99% by weight of the composition.