DESC:FIELD OF THE INVENTION:

The present invention relates to a synergistic herbicidal composition comprising A) Metamifop B) at least one herbicide selected from Bispyribac sodium, Fenoxaprop-P-Ethyl and Cyhalofop butyl C) at least one more herbicide selected from Pyrazosulfuron Ethyl, Ethoxysulfuron, Metsulfuron methyl, Imazosulfuron, Propyrisulfuron, Azimsulfuron, Tefuryltrione, Penoxsulam, Pyribenzoxim, Bentazon, Saflufenacil, 2,4-D and salts thereof with one or more inactive excipients. The present invention also relates to process for preparing the said composition and its use as herbicide.

BACKGROUND OF THE INVENTION

Metamifop is chemically known as (2R)-2-[4-[(6-chloro-2-benzoxazolyl)oxy]-phenoxy]-N-(2-fluorophenyl)-N-methylpropanamide. and chemical structure is as below;

Metamifop is an aryloxyphenoxypropionate herbicide under evaluation in the United States for annual grass control in cool-season turfgrasses. Insufficient information is available on the most effective metamifop application timings and mixtures for POST smooth crabgrass control.

Bispyribac-sodium is a new post-emergence pyrimidinyl carboxy herbicide for the control of a wide range of weeds, in particular on Echinochloa crus-galli; the application done from the fourth unfolded leaf up to the tillering stage presents a good plant compatibility in direct-seed rice. Bispyribac-sodium mode of action consists in the inhibition of the branched amino acid biosynthesis. This compound presents a good eco-toxicology profile; it is suitable for application on paddy rice.

Fenoxaprop-p-ethyl as active ingredient which is a selective herbicide having action against Echinochloa sp. and other grassy weeds in soybean, rice, cotton, black gram and onion. It is a post-emergent herbicide having action on broad spectrum of grasses. Fenoxaprop-p-ethyl is quickly taken up by the leaves and stems of the grassy weeds.

Cyhalofop butyl is a systemic post-emergence herbicide for the control of grassy weeds in direct seeded rice. It can be used with fields that are partially flooded or drained provided weeds are exposed to spray; thus provides flexibility for various water management practices. It has wide window of application, low potential for drift issues to neighboring broadleaf crops.

Pyrazosulfuron-ethyl(code name NC-311, trade name Sirius) is a new sulfonylurea herbicide for rice, being developed and launched in major rice producing countries. In greenhouse studies, NC-311 demonstrated excellent herbicidal activity with both pre and post emergence applications. I75 values of NC-311 pre-emergence were below 10 g a. i./ha except for Echinochloa crus-galli.

Ethoxysulfuron is is a post-emergent broad spectrum herbicide very effective for the control of sedges and broad leaf weeds in transplanted rice. Sun rice contains Ethoxysulfuron as active ingredient which belongs to sulfonyl urea group of herbicides. When combined with grass herbicide like Ricestar as tank mix it can offer total weed control in rice.

Ethoxysulfuron is mainly taken up by the leaves and is translocated within the plant. After inhibition of plant growth, chlorotic patches develop and spread at first acropetally, then basipetally. The action of the product reaches its conclusion about 3-4 weeks after application with the death of the whole plant. Ethoxysulfuron acts by inhibition of the acetolactate.

Metsulfuron-methyl, also known as MSM, is a sulfonylurea herbicide (WSSA group 2) that is used to control broadleaf weeds and certain grass weeds (including bahiagrass) post-emergence in Bermuda grass, St. Augustine, and other warm season turfgrasses. Metsulfuron-methyl is a very popular herbicide because it provides effective control of some of the most problematic turfgrass weeds, such as wild garlic (Allium vineale), Florida betony (Stachys floridana), dollar weed (Hydrocotyle umbellata), and small Virginia button weed (Diodia virginiana). It is usually formulated as a dispersible granule containing 60% of the active ingredient. The use rates are much lower than for most turf herbicides, ranging from 0.25 to 1 ounce of formulated product per acre, depending on the weed species to be controlled.

Metsulfuron-methyl is a systemic herbicide (meaning that it is translocated and moves throughout the plant) that inhibits the production of three essential amino acids that plants need in order to survive. When susceptible weeds are treated, injury symptoms like chlorosis (yellowing of foliage) and necrosis (brown or black dying foliage) usually appear within one to two weeks after application (Figure 2). Metsulfuron-methyl is absorbed by plant foliage, so if ornamentals come into contact with the spray or drift, injury is likely to result. However, metsulfuron-methyl has low drift potential when label precautions are followed, and off-target movement does not appear to be the primary cause of injury on ornamental plants.

Imazosulfuron is a new post-emergence sulfonylurea herbicide. It is highly active at low application rates to control annual and perennial broad-leaf weeds and sedges in rice. There is increasing concerned about the persistence of pesticide residues in soils, crop produce and subsequent contamination of groundwater. Imazosulfuron is a solfonylurea herbicide, it has sistemic activity and controls a broad spectrum of perennial and annual weeds. Imazosulfuron has a favourable toxicological and ecotoxicological profile and is applied on flooded or drained fields in early post emergence of the crop

Propyrisulfuron is a novel sulfonylurea herbicide with a fused heterocyclic moiety, developed by Sumitomo Chemical Co., Ltd. Propyrisulfuron is used as a rice herbicide to control annual and perennial paddy weeds, including Echinochloa spp., sedges and broadleaf weeds. Propyrisulfuron controls weed biotypes that have developed resistance to the commercialized sulfonylurea herbicides. Propyrisulfuron shows safer profiles for human health and the environment. The granular formulation, suspension concentrate formulation and jumbo formulation (granules packed in water-soluble film) are available in Japan with the brand name of ZETA-ONE.

Azimsulfuron is a herbicide, as a member of the sulfonylurea group of herbicides, has a mode of action of inhibiting of the biosynthesis of essential amino acids insusceptible plants, through the inhibition of acetolactate synthase (ALS). As a member of the sulfonylurea group of herbicides, it is a weed resistance management Group B herbicide. The proposed use for Azimsulfuron herbicide is post-emergent control of certain aquatic broadleaf weeds, and the suppression of Barnyard grass in rice.

Penoxsulam is a systemic herbicide for broad spectrum weed control in rice crop.
It controls key grass (annual species of Echinochloa), broadleaf and sedge weeds.
It is a completely safe to the rice crop as well as succeeding crops at recommended dose. causes death of target weeds by inhibiting the plant enzyme Aceto Lactate Synthase (ALS). Inhibition of ALS stops synthesis of amino acids which affects protein synthesis and cell division ultimately leading to death of target weeds.

Penoxsulam provides dual action to control target weeds: Its application at 1-3 leaf stage which generally coincides with 8-12 days after transplanting, controls germinated weeds present in the field (1st action). Application at this stage also reduces fresh germination of weeds which was expected to come from subsequent flushes of weeds (2nd action).

Pyribenzoxim is a Broad-spectrum post-emergence herbicide used to control grasses and polygonums in rice, wheat and other crops. Its mode of action is via the inhibition of acetolactate synthase ALS (acetohydroxyacid synthase AHAS).

Bentazon, 3-(1-methylethyl)-1H-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide, is a herbicide used in agriculture for control of broadleaf weeds in crops such as soybeans, rice, corn, peanuts, and lima beans. As summarized from U.S. EPA reports (1998b,g), bentazon is not chemically reactive and no highly reactive species have been identified during its metabolism. Bentazon was negative in bacterial mutation assays, in a mammalian cell assay, in the unscheduled DNA synthesis assay, and in the mouse micronucleus assay in vivo. Bentazon is a colorless to white crystalline powder. Commercial product can be a soluble concentrate that may be mixed with water and used as a spray.

Saflufenacil is a new herbicide of the pyrimidinedione chemical class for preplant burndown and selective pre-emergence dicot weed control in multiple crops, including corn. Saflufenacil has pre-emergence selectivity based on physical placement and in planta crop tolerance. In corn, saflufenacil can be used pre-emergence at 63 to 125 g ai ha21 for broad dicot weed control, including large-seeded species such as velvetleaf and common cocklebur (Xanthium strumarium L.) (Liebl et al. 2008). After application, saflufenacil elicits the same type of phytotoxic symptoms, with rapid light dependent wilting and necrosis of the shoot tissue, as protoporphyrinogen IX oxidase (PPO)–inhibiting, peroxidizing herbicides in susceptible plant species.

2,4-Dichlorophenoxyacetic acid (usually called 2,4-D) is a systemic herbicide which selectively kills most broadleaf weeds by causing uncontrolled growth in them, but leaves most grasses such as cereals, lawn turf, and grassland relatively unaffected.
2,4-D is primarily used as a selective herbicide which kills many terrestrial and aquatic broadleaf weeds, but not grasses. It acts by mimicking the action of the plant growth hormone auxin, which results in uncontrolled growth and eventually death in susceptible plants. Because it was discovered in the 1940s, a patent no longer governs the manufacture and sale of 2,4-D, and any company is free to produce it. Thus, it is sold in various formulations under a wide variety of brand names. 2,4-D can be found in commercial lawn herbicide mixtures, which often contain other active ingredients including mecoprop and dicamba.

CN106719704A discloses a weeding composition containing metamifop, clomazone and bispyribac-sodium, which is prepared from the following effective components: metamifop, clomazone and bispyribac-sodium, wherein the weight ratio of metamifop, clomazone and bispyribac-sodium is (10-50):(5-45):(1-9). According to the weeding composition, the herbicide controlling spectrum can be obviously expanded, and the overall prevention and removal effect on rice field weeds is enhanced; meanwhile, the composition is high in safety to rice, and is a very good novel drug composition for preventing and removing annual weeds in a rice field.

CN102792954A relates to the technical field of pesticides, and discloses a rice mixed herbicide. The herbicide comprises two active ingredients of metamifop and pyrazosulfuron-ethyl, wherein the weight ratio of the two active ingredients is 1:3.3-70:1; and the mass percentage of the two active ingredients is 1-85% of the mixed herbicide. By mixing the two active ingredients of metamifop and pyrazosulfuron-ethyl, complementarity of each ingredient for eradicating weeds is increased and shortages when each ingredient is used alone are supplemented. The herbicide can not only prevent and eradicate annual gramineae weeds in rice fields, but also can prevent and eradicate broadleaf weeds and cyperaceae weeds, and has significant synergistic effects. The herbicide composition has not only obvious effects for eradicating weeds but also good security for the rice, has no influence on subsequent crops, and is an ideal herbicide.

CN104824003A relates to a herbicidal composition containing propyrisulfuron, cyhalofop-butyl and metamifop, which comprises the active ingredients of propyrisulfuron, cyhalofop-butyl and metamifop, wherein the weight ratio of propyrisulfuron, to cyhalofop-butyl to metamifop is (1-20): (1-40): (1-30). The herbicidal composition provided by the invention has synergy against weeds in a paddy field, can expand a weed control spectrum and reduce the risk of weed resistance, and is suitable for controlling the annual weeds in the paddy rice.

CN102461554A relates to a mixed weeding composite containing bispyribac and pyrazosulfuron. The weeding composite takes the bispyribac and the pyrazosulfuron as main active ingredients, and the mass ratio of the bispyribac and the pyrazosulfuron is 1-99/1-99. The composite and agricultural agent-allowed auxiliary agents are processed into missible oils, suspending agents, water dispersible granules, wettable powder and various dosage forms. The weeding composite can prevent and weed ephemeral weeds of grass families, broad leaves and sedge families in paddy field, compared with a single herbicide, under the premise of improving the efficacy, the mixed weeding composite has the weakened herbicide resistance, wide weeding scope and long duration, is safe to paddy and succeeding crops, and is an ideal weeding composite for the paddy field.

CN106508940A describes (pyrazosulfuron-ethyl)-(cyhalofop-butyl)-(bispyribac-sodium) dispersible oil suspending agent, a processing method thereof and uses of the dispersible oil suspending agent are disclosed. The dispersible oil suspending agent comprises 20.3-23.7% by mass of pyrazosulfuron-ethyl, cyhalofop-butyl and bispyribac-sodium active compounds, wherein the mass percentage of the pyrazosulfuron-ethyl active compound is 1.7-2.3%, the mass percentage of the cyhalofop-butyl active compound is 14.1-15.9% and the mass percentage of the bispyribac-sodium active compound is 4.5-5.5%. The dispersible oil suspending agent is used for control of annual gramineous and cyperaceae weeds and a part of broad-leafed weeds in direct seeded rice fields, a preparation using amount is 35-45 g per mu, and stems and leaves are sprayed with mist in a 2-3 leaf stage of the weeds. The dispersible oil suspending agent is prepared by blending the pyrazosulfuron-ethyl, the cyhalofop-butyl and the bispyribac-sodium, and is safe to rice and wide in weed control spectrum. Control effects of the blending product of the pyrazosulfuron-ethyl, the cyhalofop-butyl and the bispyribac-sodium for the annual gramineous and cyperaceae weeds and a part of broad-leafed weeds in the direct seeded rice fields are good.

However still there is a need for a synergistic herbicidal composition which overcomes some of the existing problems and can be prepared easily without much complex manufacturing process and exhibits synergism.

Inventors of the present invention have surprisingly found that the synergistic herbicidal composition comprising A) Metamifop B) at least one herbicide selected from Bispyribac sodium, Fenoxaprop-P-Ethyl and Cyhalofop butyl C) at least one more herbicide selected from Pyrazosulfuron Ethyl, Ethoxysulfuron, Metsulfuron methyl, Imazosulfuron, Propyrisulfuron, Azimsulfuron, Tefuryltrione, Penoxsulam, Pyribenzoxim, Bentazon, Saflufenacil, 2,4-D and salts thereof with one or more inactive excipients described herein can provide solution to the above mentioned problems.

SUMMARY OF THE INVENTION

It is an aspect of the present invention is to provide, with a view to effective resistance management and effective control of weeds especially grassy weeds, at application rates which are as low as possible, compositions which, at a reduced total amount of active compounds applied, have improved activity against the harmful weeds and a broadened activity spectrum, in particular for certain indications.

We have accordingly found that this object is achieved by synergistic herbicidal composition comprising A) Metamifop B) at least one herbicide selected from Bispyribac sodium, Fenoxaprop-P-Ethyl and Cyhalofop butyl C) at least one more herbicide selected from Pyrazosulfuron Ethyl, Ethoxysulfuron, Metsulfuron methyl, Imazosulfuron, Propyrisulfuron, Azimsulfuron, Tefuryltrione, Penoxsulam, Pyribenzoxim, Bentazon, Saflufenacil, 2,4-D and salts thereof with one or more inactive excipients.

Accordingly, in a main aspect of the present invention provides a synergistic herbicidal composition comprising A) Metamifop B) at least one herbicide selected from Bispyribac sodium, Fenoxaprop-P-Ethyl and Cyhalofop butyl C) at least one more herbicide selected from Pyrazosulfuron Ethyl, Ethoxysulfuron, Metsulfuron methyl, Imazosulfuron, Propyrisulfuron, Azimsulfuron, Tefuryltrione, Penoxsulam, Pyribenzoxim, Bentazon, Saflufenacil, 2,4-D and salts thereof with one or more inactive excipients.

Accordingly, in a second aspect, the present invention provides a method of preparing the synergistic herbicidal composition comprising A) Metamifop B) at least one herbicide selected from Bispyribac sodium, Fenoxaprop-P-Ethyl and Cyhalofop butyl C) at least one more herbicide selected from Pyrazosulfuron Ethyl, Ethoxysulfuron, Metsulfuron methyl, Imazosulfuron, Propyrisulfuron, Azimsulfuron, Tefuryltrione, Penoxsulam, Pyribenzoxim, Bentazon, Saflufenacil, 2,4-D and salts thereof with one or more inactive excipients.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides solution to all the problems mentioned above by providing the synergistic herbicidal composition.

The present invention provides a synergistic herbicidal composition comprising A) Metamifop B) at least one herbicide selected from Bispyribac sodium, Fenoxaprop-P-Ethyl and Cyhalofop butyl C) at least one more herbicide selected from Pyrazosulfuron Ethyl, Ethoxysulfuron, Metsulfuron methyl, Imazosulfuron, Propyrisulfuron, Azimsulfuron, Tefuryltrione, Penoxsulam, Pyribenzoxim, Bentazon, Saflufenacil, 2,4-D and salts thereof with one or more inactive excipients.

"Effective amounts” as mentioned herein means that amount which, when applied treatment of crops, is sufficient to effect such treatment.

As used herein, the term "synergistic" means a combination of components wherein the activity of the combination is greater than the sum of the individual activities of each component of the combination.

As per one embodiment, the active herbicidal compound as mentioned above to be used in the composition of present invention can be in the form of base or any salts form known in the art.

The formulation or composition of the present invention can be in various physical forms, for example in the form of a dustable powder (DP), a gel, a wettable powder (WP), a granule (GR) (such as an emulsifiable granule (EG) or more particularly a water-dispersible granule (WG)), a water-dispersible tablet (WT), an emulsifiable concentrate (EC), a micro- emulsifiable concentrate, an oil-in-water emulsion (EW), an oil flowable ( a spreading oil (SO)), an aqueous dispersion ( aqueous suspension concentrate (SC)), an oily dispersion (OD), a suspo-emulsion (SE), a capsule suspension (CS), a soluble liquid, a water-soluble concentrate (with water or a water-miscible organic solvent as carrier), ZC (Mixed formulation of CS and SC), ZE (Mixed formulation of CS and SE), ZW (Mixed formulation of CS and EW).

In a preferred embodiment, the formulation comprising composition of present invention is selected from Suspension Concentrate (SC), Suspo emulsion (SE), Capsule Suspension (CS), Oil Dispersion (OD), Micro emulsion (ME), Dispersal concentrate (DC), Soluble liquid (SL), Emusifiable concentrate (EC), Emulsion in water (EW), Soluble liquid (SL), mixed formulation of CS and SC (ZC), a mixed formulation of CS and SE (ZE), a mixed formulation of CS and EW (ZW), Granules (Soil Applied Granules), Controlled Release Granules (CR Granules), Slow release and Fast release microsphere Granules (MS Granules), Water Soluble Granules (SG), Water dispersible granule (WDG or WG), Capsulated dry flowable (CDF), Dry flowalbe (DF), Jumbo ball formulation, Water soluble bag formulation, Wettable Powder (WP), Soluble Powder (SP), Dusting Powder (DP).

As per one embodiment, the synergistic herbicidal composition comprising A) Metamifop B) at least one herbicide selected from Bispyribac sodium, Fenoxaprop-P-Ethyl and Cyhalofop butyl C) at least one more herbicide selected from Pyrazosulfuron Ethyl, Ethoxysulfuron, Metsulfuron methyl, Imazosulfuron, Propyrisulfuron, Azimsulfuron, Tefuryltrione, Penoxsulam, Pyribenzoxim, Bentazon, Saflufenacil, 2,4-D and salts thereof with one or more inactive excipients., wherein active ingredients are present in concentration as described below;

Compound A Compound B Compound C
Active Ingredient Metamifop Bispyribac sodium, Fenoxaprop-P-Ethyl,
Cyhalofop butyl Pyrazosulfuron Ethyl, Ethoxysulfuron, Metsulfuron methyl, Imazosulfuron, Propyrisulfuron, Azimsulfuron, Tefuryltrione, Penoxsulam, Pyribenzoxim, Bentazon, Saflufenacil,
2,4-D
Concentration 0.1-20% 0.1-30% 0.1-50%

In another embodiment of the present invention the synergistic herbicidal composition comprising A) Metamifop B) at least one herbicide selected from Bispyribac sodium, Fenoxaprop-P-Ethyl and Cyhalofop butyl C) at least one more herbicide selected from Pyrazosulfuron Ethyl, Ethoxysulfuron, Metsulfuron methyl, Imazosulfuron, Propyrisulfuron, Azimsulfuron, Tefuryltrione, Penoxsulam, Pyribenzoxim, Bentazon, Saflufenacil, 2,4-D and salts thereof with one or more inactive excipients effective for controlling or killing of resistant and tough to control weeds.

An herbicidal synergistic composition of present invention controls all kind of monocots, dicots and sedges weeds. The most common weeds controlled are selected from several species of grasses, broad leaf weeds and sedges.
Aeschynomene aspera, Aeschynomene indica, Ageratum conyzoides, Alternanthera sessilis, Alternanthera philoxeroides, Amaranthus spinosus, Amaranthus viridis, Ammania baccifera, Cynodon dactylon, Dactyloctenium aegyptium, Digitaria ciliaris, Digitaria setigera, Ischaemum rugosum, Echinochloa colona, Echinochloa crus-galli, Echinochloa glabrescens, Echinochloa crus-pavonis, Echinochloa esculenta, Echinochloa frumentacea, Echinochloa muricata, Echinochloa oryzoides, Echinochloa paludigena, Eleocharis kuruguwai, Laptochloa chinensis, Eleusine indica, Eclipta alba, Eclipta prostate, Imperata cylindrical, Leersia hexandra, Leptochloa chinensis, Oryza sativa, Panicum repens, Paspalum distichum, Paspalum scrobiculatum, Rottboellia cochinchinensis, Setaria glauca, Bolboschoenus maritimus, Bergia capensis, Commelina benghalensis, Commelina diffusa, Cyanotis axillaris, Eclipta alba, Eclipta prostrate, Eichhornia crassipes, Ipomoea aquatic, Ludwigia adscendens, Ludwigia hyssopifolia, Ludwigia octovalvis, Ludwigia parviflora, Marsilea minuta, Marsilea quadrifoliata, Mimosa diplotricha, Monochoria vaginalis, Pistia stratiotes, Polygonum hydropiper, Portulaca oleracea, Sagittaria milliacea, Sagittaria sagittifolia, Sphenoclea zeylanica, Trianthema portulacastrum, Typha spp., Isachne globosa, Paspalum distichum, Cyperus difformis, Cyperus haspen, Cyperus iria, Cyperus rotundus, Fimbristylis dichotoma, Fimbristylis miliacea, Scirpus juncoides, Scirpus nipponicus, Scirpus planiculmis, Scirpur royelei, Scirpus juncoides. In a preferred embodiment, the composition of present invention especially effective for control of Dactyloctenium aegyptium, Digitaria ciliaris, Ischaemum rugosum and Laptochloa chinensis and Oryza sativa (Red rice).

In one embodiment of the present invention, the synergistic herbicidal composition of present invention is effective in controlling the growth of undesirable vegetation in GMO (Genetically Modified) Paddy or non GMO varieties of Paddy or Rice (Oryza sativa L.) including Indica, Japonica and Javanica race.

The synergistic herbicidal compositions can be also employed to promote non-selection and selective herbicidal action in fallow land, non-cropped industrial land, road and highway sides.

The present invention of synergistic herbicidal composition comprising A) Metamifop B) at least one herbicide selected from Bispyribac sodium, Fenoxaprop-P-Ethyl and Cyhalofop butyl C) at least one more herbicide selected from Pyrazosulfuron Ethyl, Ethoxysulfuron, Metsulfuron methyl, Imazosulfuron, Propyrisulfuron, Azimsulfuron, Tefuryltrione, Penoxsulam, Pyribenzoxim, Bentazon, Saflufenacil, 2,4-D and salts thereof with one or more inactive excipients has advantages as mentioned below;
1. Synergism between three active ingredients in comparison to activity of single ingredients,
2. Covers broad spectrum of weeds
3. Synergism will be useful for control/kill of resistant and tough to control weeds.
4. Offer longer residual control

• Weed stage:
Actively growing weeds from 2 leaf stage to fully grown weeds. 1 leaf to full grown weeds. 1 cm to 50 cm height. Vegetative to reproductive stage of weeds. It can be applied in nursery as well as main field after sowing or transplanting.
The herbicidal compositions according to the present invention can be applied post- emergence. If any active ingredient of the inventive compositions, is less well tolerated by certain crop plants, application techniques may be used in which the herbicidal compositions are sprayed, with the aid of the spraying equipment, in such a way that as far as possible they do not come into contact with the leaves of the sensitive crop plants, while the active compounds reach the leaves of undesirable plants growing underneath, or the bare soil surface (post- directed, lay-by).

Moreover, it may be advantageous to apply the compositions of the present invention on their own or jointly in combination with other crop protection agents, for example with agents for controlling pests or phytopathogenic fungi or bacteria or with groups of active compounds which regulate growth. Also of interest is the miscibility with mineral salt solutions which are employed for treating nutritional and trace element deficiencies. Non-phytotoxic oils and oil concentrates can also be added.

When employed in plant protection, the amounts of active substances applied, i.e. active ingredient I, II and III without formulation auxiliaries, are, depending on the kind of effect desired, from 0.1 to 10000 grams per hectare (g/ha), preferably from 1 to 1000 g/ha, more preferably from 1 to 500 g/ha.

The formulation may or may not containing crop safener, especially the safener for rice/paddy crop along with active ingredients and formulation auxiliaries. The amount of crop safener varies from 0.1 to 10%.

According to the invention the amount of composition of present invention is to be applied depending upon the kind of effect desired, from 1 to 10000 ml or g per hectare, preferable from 10 to 5000 ml or g per hectare, more preferably from 100 to 2000 ml or g per hectare.

The addition of additives may be combined with the synergistic mixture formulations, are organo silicone surfactant, non-ionic surfactant, ammonium sulphate, urea ammonium nitrate, crop oil concentrates to increase the control of weeds, to improve the control of target weeds, enhance the speed of kill of weeds and to control hardy weeds. The organo silicone surfactant or non-ionic surfactant can be added from 0.01% to 1%, most preferable from 0.01% to 0.5%. The ammonium sulphate and urea ammonium nitrate can be added from 0.01% to 2%, most preferable from 0.1% to 0.5%. The crop oil concentrate must contain either a petroleum or vegetable and petroleum oil concentrates should contain emulsifier to have good mixing properties. Highly refined vegetables oil have been shown to be more successful as additives than those that unrefined.

One or more inactive excipient is selected from including but not limited to dispersant, anti-freezing agent, anti-foam agent, wetting agent, suspension aid, anti-microbial agent, thickener, quick coating agent or sticking agents (also referred to as “stickers” or “binders”) and buffering agent.

Surfactants that are used as dispersants have the ability to adsorb strongly onto a particle surface and provide a charged or stearic barrier to re-aggregation of particles. The most commonly used surfactants are anionic, non-ionic, or mixtures of the two types. For wettable powder formulations, the most common dispersants are sodium lignosulphonates. For suspension concentrates, very good adsorption and stabilization are obtained using polyelectrolytes, such as sodium naphthalene sulphonate formaldehyde condensates. Tristyrylphenolethoxylate phosphate esters are also used. Nonionics such as alkylarylethylene oxide condensates and EO-PO block copolymers are sometimes combined with anionics as dispersants for suspension concentrates. In recent years, new types of very high molecular weight polymeric surfactants have been developed as dispersants. These have very long hydrophobic ‘backbones’ and a large number of ethylene oxide chains forming the ‘teeth’ of a ‘comb’ surfactant. These high molecular weight polymers can give very good long-term stability to suspension concentrates because the hydrophobic backbones have many anchoring points onto the particle surfaces. Examples of dispersants used herein include but not limited to sodium lignosulphonates; sodium naphthalene sulphonate formaldehyde condensates; tristyrylphenolethoxylate phosphate esters; aliphatic alcohol ethoxylates; alky ethoxylates; EO-PO block copolymers; and graft copolymers or mixtures thereof.

Anti-freezing agent as used herein can be selected from the group consisting of polyethylene glycols, methoxypolyethylene glycols, polypropylene glycols, polybutylene glycols, glycerin and ethylene glycol.

Water-based formulations often cause foam during mixing operations in production. In order to reduce the tendency to foam, anti-foam agents are often added either during the production stage or before filling into bottles. Generally, there are two types of anti-foam agents, namely silicones and non-silicones. Silicones are usually aqueous emulsions of dimethyl polysiloxane while the non-silicone anti-foam agents are water-insoluble oils, such as octanol and nonanol, or silica. In both cases, the function of the anti-foam agent is to displace the surfactant from the air-water interface.

A wetting agent is a substance that when added to a liquid increases the spreading or penetration power of the liquid by reducing the interfacial tension between the liquid and the surface on which it is spreading. Wetting agents are used for two main functions in agrochemical formulations: during processing and manufacture to increase the rate of wetting of powders in water to make concentrates for soluble liquids or suspension concentrates; and during mixing of a product with water in a spray tank or other vessel to reduce the wetting time of wettable powders and to improve the penetration of water into water-dispersible granules. Examples of wetting agents used in wettable powder, suspension concentrate, and water-dispersible granule formulations include but not limited to sodium lauryl sulphate; sodium dioctylsulphosuccinate; alkyl phenol ethoxylates; and aliphatic alcohol ethoxylates and the salts thereof which are standard in agriculture or mixtures thereof.

Suspension aid in the present description denotes a natural or synthetic, organic or inorganic material with which the active substance is combined in order to facilitate its application to the plant, to the seeds or to the soil. This carrier is hence generally inert, and it must be agriculturally acceptable, in particular to the plant being treated. The carrier may be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, and the like or mixtures thereof) or liquid (water, alcohols, ketones, petroleum fractions, aromatic or paraffinic hydrocarbons, chlorinated hydrocarbons, liquefied gases, and the like or mixtures thereof).

Biocides / Microorganisms cause spoilage of formulated products. Therefore anti-microbial agents are used to eliminate or reduce their effect. Examples of such agents include, but are not limited to: propionic acid and its sodium salt; sorbic acid and its sodium or potassium salts; benzoic acid and its sodium salt; p-hydroxy benzoic acid sodium salt; methyl p-hydroxy benzoate; and biocide such as sodium benzoate, 1,2-benzisothiazoline-3-one, 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, potassium sorbate, parahydroxy benzoates or mixtures thereof.

Thickeners or gelling agents are used mainly in the formulation of suspension concentrates, emulsions and suspo-emulsions to modify the rheology or flow properties of the liquid and to prevent separation and settling of the dispersed particles or droplets. Thickening, gelling, and anti-settling agents generally fall into two categories, namely water-insoluble particulates and water-soluble polymers. It is possible to produce suspension concentrate formulations using clays and silicas. Examples of these types of materials, include, but are limited to, montmorillonite, bentonite; magnesium aluminum silicate; and attapulgite. Water-soluble polysaccharides have been used as thickening-gelling agents for many years. The types of polysaccharides most commonly used are natural extracts of seeds and seaweeds are synthetic derivatives of cellulose or mixtures thereof. Examples of these types of materials include, but are not limited to, guar gum; locust bean gum; carrageenam; xanthan gum; alginates; methyl cellulose; sodium carboxymethyl cellulose (SCMC); hydroxyethyl cellulose (HEC) or mixtures thereof. Other types of anti-settling agents are based on modified starches, polyacrylates, polyvinyl alcohol and polyethylene oxide or mixtures.

The quick coating agent can be a conventionally available sticker, for example polyesters, polyamides, poly- carbonates, polyurea and polyurethanes, acrylate polymers and copolymers, styrene copolymers, butadiene copolymers, polysaccharides such as starch and cellulose derivatives, vinylalcohol, vinylacetate and vinylpyrrolidone polymers and copolymers, polyethers, epoxy, phenolic and melamine resins, polyolefins and define copolymersand mixtures thereof. Examples of preferred polymers are acrylate polymers such as poly(methacrylate), poly(ethyl methacrylate), poly(methylmethacrylate), acrylate copoylmers and styrene-acrylic copolymers as defined herein below, poly(styrene-co maleic anhydride), cellulosic polymers such as ethyl cellulose, cellulose acetate, cellulose acetatebutyrate, acetylated mono, di, and triglycerides, poly(vinylpyrrolidone), vinyl acetate polymers and copolymers, poly(alkylene glycol), styrene butadiene copolymers, poly(orthoesters), alkyd resins, and mixtures of two or more of these. Polymers that are biodegradable are also useful in the present invention. As used herein, a polymer is biodegradable if is not water soluble, but is degraded over a period of several weeks when placed in an application environment. Examples of biodegradable polymers that are useful in the present invention include biodegradable polyesters, starch, polylactic acid starch blends, polylactic acid, poly(lactic acid-glycolic acid) copolymers, polydioxanone, cellulose esters, ethyl cellulose, cellulose acetate butyrate, starch esters, starch esteraliphatic polyester blends, modified corn starch, polycaprolactone, poly(namylmethacrylate), wood rosin, polyanhydrides, polyvinylalcohol, polyhydroxybutyratevalerate, biodegradable aliphatic polyesters, and polyhydroxybutyrate or mixtures thereof.

Buffering agent as used herein is selected from group consisting of calcium hydroxyapatite, Potassium Dihydrogen Phosphate, Sodium Hydroxide, carbonated apatite, calcium carbonate, sodium bicarbonate, tricalcium phosphate, calcium phosphates, carbonated calcium phosphates, amine monomers, lactate dehydrogenase and magnesium hydroxide.

The solvent for the formulation of the present invention may include water, water-soluble alcohols and dihydroxy alcohol ethers. The water-soluble alcohol which can be used in the present invention may be lower alcohols or water-soluble macromolecular alcohols. The term "lower alcohol", as used herein, represents an alcohol having 1-4 carbon atoms, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, etc. Macromolecular alcohol is not limited, as long as it may be dissolved in water in a suitable amount range, polyethylene glycol, sorbitol, glucitol, etc. The examples of suitable dihydroxy alcohol ethers used in the present invention may be dihydroxy alcohol alkyl ethers or dihydroxy alcohol aryl ethers. The examples of dihydroxy alcohol alkyl ether include ethylene glycol methyl ether, diethylene glycol methyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol ethyl ether, propylene glycol ethyl ether, dipropylene glycol ethyl ether, etc. The examples of dihydroxy alcohol aryl ethers include ethylene glycol phenyl ether, diethylene glycol phenyl ether, propylene glycol phenyl ether, dipropylene glycol phenyl ether, and the like. Any of the above mentioned solvent can be used either alone or in combination thereof.

The compositions according to the invention control vegetation on non-crop areas very efficiently, especially at high rates of application.
The compositions according to the invention are applied to the plants mainly by spraying. Here, the application can be carried out using, for example, water as carrier by customary spraying techniques using spray liquor amounts of from about 50 to 1000 l/ha (for example from 200 to 600 l/ha). The herbicidal compositions may also be applied by the low-volume or the ultra-low- volume method, or in the form of microgranules. The herbicidal compositions according to the present invention can be applied post- emergence. If any active ingredient of the inventive compositions, is less well tolerated by certain crop plants, application techniques may be used in which the herbicidal compositions are sprayed, with the aid of the spraying equipment, in such a way that as far as possible they do not come into contact with the leaves of the sensitive crop plants, while the active compounds reach the leaves of undesirable plants growing underneath, or the bare soil surface (post- directed, lay-by).
Non-phytotoxic oils and oil concentrates can also be added.
When employed in plant protection, the amounts of active substances applied, i.e. active ingredient I, II and III without formulation auxiliaries, are, depending on the kind of effect desired, from 0.1 to 10000 grams per hectare (g/ha), preferably from 10 to 1000 g/ha, more preferably from 25 to 500 g/ha and in particular from 50 to 300 g/ ha.
According to the invention the amount of formulated product applied depending upon the kind of effect desired, from 1 to 10000 ml or g per hectare, preferable from 10 to 5000 ml or g per hectare, more preferably from 100 to 2000 ml or g per hectare.

Application Method:
• Foliar application: spraying with manually operated knapsack or backpack sprayer fitted with flood jet or flat fan nozzles or multi nozzles with boom, machine or power operated sprayer. Spray over the top to crop and weeds. The application can be carried out using water as carrier by customary spraying techniques using spray liquor amounts of from about 50 to 500 liter per hectare. The herbicidal compositions may also be applied by the low-volume or the ultra-low- volume method, or in the form of micro granules.
• Broadcasting: Manual broadcasting or broadcasting through machine. Broad casting the required quantity of product as alone or by mixing with sand or fertilizers or any other suitable material to bulk out the product. The quantity of sand or fertilizer or other bulking material varies from 2 to 100 kg per hectare.
• Application through shaker bottles. The required quantity of product is further diluted with water (500 ml to 50 liters water) and applied manually using shaker bottles.
• Jumbo ball application (water soluble bags): The required quantity of formulation is to be applied as jumbo ball/ water soluble bags. (250 g to 5 kg per hectare)

Application Time:
• Pre emergence application:
Transplanted rice: 0 to 3 days after transplanting
Direct sown / seeded rice: 0 to 10 days after sowing
• Post emergence application:
Transplanted rice: 7 to 30 days after transplanting.
Direct sown / seeded rice: 1 to 30 days after sowing.
• Weed stage:
Actively growing weeds from 2 leaf stage to fully grown weeds.
1 leaf to full grown weeds. 1 cm to 50 cm height. Vegetative to reproductive stage of weeds. It can be applied in nursery as well as main field after sowing or transplanting.
The herbicidal compositions according to the present invention can be applied post- emergence. If any active ingredient of the inventive compositions, is less well tolerated by certain crop plants, application techniques may be used in which the herbicidal compositions are sprayed, with the aid of the spraying equipment, in such a way that as far as possible they do not come into contact with the leaves of the sensitive crop plants, while the active compounds reach the leaves of undesirable plants growing underneath, or the bare soil surface (post- directed, lay-by).
Moreover, it may be advantageous to apply the compositions of the present invention on their own or jointly in combination with other crop protection agents, for example with agents for controlling pests or phytopathogenic fungi or bacteria or with groups of active compounds which regulate growth. Also of interest is the miscibility with mineral salt solutions which are employed for treating nutritional and trace element deficiencies. Non-phytotoxic oils and oil concentrates can also be added.

EXAMPLES

The present invention will now be explained in detail by reference to the following formulation examples and a test example, which should not be construed as limiting the scope of the present invention.

Example 1: Suspension concentrate (SC) formulation of Metamifop 12.50%+Bispyribac sodium 5%+Pyrazosulfuron Ethyl 5%

Chemical composition % (w/w)
Metamifop a.i. 12.50
Bispyribac sodium a.i. 5.00
Pyrazosulfuron Ethyl a.i. 5.00
Ethoxylated fatty alcohol 2.00
Acrylic graft copolymer 3.00
Alkylated napthalene sulfonate, sodium salt 0.50
Precipitated Silica 0.50
Polydimethyl siloxane 0.30
1,2-benzisothiazol-3-one 0.20
Glycol 5.00
Xanthan gum 0.15
Polyalkoxylated butyl ether 1.00
D.M. Water q.s.
Total 100.00

Procedure: Process for preparation of Suspension concentrate (SC) formulation

Step 1 Gum Solution should be made 12-18 hour prior to use. Take required quantity of water, biocide, and defoamer and homogenise, then slowly add gum powder to it and stir till complete dissolution.
Step 2 Charge required quantity of DM water need to be taken in designated vessel for Suspension concentrate production.
Step 3 Add required quantity of Wetting agent, antifreeze, dispersing agent & suspending agents and homogenise the contents for 45 – 60 minutes using high shear homogeniser.
Step 4 Then add technical and other remaining adjuvants excluding ‘thickener’ are added to it and homogenised to get uniform slurry ready for grinding.
Step 5 Before grinding half the quantity of antifoam was added and then material was subjected to grinding in Dyno mill till desired particle size is achieved.
Step 6 Half quantity of the antifoam was added after grinding process completes and before sampling for in process analysis.
Step 7 Finally add gum solution to this formulation and send to QC for quality check.

Storage stability of suspension concentrate (SC) of Metamifop 12.5%+Bispyribac sodium 5%+Pyrazosulfuron Ethyl 5%

Laboratory storage stability for 14 days
parameters specification (in house) initial heat stability study at 54±2 0C cold storage stability at 0±2 0C
Metamifop content percent by mass 11.88 to 13.12 12.72 12.75 12.73
Bispyribac sodium content percent by mass 4.75 to 5.5 5.14 5.18 5.15
Pyrazosulfuron Ethyl content percent by mass 4.75 to 5.5 5.13 5.15 5.14
Metamifop suspensibility percent min. 80 96.14 95.15 96.03
Bispyribac sodium suspensibility percent min. 80 97.16 97.10 96.80
Pyrazosulfuron Ethyl suspensibility percent min. 80 97.96 97.45 97.10
pH range (1% aq. Suspension) 5.5 to 7.5 7.12 6.99 7.03
pourability 95% min. 97.4 97.2 96.5
specific gravity 1.05-1.15 1.08 1.09 1.09
viscosity at spindle no. 62, 20 rpm 350-800 cps 510 518 520
particle size (micron) D50<3, D90<10 2.2,8.6 2.4,8.8 2.5,8.9
persistent foam ml (after 1 minute) max. 60 nil 5 nil
Room temperature storage stability up to 12 months
Parameters specification (in house) 1 month 6 month 12 month
Metamifop sodium content percent by mass 11.88 to 13.12 12.72 12.76 12.77
Bispyribac sodium content percent by mass 4.75 to 5.5 5.15 5.19 5.21
Pyrazosulfuron Ethyl content percent by mass 4.75 to 5.5 5.13 5.16 5.19
Metamifop suspensibility percent min. 80 96.17 95.13 95.32
Bispyribac sodium suspensibility percent min. 80 97.16 96.10 96.20
Pyrazosulfuron Ethyl suspensibility percent min. 80 97.70 97.45 97.10
pH range (1% aq. Suspension) 5.5 to 7.5 7.12 7.14 7.08
pourability 95% min. 97.4 97.4 97.3
specific gravity 1.05-1.15 1.08 1.08 1.09
viscosity at spindle no. 62, 20 rpm 350-800 cps 515 520 523
particle size (micron) D50<3, D90<10 2.2,8.6 2.2,8.6 2.2,8.7
persistent foam ml (after 1 minute) max. 60 nil nil 2

Example 2: Suspension concentrate (SC) formulation of Metamifop 4%+Bispyribac sodium 1.6%+2,4-D Amine salt 30%

Chemical composition % (w/w)
Metamifop a.i. 4.00
Bispyribac sodium a.i. 1.60
2,4-D Amine salt a.i. 30.00
Ethoxylated fatty alcohol 2.00
Acrylic graft copolymer 3.00
Alkylated napthalene sulfonate, sodium salt 0.50
Precipitated Silica 0.50
Polydimethyl siloxane 0.30
1,2-benzisothiazol-3-one 0.20
Glycol 5.00
Xanthan gum 0.15
Polyalkoxylated butyl ether 1.00
D.M. Water q.s.
Total 100.00

Procedure: Process for preparation of Suspension concentrate (SC) formulation as per Example 1

Example 3: Suspo Emulsion (SE) formulation of Metamifop 12.50%+Bispyribac sodium 5%+Pyrazosulfuron Ethyl 5%

Chemical composition % (w/w)
Metamifop a.i. 12.50
Bispyribac sodium a.i. 5.00
Pyrazosulfuron Ethyl a.i. 5.00
n-Octanol 10.00
Tristyryl Phenol Ethoxylates 4.00
Polyalkoxylated Butyl Ether 3.00
Polyethylene Glycol 6.00
Alkylated napthalene sulfonate, sodium salt 1.00
Silicon based Antifoam 0.50
1,2-benzisothiazol-3-one 0.30
Xanthan powder 0.15
D.M. Water q.s.
Total 100.00

Procedure: Process for preparation of Suspo Emulsion (SE) formulation:
Step 1 Gum Solution should be made 12-18 hour prior to use. Take required quantity of water, biocide, and defoamer and homogenise, then slowly add gum powder to it and stir till complete dissolution.
Step 2 Oil Phase : Technical dissolved in solvent and emulsifier.
Step 3 Aqueous phase: Charge 90% of total quantity of water in a vessel and then add preservative and MEG and stir well.
Step 4 Add required quantity of Wetting agent, dispersing agent & suspending agents and homogenise the contents for 45 – 60 minutes using high shear homogeniser.
Step 5 Then add technical and other remaining adjuvants excluding ‘antifreeze & thickeners’ are added to it and homogenised to get uniform.
Step 6 Now add oil phase in aqueous phase and stir for 30 minutes using homogeniser.
Step 6 Before grinding of step no. 6, half quantity of antifoam was added and then material was subjected to three cycles of grinding in bead mill.
Step 7 Half quantity of the antifoam was added along with antifreeze after grinding process completes and before sampling for in process analysis.
Step 8 Finally add gum solution to this formulation and Send to QC for quality check.

Storage stability of suspo emulsion (SE) of Metamifop 12.5%+Bispyribac sodium 5%+Pyrazosulfuron Ethyl 5%
Laboratory storage stability for 14 days
parameters specification (in house) initial heat stability study at 54±2 0C cold storage stability at 0±2 0C
Metamifop content percent by mass 11.88 to 13.12 12.58 12.62 12.57
Bispyribac sodium content percent by mass 4.75 to 5.5 5.17 5.12 5.15
Pyrazosulfuron Ethyl content percent by mass 4.75 to 5.5 5.16 5.13 5.14
Metamifop suspensibility percent min. 80 97.96 96.05 96.1
Bispyribac sodium suspensibility percent min. 80 97.2 95.65 97.1
Pyrazosulfuron Ethyl suspensibility percent min. 80 96.2 95.15 96.03
pH range (1% aq. Suspension) 5.5 to 7.5 7.11 6.99 7.09
pourability 95% min. 97.4 97.2 96.5
specific gravity 1.05-1.15 1.078 1.078 1.079
viscosity at spindle no. 62, 20 rpm 350-800 cps 480 485 505
particle size (micron) D50<3, D90<10 2.2,8.6 2.4,8.8 2.5,8.9
persistent foam ml (after 1 minute) max. 60 nil 5 nil
Room temperature storage stability up to 12 months
Parameters specification (in house) 1 month 6 month 12 month
Metamifop sodium content percent by mass 11.88 to 13.12 12.57 12.60 12.61
Bispyribac sodium content percent by mass 4.75 to 5.5 5.17 5.15 5.17
Pyrazosulfuron Ethyl content percent by mass 4.75 to 5.5 5.15 5.14 5.16
Metamifop suspensibility percent min. 80 97.9 96.2 96.5
Bispyribac sodium suspensibility percent min. 80 97.3 95.7 96.1
Pyrazosulfuron Ethyl suspensibility percent min. 80 96.2 95.3 96.3
pH range (1% aq. Suspension) 5.5 to 7.5 7.13 7.09 7.02
pourability 95% min. 97.2 97.1 96.8
specific gravity 1.05-1.15 1.08 1.08 1.09
viscosity at spindle no. 62, 20 rpm 350-800 cps 530 525 524
particle size (micron) D50<3, D90<10 2.2,8.6 2.2,8.6 2.2,8.7
persistent foam ml (after 1 minute) max. 60 nil nil 2

Example 4: Soluble Liquid (SL) formulation of Metamifop 4%+Bispyribac sodium 1.6%+2,4-D Amine salt 30%

Chemical composition % (w/w)
Metamifop a.i. 4.00
Bispyribac sodium a.i. 1.60
2,4-D Amine salt a.i. 30.00
Alky glyceride ethylene oxide 5.00
N-Methyl-2-pyrrolidone 21.40
Dimethyl sulfoxide 38.00
TOTAL 100.00

Procedure: Process for preparation of Soluble Liquid (SL) formulation:
Step 1 Charge require quantity of solvent and then mix the technical into this solvent until completely soluble.
Step 2 Now add Emulsifier and other adjuvants dose as per ratio.
Step 3 Final product is sent for QC approval.
Step 4 After approval material is packed in required pack sizes.

Storage stability of soluble liquid (SL) of Metamifop 4%+Bispyribac sodium 1.6%+2,4-D Amine salt 30%
Laboratory storage stability for 14 days
parameters specification (in house) initial heat stability study at 54±2 0C cold storage stability at 0±2 0C
Metamifop content percent by mass 3.80 to 4.40 4.15 4.18 4.14
Bispyribac sodium content percent by mass 1.52 to 1.76 1.63 1.65 1.64
2,4-D Amine salt content percent by mass 28.5 to 31.5 30.41 30.35 30.35
pH range (1% aq. Suspension) 5.0 to 9.0 7.23 7.15 7.25
specific gravity 1.05-1.20 1.14 1.15 1.14
persistent foam ml (after 1 minute) max. 60 5 7 5
Room temperature storage stability up to 12 months
Parameters specification (in house) 1 month 6 month 12 month
Metamifop content percent by mass 3.80 to 4.40 4.13 4.15 4.17
Bispyribac sodium content percent by mass 1.52 to 1.76 1.62 1.64 1.63
2,4-D Amine salt content percent by mass 28.5 to 31.5 30.41 30.40 30.39
pH range (1% aq. Suspension) 5.0 to 9.0 7.27 7.21 7.15
specific gravity 1.05-1.20 1.14 1.14 1.15
persistent foam ml (after 1 minute) max. 60 5 5 5

Example 5: Soluble Liquid (SL) of Metamifop 2%+Bispyribac sodium 1%+ Bentazone 48%

Chemical composition % (w/w)
Metamifop a.i. 4.00
Bispyribac sodium a.i. 1.60
Bentazone a.i. 48.00
Alky glyceride ethylene oxide 5.00
N-Methyl-2-pyrrolidone 18.00
Dimethyl sulfoxide 23.40
TOTAL 100.00

Procedure: Process for preparation of Suspension concentrate (SC) formulation as per Example 4

Example 6: Water dispersible granule (WG) formulation of Metamifop 20%+Bispyribac sodium 8%+Pyrazosulfuron Ethyl 8%
Chemical composition % (w/w)
Metamifop a.i. 12.50
Bispyribac sodium a.i. 5.00
Pyrazosulfuron Ethyl a.i. 5.00
Alkyl sulfonate 6.00
sodium salt of sulphonate napthalene formaldehyde condensate 3.00
Alkylated naphthalene sulfonate, sodium salt 2.00
Corn starch 15.00
Lactose 13.00
Silicon Antifoam 0.50
Silicon Dioxide 3.00
China clay Q.S
Total 100.00

Procedure: Process for preparation of Water dispersible granule (WG) formulation
Step 1 Charge the required quantity of filler, wetting agent, dispersing agent, and suspending agent, & technical in premixing blender for homogenization for 30 minutes.
Step 2 Pre-blended material is than grinded through Jet mill/ air classifier mills. Finely grinded material is blended in post blender till it becomes homogeneous. (for approx.. 1.5 hr)
Step 3 Homogeneous material is analysed. After getting approval from QC dept. material is unloaded into 25 kg. HDPE bag with LDPE liner inside.
Step 4 Finely grinded powder is mixed with required quantity of water to form extrudable dough.
Step 5 Dough is passed through extruder to get granules of required size.
Step 6 Wet granules are passed through Fluidised bed drier and further graded using vibrating screens.
Step 7 Final product is sent for QC approval.
Step 8 After approval material is packed in required pack sizes.

Storage stability of Water Dispersible Granules (WG) of Metamifop 20%+Bispyribac sodium 8%+Pyrazosulfuron Ethyl 8%

Laboratory storage stability for 14 days
parameters specification (in house) initial heat stability study at 54±2 0C cold storage stability at 0±2 0C
Metamifop content percent by mass 19.00 to 21.00 20.22 20.24 20.21
Bispyribac sodium contnet percent by mass 7.60 to 8.80 8.16 8.18 8.15
Pyrazosulfuron ethyl content percent by mass 7.60 to 8.80 8.21 8.23 8.19
Metamifop suspensibility percent min. 70 97.05 96.95 96.14
Bispyribac sodium suspensibility percent min. 70 96.02 95.62 95.51
Pyrazosulfuron ethyl suspensibility percent min. 70 96.65 96.61 96.15
pH range (1% aq. Suspension) 5.5 to 7.5 6.99 6.99 7.01
wettability sec. max. 60 9 10 10
wet sieve (45 micron) percent by mass min. 98.5 99.5 99.2 99.3
bulk density (g/ml) 0.45 to 0.75 0.48 0.48 0.48
moisture content percent by mass max. max. 2% 1.4 1.2 1.1
Room temperature storage stability up to 12 months
Parameters specification (in house) 1 month 6 month 12 month
Bispyribac sodium contnet percent by mass 19.00 to 21.00 20.22 20.26 20.23
Pyrazosulfuron ethyl content percent by mass 7.60 to 8.80 8.18 8.20 8.19
Metamifop suspensibility percent min. 7.60 to 8.80 8.22 8.24 8.25
Bispyribac sodium suspensibility percent min. 70 97.05 96.95 96.14
Pyrazosulfuron ethyl suspensibility percent min. 70 96.02 95.62 95.51
chlorantraniliprole suspensibility percent min. 70 96.65 96.61 96.15
pH range (1% aq. Suspension) 5.5 to 7.5 6.99 6.99 7.01
wettability sec. max. 60 9 10 10
wet sieve (45 micron) percent by mass min. 98.5 99.5 99.2 99.3
bulk density (g/ml) 0.45 to 0.75 0.46 0.46 0.46
moisture content percent by mass max. max. 2% 1.4 1.2 1.1

Biological Examples:

The synergistic pesticide action of the inventive mixtures can be demonstrated by the experiments below. A synergistic effect exists wherever the action of a combination (ready-mix) of active ingredient is greater than the sum of the action of each of the components alone. Therefore a synergistically effective amount or an effective amount of a synergistic composition or combination is an amount that exhibits greater pesticide activity than the sum of the pesticide activities of the individual components. In the field of agriculture, it is often understood that the term “synergy” is as defined by Colby S.R. in an article entitled “ Calculation of the synergistic and antagonistic responses of herbicide combinations” published in the journal Weeds, 1967, 15, p.20-22, incorporated herein by reference in its entirety. The action expected for a given combination of two active components can be calculated as follows:
Colby’s Formula:

The field experiments on present invention concerns a synergistic herbicidal mixture comprising of metamifop, one more herbicide selected from the group of bispyribac sodium, fenoxaprop-P-ethyl, cyhalofop butyl and one more herbicide selected from pyrazosulfuron ethyl, ethoxysulfuron, metsulfuron methyl, imazosulfuron, propyrisulfuron, azimsulfuron, tefuryltrione, penoxsulam, pyribenzoxim, bentazon, saflufenacil, 2,4-D (different salt) were carried out to evaluate the bio efficacy against different weed flora and phyto-toxicity in rice/paddy crop.
Example 1: Synergistic weed control in paddy/rice, Oryza sativa
The field experiment were conducted in paddy crop and the experimental details are as below:
Crops & Varieties: Paddy (Direct seeded), Local
Experimental design: Randomized block design (R.B.D)
Replications: Three
No. of Treatments: As per treatment details
Plot size: 30 sq. mt.
Application Time: 12 DAS (Days after sowing)
Observations: species wise weed count at 15 and 30 DAA (Days after Application)
Spray Volume: 400 liter water per hectare
Application Equipment: Manually operated knapsack sprayer fitted with flat fat nozzle
Experiment method: The trials were laid out in Randomized Block design (RBD) with sixteen (16) treatments, replicated thrice. For each treatment plot size of 30 sq. mt. was maintained. To raise the crops all the agronomic practices were followed as usually adopted. The treatments were applied as per the calculated dosages, using manually operated knap sack sprayer, fitted with flat fan nozzle. Water was drained off before one day of application and re-irrigated the field after 48 hrs. of application. The spray volume was used at 400 l/ha for application of all herbicidal treatments. Species wise weed count recorded at 15 and 30 DAA (Days after Application) by using 0.25 m2 quadrant treatment wise in minimum 3 places randomly selected in the plot per replication. The species wise weed count further grouped in to Grasses and Broad Leaf weeds (BLW) and sedges. The average of each variable was used together with the sum of all the variables per plot to calculate the percentage of control.
% Weed Control =

Mean weed count in untreated plot – Mean weed control in treated plot
1- -----------------------------------------------------------------------------------------X 100
Mean weed count in untreated plot

The % weed control data used in Colby’s formula to calculate the synergism between three herbicides.
Table 1: Treatment details
Treatment Number Treatment Details Formulation (ml or g per h) Active Ingredient (g/h)

T1 Metamifop 12.5%+Bispyribac sodium 5%+Pyrazosulfuron ethyl 5% SC 400 50+20+20
T2 Metamifop 4%+Bispyribac sodium 1.6%+,2,4-D amine salt 30% SC 1250 50+20+375
T3 Metamifop 12.5%+Bispyribac sodium 5%+Metsulfuron methyl 1% SC 400 50+20+4
T4 Metamifop 12.5%+Bispyribac sodium 5% SC (Prior art 1) 400 50+20
T5 Metamifop 12.5%+Pyrazosulfuron ethyl 5% SC (Prior art 2) 400 50+20
T6 Metamifop 4%+2,4-D amine salt 30% SC (Prior art 3) 1250 50+375
T7 Metamifop 12.5%+Metsulfuron methyl 1% SC (Prior art 4) 400 50+4
T8 Bispyribac sodium 5%+Pyrazosulfuron ethyl 5% SC (Prior art 5) 400 20+20
T9 Bispyribac sodium 1.6%+,2,4-D amine salt 30% SC (Prior art 6) 1250 20+375
T10 Bispyribac sodium 5%+Metsulfuron methyl 1% SC (Prior art 7) 400 20+4
T11 Metamifop 10% EC (Prior art 8) 500 50
T12 Bispyribac sodium 10% SC (Prior art 9) 200 20
T13 Pyrazosulfuron Ethyl 10% WP (Prior art 10) 200 20
T14 2,4-D Amine salt 58% SL (Prior art 11) 647 375
T15 Metsulfuron Methyl 20% WP 20 4
T16 Unweeded control 0 0
ml- milli liter, g- gram, h-hectare, DAA- Days after Application, EC Emulsifiable concentrate, SL Suspension Liquid, WP Wettable Powder.

Table 2: Synergistic weed control in Paddy (direct seeded)
Treatment Details % Weed Control Observed % Weed Control Expected Colby Ratio o/e
15 DAA 30 DAA 15 DAA 30 DAA 15 DAA 30 DAA
T1 99.6 99.2 83.02 80.76 1.20 1.23
T2 98.2 96.8 79.20 76.30 1.24 1.27
T3 97.2 95.2 80.20 77.55 1.21 1.23
T4 72.0 68.8 72.35 70.30 1.00 0.98
T5 65.8 63.6 66.97 64.23 0.98 0.99
T6 58.4 54.8 59.54 55.95 0.98 0.98
T7 60.2 56.8 61.48 58.27 0.98 0.97
T8 67.8 63.4 68.44 65.14 0.99 0.97
T9 61.2 56.6 61.35 57.07 1.00 0.99
T10 62.8 58.2 63.20 59.33 0.99 0.98
T11 46.2 44.8
T12 48.6 46.2
T13 38.6 35.2
T14 24.8 20.2
T15 28.4 24.4
T16 0.0 0.0
Weed flora composition- Grassy weeds (Echinochloa spp., Leptochloa spp.) approx. 50% + Broad leaf weeds (Eclipta spp., Alternenthera spp., Monochoria spp.) approx. 30%, Sedges (Cyprus spp.) approx. 20%

The bio efficacy observations given in above (Table 2), shows that the inventive mixtures (T1 Metamifop 12.5%+Bispyribac sodium 5%+Pyrazosulfuron ethyl 5% SC, T2 Metamifop 4%+Bispyibac sodium 1.6%+2,4-D amine salt 30% SC and T3 Metamifop 12.5%+Bispyribac sodium 5%+Metsulfuron methyl 1% SC) shows synergistic weed control (Colby ratio > 1) and provide excellent control of grasses, broad leaf weeds, sedges and longer residual control compared to all prior art treatments.

Example 2: Phytotoxicity studies on paddy (direct seeded)
Crop & Variety: Paddy (direct seeded), local
Experimental design: Randomized block design (R.B.D)
Replications: Three
No. of Treatments: as given in the treatment details
Plot size: 30 sq. mt.
Application Time: 12 DAS (Days after sowing)
Spray Volume: 400 liter water per hectare
Application Equipment: Hand operated knapsack sprayer fitted with flat fan nozzle
Observations: Observations on phytotoxicity viz., leaf scorching, leaf yellowing, plant stunting or any other visible symptoms were recorded at 5, 10 and 15 days after spraying, by adopting 0-10 rating scale as below :
0= No phytotoxicity, 1 =1-10% leaf scorching/yellowing, 2=11-20% leaf scorching/yellowing… 9=81-90% leaf scorching/yellowing, 10=91-100% leaf scorching/yellowing.
Percent phytotoxicity was calculated by following formula:
Sum of all scores
% Phytotoxicity = ------------------------------------------------------------- X 100
Number of samples x highest rating scale

Table 3: Treatments details
Treatment No. Treatment Details Formulation (ml or g per h) Active Ingredient (g/h)

T1 Metamifop 12.5%+Bispyribac sodium 5%+Pyrazosulfuron ethyl 5% SC 400 50+20+20
T2 Metamifop 12.5%+Bispyribac sodium 5%+Pyrazosulfuron ethyl 5% SE 400 50+20+20
T3 Metamifop 4%+Bispyribac sodium 1.6%+,2,4-D amine salt 30% SC 1250 50+20+375
T4 Metamifop 4%+Bispyribac sodium 1.6%+2,4-D amine salt 30% SL 1250 50+20+375
T5 Metamifop 12.5%+Bispyribac sodium 5%+Metsulfuron methyl 1% SC 400 50+20+4
T6 Metamifop 12.5%+Bispyribac sodium 5%+Metsulfuron methyl 1% SE 400 50+20+4
T7 Metamifop 12.5%+Bispyribac sodium 5% SC 400 50+20
T8 Metamifop 12.5%+Pyrazosulfuron ethyl 5% SC 400 50+20
T9 Bispyribac sodium 5%+Pyrazosulfuron ethyl 5% SC 400 20+20
T10 Metamifop 4%+2,4-D amine salt 30% SC 1250 50+375
T11 Bispyribac sodium 1.6%+2,4-D amine salt 30% SL 1250 20+375
T12 Metamifop 10% EC 500 50
T13 Bispyribac sodium 10% SC 200 20
T14 Pyrazosulfuron Ethyl 10% WP 200 20
T15 2,4-D Amine salt 58% SL 647 375
T16 Metsulfuron methyl 20% WP 20 4
T17 Untreated Control (UTC) water spray only - -

Table 4: Phytotoxicity observations on paddy (direct seeded)
Treatment No. Leaf scorching (%) Stunting (%)
5 DAA 10 DAA 15 DAA 5 DAA 10 DAA 15 DAA
T1 5.0 0.0 0.0 0.0 5.0 0.0
T2 5.0 0.0 0.0 0.0 5.0 0.0
T3 10.0 5.0 0.0 0.0 10.0 0.0
T4 10.0 5.0 0.0 0.0 10.0 0.0
T5 5.0 0.0 0.0 0.0 5.0 0.0
T6 5.0 0.0 0.0 0.0 5.0 0.0
T7 5.0 0.0 0.0 0.0 5.0 0.0
T8 5.0 0.0 0.0 0.0 5.0 0.0
T9 5.0 0.0 0.0 0.0 5.0 0.0
T10 10.0 5.0 0.0 0.0 10.0 0.0
T11 10.0 5.0 0.0 0.0 10.0 0.0
T12 5.0 0.0 0.0 0.0 0.0 0.0
T13 5.0 0.0 0.0 0.0 0.0 0.0
T14 0.0 0.0 0.0 0.0 0.0 0.0
T15 10.0 5.0 0.0 0.0 5.0 0.0
T16 5.0 0.0 0.0 0.0 5.0 0.0
T17 0.0 0.0 0.0 0.0 0.0 0.0

All the inventive mixtures shows mild toxicity in terms of leaf scorching which was completely recovered after 10 days of application, whereas the planting completely recovers at 15 days after application.
,CLAIMS:CLAIMS
We claim;
[CLAIM 1]. A synergistic herbicidal composition comprising
A) Metamifop;
B) at least one herbicide selected from Bispyribac sodium, Fenoxaprop-P-Ethyl and Cyhalofop butyl;
C) at least one more herbicide selected from Pyrazosulfuron Ethyl, Ethoxysulfuron, Metsulfuron methyl, Imazosulfuron, Propyrisulfuron, Azimsulfuron, Tefuryltrione, Penoxsulam, Pyribenzoxim, Bentazon, Saflufenacil, 2,4-D and salts thereof; and
D) one or more other inactive excipients.

[CLAIM 2]. The synergistic composition as claimed in claim 1 wherein the component (A) Metamifop is in ratio of 0.1 to 20%, component (B) at least one herbicide selected from Bispyribac sodium, Fenoxaprop-P-Ethyl and Cyhalofop butyl is in ratio of 0.1 to 30% and component (C) at least one more herbicide selected from Pyrazosulfuron Ethyl, Ethoxysulfuron, Metsulfuron methyl, Imazosulfuron, Propyrisulfuron, Azimsulfuron, Tefuryltrione, Penoxsulam, Pyribenzoxim, Bentazon, Saflufenacil, 2,4-D is in ratio of 0.1 to 50%.

[CLAIM 3]. The synergistic composition as claimed in claim 1 or 2, wherein inactive excipients are selected from the group consisting of dispersant, anti-freezing agent, anti-foam agent, wetting agent, suspension aid, anti-microbial agent, thickener, quick coating agent or sticking agents (also referred to as “stickers” or “binders”) and buffering agent.

[CLAIM 4]. The synergistic composition as claimed in claim 1-3, wherein the formulations comprises of Suspension Concentrate (SC), Suspo emulsion (SE), Capsule Suspension (CS), Oil Dispersion (OD), Micro emulsion (ME), Dispersal concentrate (DC), Soluble liquid (SL), Emusifiable concentrate (EC), Emulsion in water (EW), Soluble liquid (SL), mixed formulation of CS and SC (ZC), a mixed formulation of CS and SE (ZE), a mixed formulation of CS and EW (ZW), Granules (Soil Applied Granules), Controlled Release Granules (CR Granules), Slow release and Fast release microsphere Granules (MS Granules), Water Soluble Granules (SG), Water dispersible granule (WDG or WG), Capsulated dry flowable (CDF), Dry flowable (DF), Jumbo ball formulation, Water soluble bag formulation, Wettable Powder (WP), Soluble Powder (SP), Dusting Powder (DP).

[CLAIM 5]. The synergistic composition as claimed in claim 4, wherein Suspension concentrate (SC) formulation comprises:
i. Metamifop;
ii. at least one herbicide selected from Bispyribac sodium, Fenoxaprop-P-Ethyl and Cyhalofop butyl;
iii. at least one more herbicide selected from Pyrazosulfuron Ethyl, Ethoxysulfuron, Metsulfuron methyl, Imazosulfuron, Propyrisulfuron, Azimsulfuron, Tefuryltrione, Penoxsulam, Pyribenzoxim, Bentazon, Saflufenacil, 2,4-D and salts thereof; and
iv. Ethoxylated fatty alcohol
v. Acrylic graft copolymer
vi. Alkylated napthalene sulfonate, sodium salt
vii. Precipitated Silica
viii. Polydimethyl siloxane
ix. 1,2-benzisothiazol-3-one
x. Glycol
xi. Xanthan gum
xii. Polyalkoxylated butyl ether
xiii. D.M. Water

[CLAIM 6]. The synergistic composition as claimed in claim 4, wherein Suspo Emulsion (SE) formulation comprises:
i. Metamifop;
ii. at least one herbicide selected from Bispyribac sodium, Fenoxaprop-P-Ethyl and Cyhalofop butyl;
iii. at least one more herbicide selected from Pyrazosulfuron Ethyl, Ethoxysulfuron, Metsulfuron methyl, Imazosulfuron, Propyrisulfuron, Azimsulfuron, Tefuryltrione, Penoxsulam, Pyribenzoxim, Bentazon, Saflufenacil, 2,4-D and salts thereof; and
iv. n-Octanol
v. Tristyryl Phenol Ethoxylates
vi. Polyalkoxylated Butyl Ether
vii. Polyethylene Glycol
viii. Alkylated napthalene sulfonate, sodium salt
ix. Silicon based Antifoam
x. 1,2-benzisothiazol-3-one
xi. Xanthan powder
xii. D.M. Water.

[CLAIM 7]. The synergistic composition as claimed in claim 4, wherein Soluble Liquid (SL) formulation comprises:
i. Metamifop;
ii. at least one herbicide selected from Bispyribac sodium, Fenoxaprop-P-Ethyl and Cyhalofop butyl;
iii. at least one more herbicide selected from Pyrazosulfuron Ethyl, Ethoxysulfuron, Metsulfuron methyl, Imazosulfuron, Propyrisulfuron, Azimsulfuron, Tefuryltrione, Penoxsulam, Pyribenzoxim, Bentazon, Saflufenacil, 2,4-D and salts thereof; and
iv. 2,4-D Amine salt a.i.
v. Alky glyceride ethylene oxide
vi. N-Methyl-2-pyrrolidone
vii. Dimethyl sulfoxide

[CLAIM 8]. The synergistic composition as claimed in claim 4, wherein Water dispersible granule (WG) formulation comprises:
i. Metamifop;
ii. at least one herbicide selected from Bispyribac sodium, Fenoxaprop-P-Ethyl and Cyhalofop butyl;
iii. at least one more herbicide selected from Pyrazosulfuron Ethyl, Ethoxysulfuron, Metsulfuron methyl, Imazosulfuron, Propyrisulfuron, Azimsulfuron, Tefuryltrione, Penoxsulam, Pyribenzoxim, Bentazon, Saflufenacil, 2,4-D and salts thereof; and
iv. Alkyl sulfonate
v. sodium salt of sulphonate napthalene formaldehyde condensate
vi. Alkylated naphthalene sulfonate, sodium salt
vii. Corn starch
viii. Lactose
ix. Silicon Antifoam
x. Silicon Dioxide
xi. China clay

[CLAIM 9]. The synergistic composition as claimed in any of the preceding claims, wherein the said composition is to be used to manage or control weeds controlled are selected from several species of grasses, broad leaf weeds and sedges. Aeschynomene aspera, Aeschynomene indica, Ageratum conyzoides, Alternanthera sessilis, Alternanthera philoxeroides, Amaranthus spinosus, Amaranthus viridis, Ammania baccifera, Cynodon dactylon, Dactyloctenium aegyptium, Digitaria ciliaris, Digitaria setigera, Ischaemum rugosum, Echinochloa colona, Echinochloa crus-galli, Echinochloa glabrescens, Echinochloa crus-pavonis, Echinochloa esculenta, Echinochloa frumentacea, Echinochloa muricata, Echinochloa oryzoides, Echinochloa paludigena, Eleocharis kuruguwai, Laptochloa chinensis, Eleusine indica, Eclipta alba, Eclipta prostate, Imperata cylindrical, Leersia hexandra, Leptochloa chinensis, Oryza sativa, Panicum repens, Paspalum distichum, Paspalum scrobiculatum, Rottboellia cochinchinensis, Setaria glauca, Bolboschoenus maritimus, Bergia capensis, Commelina benghalensis, Commelina diffusa, Cyanotis axillaris, Eclipta alba, Eclipta prostrate, Eichhornia crassipes, Ipomoea aquatic, Ludwigia adscendens, Ludwigia hyssopifolia, Ludwigia octovalvis, Ludwigia parviflora, Marsilea minuta, Marsilea quadrifoliata, Mimosa diplotricha, Monochoria vaginalis, Pistia stratiotes, Polygonum hydropiper, Portulaca oleracea, Sagittaria milliacea, Sagittaria sagittifolia, Sphenoclea zeylanica, Trianthema portulacastrum, Typha spp., Isachne globosa, Paspalum distichum, Cyperus difformis, Cyperus haspen, Cyperus iria, Cyperus rotundus, Fimbristylis dichotoma, Fimbristylis miliacea, Scirpus juncoides, Scirpus nipponicus, Scirpus planiculmis, Scirpur royelei, Scirpus juncoides, Dactyloctenium aegyptium, Digitaria ciliaris, Ischaemum rugosum and Laptochloa chinensis and Oryza sativa (Red rice).

[CLAIM 10]. The synergistic composition as claimed in any of the preceding claims, wherein the said composition effective in controlling the growth of undesirable vegetation in GMO (Genetically Modified) Paddy or non GMO varieties of Paddy or Rice (Oryza sativa L.) including Indica, Japonica and Javanica race.