Description:FIELD OF INVENTION:

The present invention relates to a synergistic herbicidal composition comprising a) a herbicide A which is N-(1-Ethylpropyl)-3,4-dimethyl-2,6-dinitro benzenamine and their salts and esters, b) a single herbicide B which is 5-ethyl-2-(4-methyl-5-oxo-4-propan-2-yl-1H-imidazol-2-yl)pyridine-3-carboxylic acid and their salts and esters, and c) at least one herbicide C is selected from diclosulam, chlorimuron ethyl, sulfentrazone, clomazone, pyroxasulfone, oxyfluorfen, metribuzin. The present invention also relates to process for preparing the said composition and its use as herbicide.

BACKGROUND OF THE INVENTION:

These days cultivation of crops and agriculture in general is cost intensive. Receiving a high yield from the cultivated crops is a key. Hence, to achieve higher yield, protecting crops from pests and diseases and weeds is vital.

In earlier days man power was utilized to remove weeds. Due to research and development in the field of agriculture now a days chemicals are being used to kill or control the weeds. The protection of crops from weeds and other vegetation that inhibit crop growth is a constantly recurring problem in agriculture and turf management. In addition, aesthetically, it may be of interest to remove such unwanted weeds and vegetation, for example, when growing turf in areas such as golf courses, lawns and public parks.

It is desirable for the crop protection product to control the harmful plants effectively and, at the same time, to be tolerated by the useful plants in question. Thus selectivity of the crop protection product is essential to selectively kill the unwanted crops and saves the desired crop in the field.
The control of undesired vegetation is extremely important in order to achieve high crop efficiency. In many cases, herbicides have an effect against a spectrum of weeds; however, these herbicides may not be effective on certain type of other weeds, which may also be present in the crop to be protected. Therefore, there is a strong need for mixing two or more herbicides. To help combat these problems, researchers in the field of synthetic chemistry have produced an extensive variety of chemicals and chemical formulations effective in the control of such unwanted growth. Chemical herbicides of many types have been disclosed in the literature and a large number are in commercial use.

Hence, the most effective way to control weeds is the application of herbicide in accordance with the appropriate management practices with proper formulation thereof.

Treating plants with such a weedicide/herbicide(s) in appropriate formulation helps to control the weeds.

A dinitroaniline class of herbicides “N-(1-Ethylpropyl)-3,4-dimethyl-2,6-dinitrobenzenamine” (Pendimethalin), is a selective herbicide which acts as a cell division inhibitor by inhibiting microtubule assembly. The structure can be represented as:

Pendimethalin is a selective herbicide, absorbed by the roots and leaves. Affected plants die shortly after germination or following emergence from the soil. Pendimethalin is used to control of most annual grasses and many annual broad leaf weeds at 0.4- 2.0 kg a.i./ha in cereals, onions, leeks, garlic, fennel, maize, sorghum, rice, soya beans, peanuts, brassicas, carrots, celery, black salsify, peas, field beans, lupins, evening primrose, tulips, potatoes, cotton, hops, pome fruit, stone fruit, berry fruit (including strawberries), citrus fruit, lettuce, aubergines, capsicums, established turf, and in transplanted tomatoes, sunflowers, and tobacco, applied pre-plant incorporated, pre-emergence, pre-transplanting, or early post-emergence. Also, Pendimethalin is used for control of suckers in tobacco. Pendimethalin is used for weed control management for numerous major crops such as rice, wheat, maize and soybean as well as minor crops such as fruits and vegetables.

Imazethapyr, (R5)-5-ethyl-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) nicotinic acid, disclosed in US 4,798,619, is a branched chain amino acid synthesis (ALS or AHAS) inhibitor. Hence reduces levels of valine, leucine and isoleucine, leading to disruption of protein and DNA synthesis. Imazethapyr is a systemic herbicide, absorbed by the roots and foliage. Imazethapyr control many major annual and perennial grass and broad leaf weeds.

Diclosulam, N-(2,6-dichlorophenyl)-5-ethoxy-7-fluoro-[1,2,4]triazolo[1,5-c]pyrimidine-2-sulfonamide is primarily used for control of annual and certain perennial broadleaf weeds when applied as soil, foliar, or burndown treatments in crops such as sugar cane, peanuts and soybeans, as well as forestry applications.

Sulfentrazone, N-{2, 4-Dichloro-5-[4-(difluoromethyl)-3-methyl-5-oxo-4,5-dihydro-1H-1,2,4-triazol-1-yl]phenyl}methanesulfonamide is an organic compound used as a broad-spectrum herbicide. It acts by inhibiting the enzyme protoporphyrinogen oxidase. [4] It was first marketed in the US in 1997 by FMC Corporation with the brand name Authority.

Various kinds of agrochemical formulations are developed based upon active ingredients and scope of application thereof. Pesticides for agriculture purpose are available both in the pure form and as well as incorporated into agrochemical formulations, which typically comprise one or more active ingredients (AIs) and additional excipients substances that enhance the effects and facilitate the application thereof, such as carriers, adjuvants or additives. These formulations can be directly applied after being diluted and the spray mixture formed. The formulation type to be used is primarily defined on the basis of physicochemical characteristics of the AI(s) and can be: Capsule suspension (CS), Dispersible concentrate (DC), Emulsifiable concentrate (EC), Emulsion-water in oil (EO), Emulsion-oil in water (EW), Jambo balls or bags (bags in water soluble pouch), Micro-emulsion (ME), Oil dispersion (OD), Oil miscible flowable concentrate (oil miscible suspension (OF), Oil miscible liquid (OL), Suspension concentrate (SC), Suspo-emulsion (SE), Soluble concentrate (SL), Water dispersible granule (WG or WDG), Water soluble granule (SG), Water soluble powder (SP), Wettable powder (WP), A mixed formulation of CS and SC (ZC), A mixed formulation of CS and SE (ZE), A mixed formulation of CS and EW (ZW), Granule (GR) / Soil Applied Granules (SAG), Controlled release granules (CR).

Therefore there is further need and scope in the formulation development of comprising one or more active ingredients with better stability profile and increases the synergistic effect of the active ingredients, reduces the toxicity with less introduction of toxic material in environment, which may reduce the dose of the pesticides and eventually produce less chemicals in environment, with better safety profile for contact herbicides.

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

The main objective of the present invention is to provide a synergistic herbicidal composition effective for controlling undesired vegetation including weeds such as monocots (grasses), dicots (broad leaf) and sedges.. The combination is particularly useful for preplant burndown. Burndown, i.e. the complete removal of weeds from the soil by application of herbicides prior to planting or emergence of a crop, is an important tool of modern weed management. Weeds present at planting will generally grow much quicker than crop plants and thus compete very early in the growing season thereby damaging the crop plants and reducing crop yield. Thus, it is desirable to plant the crop in a weed-free seed bed or to assure that essentially no weeds are present when the crop emerges.

Another objective of the present invention is to provide a synergistic herbicidal one-shot formulation effective for controlling undesired vegetation including weeds such as grassy weeds, broad leaf weeds and sedges.

Yet another objective of the present invention is to provide a synergistic herbicidal which can quickly absorb by the treated leaves of the weeds and germination weed’s roots and shoots.

Yet another objective of the present invention is to provide a synergistic herbicidal which can overcome the crop injury.

Yet another objective of the present invention is to provide a synergistic herbicidal formulation/composition which can help in controlling undesired vegetation when applying before and after germination of undesired vegetation, i.e. as pre-emergence (before weed and crop germination), post-emergence (after weed and crop germination)

Yet another objective of the present invention is to provide a process for the preparation of a synergistic herbicidal composition comprising the active ingredients of the present invention and excipients suitable for such an herbicidal composition.

Therefore an aspect of the present invention is to provide novel synergistic herbicidal composition comprising a) a herbicide A which is N-(1-Ethylpropyl)-3,4-dimethyl-2,6-dinitrobenzenamine and their salts and esters, b) a single herbicide B which is 5-ethyl-2-(4-methyl-5-oxo-4-propan-2-yl-1H-imidazol-2-yl)pyridine-3-carboxylic acid and their salts and esters, and c) at least one herbicide C which is selected from diclosulam, chlorimuron ethyl, sulfentrazone, clomazone, pyroxasulfone, oxyfluorfen, metribuzin can provide solution to the above mentioned problems.

Further Inventors of the present invention have surprisingly found that the novel synergistic herbicidal composition comprising a) a herbicide A which is N-(1-Ethylpropyl)-3,4-dimethyl-2,6-dinitrobenzenamine and their salts and esters, b) a single herbicide B which is 5-ethyl-2-(4-methyl-5-oxo-4-propan-2-yl-1H-imidazol-2-yl)pyridine-3-carboxylic acid and their salts and esters, and c) at least one herbicide C which is selected from diclosulam, chlorimuron ethyl, sulfentrazone, clomazone, pyroxasulfone, oxyfluorfen, metribuzin, with suitable formulation provides synergistic herbicidal effect.

SUMMARY OF INVENTION:

It is an object of the present invention to provide herbicidal compositions, which show enhanced herbicide action against undesirable harmful plants and/or have improved compatibility with the useful plants (in particular crop plants).

In particular, it is an object of the present invention to provide herbicidal compositions, which provide weed control comparable to the individual compounds with significantly reduced application rates. It is also an object of the present invention to provide herbicidal compositions, which provide significantly enhanced weed control with application rates comparable to those of the individual compounds.

Furthermore, it is an object of the present invention to provide herbicidal compositions, which maintain or improve the level of weed control, while showing less damage in the cultured crop in comparison to the individual compounds.

Another object of the present invention lies in the effective control of herbicide-resistant weed, in particular in herbicide-resistant undesired vegetation including weeds such as monocots, dicots and sedges.

Accordingly, in one aspect of the invention there is provided a synergistic herbicidal composition comprising a) a herbicide A which is N-(1-Ethylpropyl)-3,4-dimethyl-2,6-dinitrobenzenamine and their salts and esters, b) a single herbicide B which is 5-ethyl-2-(4-methyl-5-oxo-4-propan-2-yl-1H-imidazol-2-yl)pyridine-3-carboxylic acid and their salts and esters, and c) at least one herbicide C which is selected from diclosulam, chlorimuron ethyl, sulfentrazone, clomazone, pyroxasulfone, oxyfluorfen, metribuzin; along with formulation excipients.

Yet another object of the present synergistic herbicidal composition comprising bioactive amount of a) a herbicide A which is N-(1-Ethylpropyl)-3,4-dimethyl-2,6-dinitrobenzenamine and their salts and esters is present in the range of 15% to 50% w/w; b) a single herbicide B which is 5-ethyl-2-(4-methyl-5-oxo-4-propan-2-yl-1H-imidazol-2-yl)pyridine-3-carboxylic acid and their salts and esters is present in the range of 1% to 8 % w/w; c) at least one herbicide C which is selected from diclosulam, chlorimuron ethyl, sulfentrazone, clomazone, pyroxasulfone, oxyfluorfen, metribuzin is present in the range of 0.1% to 20% w/w or combination thereof that controls harmful weeds.

The invention furthermore relates to the use of a combination as defined herein for controlling undesirable vegetation. When using the invention of for this purpose the formulated combinations comprising the herbicide A, the herbicide B and the at least one herbicide C can be applied, where undesirable vegetation may occur.

The invention furthermore relates to the use of a combination as defined herein for controlling undesirable vegetation for burndown, i.e. for controlling undesirable vegetation in a locus, e.g. a field, where crops will be planted, before planting or emergence of the crop.

The invention furthermore relates to the use of a combination as defined herein for controlling undesirable vegetation in crops which, by genetic engineering or by breeding, are tolerant to one or more herbicides and/or pathogens such as plant-pathogenous fungi, and/or to attack by insects; preferably tolerant to saflufenacil.

Accordingly, in a yet another aspect the herbicidal composition comprising a) a herbicide A which is N-(1-Ethylpropyl)-3,4-dimethyl-2,6-dinitrobenzenamine and their salts and esters, b) a single herbicide B which is 5-ethyl-2-(4-methyl-5-oxo-4-propan-2-yl-1H-imidazol-2-yl)pyridine-3-carboxylic acid and their salts and esters, and c) at least one herbicide C which is selected from diclosulam, chlorimuron ethyl, sulfentrazone, clomazone, pyroxasulfone, oxyfluorfen, metribuzin, wherein the formulations selected from Capsule suspension (CS), Dispersible concentrate (DC), Emulsifiable concentrate (EC), Emulsion-water in oil (EO), Emulsion-oil in water (EW), Jambo balls or bags (bags in water soluble pouch), Micro-emulsion (ME), Oil dispersion (OD), Oil miscible flowable concentrate (oil miscible suspension (OF), Oil miscible liquid (OL), Suspension concentrate (SC), Suspo-emulsion (SE), Soluble concentrate (SL), Water dispersible granule (WG or WDG), Water soluble granule (SG), Water soluble powder (SP), Wettable powder (WP), Zeon Concentrate (ZC) formulation [mixed formulation of CS and SC (ZC)], A mixed formulation of CS and SE (ZE), A mixed formulation of CS and EW (ZW), Granule (GR) / Soil Applied Granules (SAG), Controlled release granules (CR).

Accordingly, in a first aspect, the present invention provides herbicidal composition comprising bioactive amount of a) a herbicide A which is N-(1-Ethylpropyl)-3,4-dimethyl-2,6-dinitrobenzenamine and their salts and esters is present in the range of 15% to 50% w/w; b) a single herbicide B which is 5-ethyl-2-(4-methyl-5-oxo-4-propan-2-yl-1H-imidazol-2-yl)pyridine-3-carboxylic acid and their salts and esters is present in the range of 1% to 8 % w/w; c) at least one herbicide C which is selected from diclosulam, chlorimuron ethyl, sulfentrazone, clomazone, pyroxasulfone, oxyfluorfen, metribuzin is present in the range of 0.1% to 20% w/w that controls harmful weeds, with suitable formulation excipients and formulations thereof show synergistic effect.

In addition, the compositions according to the invention should have a broad spectrum of activity.

DETAILED DESCRIPTION OF THE INVENTION:

Formulation technology in the field of agriculture is now seen as an “enabling technology” which can provide safe and effective products which are convenient to use. It can also modify the toxicity of active ingredients and improve their ability to target a specific pest. At a time when the discovery of new agrochemical compounds is more difficult and certainly a high risk and expensive operation, formulation technology can extent the useful patent life of an active ingredient. It can also provide a competitive edge by improving product quality of existing.
The term "synergistic", as used herein, refers 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 treatment of crops, is sufficient to effect such treatment. The term "herbicidal effective amount" denotes an amount of the active ingredients, which is sufficient for controlling unwanted plants, especially for controlling unwanted plants in cultivated plants and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as the plants to be controlled, the treated cultivated plant or material, the climatic conditions and the specific composition according to the invention used.

The terms "plants" and "vegetation", as used herein, include germinant seeds, emerging seedlings, plants emerging from vegetative propagules, and established vegetation.

The terms "controlling" and "combating", as used herein, are synonyms.

The terms "undesirable vegetation", "harmful plants", "unwanted plants", "weeds" and "weed species", as used herein, are synonyms.

The term "locus", as used herein, means the area in which the vegetation or plants are growing or will grow, typically a field.

Therefore an aspect of the present invention provides a synergistic herbicidal composition comprising a) a herbicide A which is N-(1-Ethylpropyl)-3,4-dimethyl-2,6-dinitrobenzenamine and their salts and esters, b) a single herbicide B which is 5-ethyl-2-(4-methyl-5-oxo-4-propan-2-yl-1H-imidazol-2-yl)pyridine-3-carboxylic acid and their salts and esters, and c) at least one herbicide C which is selected from diclosulam, chlorimuron ethyl, sulfentrazone, clomazone, pyroxasulfone, oxyfluorfen, metribuzin; along with formulation excipients.

In another preferred embodiment of the invention, synergistic Weed controlled according to the method of the invention.

In an embodiment present inventors combination of the present invention synergistic herbicidal composition comprising a) a herbicide A which is N-(1-Ethylpropyl)-3,4-dimethyl-2,6-dinitrobenzenamine and their salts and esters, b) a single herbicide B which is 5-ethyl-2-(4-methyl-5-oxo-4-propan-2-yl-1H-imidazol-2-yl)pyridine-3-carboxylic acid and their salts and esters, and c) at least one herbicide C which is selected from diclosulam, chlorimuron ethyl, sulfentrazone, clomazone, pyroxasulfone, oxyfluorfen, metribuzin.

The synergistic herbicidal composition comprising bioactive amount of a) a herbicide A which is N-(1-Ethylpropyl)-3,4-dimethyl-2,6-dinitrobenzenamine and their salts and esters, b) a single herbicide B which is 5-ethyl-2-(4-methyl-5-oxo-4-propan-2-yl-1H-imidazol-2-yl)pyridine-3-carboxylic acid and their salts and esters, and c) at least one herbicide C which is selected from diclosulam, chlorimuron ethyl, sulfentrazone, clomazone, pyroxasulfone, oxyfluorfen, metribuzin. An herbicidal synergistic composition of present invention controls all kind of undesired vegetation including weeds such as monocots, dicots and sedges. The present synergistic herbicidal combinations also control annual and perennial weeds.

In an another embodiment of the present synergistic herbicidal composition comprising a) a herbicide A which is N-(1-Ethylpropyl)-3,4-dimethyl-2,6-dinitrobenzenamine and their salts and esters, b) a single herbicide B which is 5-ethyl-2-(4-methyl-5-oxo-4-propan-2-yl-1H-imidazol-2-yl)pyridine-3-carboxylic acid and their salts and esters, and c) at least one herbicide C which is selected from diclosulam, chlorimuron ethyl, sulfentrazone, clomazone, pyroxasulfone, oxyfluorfen, metribuzin .The combination of the present invention allows for the control of grass and broad leaf weeds in a wide range of crops. The broad spectrum of the present combination also provides a solution for preventing the development of resistance.

In an another embodiment of the present invention synergistic herbicidal composition of the present invention is effective for controlling undesired vegetation including weeds such as grassy weeds, broad leaf weeds and sedges; and an one-shot formulation effective for controlling undesired vegetation including weeds such as grassy weeds, broad leaf weeds and sedges.

In an embodiment of the present invention synergistic herbicidal composition can quickly absorb by the treated leaves of the weeds and germination weed’s roots and shoots and provide a synergistic herbicidal which can overcome the crop injury.

In an embodiment of the present invention synergistic herbicidal composition help in controlling undesired vegetation when applying before and after germination of undesired vegetation, i.e. as pre-emergence (before weed and crop germination), post-emergence (after weed and crop germination)

In another aspect, the present invention relates to the use of the composition as defined herein for controlling undesirable vegetation.

In another aspect, the present invention relates to a method for controlling undesirable vegetation which comprises applying to the vegetation or the locus thereof or applying to the soil or water to prevent the emergence or growth of the undesirable vegetation a herbicidally effective amount of synergistic herbicidal composition comprising a) a herbicide A which is N-(1-Ethylpropyl)-3,4-dimethyl-2,6-dinitrobenzenamine and their salts and esters, b) a single herbicide B which is 5-ethyl-2-(4-methyl-5-oxo-4-propan-2-yl-1H-imidazol-2-yl)pyridine-3-carboxylic acid and their salts and esters, and c) at least one herbicide C which is selected from diclosulam, chlorimuron ethyl, sulfentrazone, clomazone, pyroxasulfone, oxyfluorfen, metribuzin.

In some embodiments of this invention, Colby's equation is applied to determine whether the combination of herbicide A and herbicide B shows a synergistic effect (see S. R. Colby,
"Calculating synergistic and antagonistic responses of herbicide combinations", Weeds 1967, 15, pp. 20-22).
E = X + Y - (??/100)
where X = effect in percent using herbicide A at an application rate a;
Y = effect in percent using herbicide B at application rate b;
E = expected effect (in %) of herbicide A + herbicide B at application rates a + b.

For three-way combinations (herbicide A + herbicide B + herbicide C) a modified Colby equation can be used:
E = X + Y + Z - [(XY+X Z + Y Z) /100] - X Y Z/10000
where E, X and Y are as defined above and Z is the herbicidal effect in percent using a herbicide C (as defined herein) at an application rate c.

In Colby's equation, the value E corresponds to the effect (plant damage or injury) which is to be expected if the activity of the individual compounds is additive. If the observed effect is higher than the value E calculated according to the Colby equation, a synergistic effect is present.

In one embodiment of the present invention, the compositions, uses and methods disclosed herein are synergistic as determined by the Colby equation. Specifically, the synergistic herbicidal effect is determined according to the Colby equation. Moreover, the compositions, uses and methods of the present invention provide excellent pre- and post-emergence control of weeds. In particular, the compositions and methods are useful for controlling undesirable vegetation before their emergence (pre-emergence). The compositions, uses and methods of the present invention also show good crop compatibility, i.e. the formulated combinations comprising of a herbicide A which is N-(1-Ethylpropyl)-3,4-dimethyl-2,6-dinitrobenzenamine and their salts and esters, b) a single herbicide B which is 5-ethyl-2-(4-methyl-5-oxo-4-propan-2-yl-1H-imidazol-2-yl)pyridine-3-carboxylic acid and their salts and esters, and c) at least one herbicide C which is selected from diclosulam, chlorimuron ethyl, sulfentrazone, clomazone, pyroxasulfone, oxyfluorfen, metribuzin in crops does not result in increased phytotoxic to the crop plants when compared to the individual application of herbicides A, B and C. Furthermore, the compositions, uses and methods of the present invention provide effective control of herbicide resistant or tolerant weed species, in particular herbicide-resistant weed. For example, the formulated compositions, uses and methods of the present invention can effectively control herbicide-resistant. And susceptible weeds such as, Abutilon indicum, Acalypha indica, Acanthospermum hispidum, Achyranthes aspera, Aerva tomentosa, Ageratum conyzoides, Alhagi camelorum, Amaranthus hybridus, Amaranthus spinosus, Amaranthus viridis, Ammannia baccifera, Anagallis arvensis, Argemone mexicana, Artemisia nilagiricia, Asphodelus tenuifolius, Avena fatua, Avena ludoviciana, Bidens pilosa, Boerhaavia diffusa, Boerhavia repanda, Brachiaria mutica, Brassica kaber, Bromus tectorum, Calotropis gigantea, Cannabis sativa, Carthamus axyacantha, Cassia tora, Celosia argentea, Centella asiatica, Chenopodium album, Chenopodium murale, Chloris barbata, Chrozophora rottlerii, Cichorium intybus, Cirsium arvense, Clitoria ternatea, Cnicus arvensis, Commelina benghalensis, Commelina communis, Commelina diffusa, Convolvulus arvensis, Conyza canadensis, Corchorus acutangulus, Coronopus didymus, Crotalaria serice, Cucumis callosus, Cuscuta campestris, Cuscuta chinensis, Cynodon dactylon, Cyanotis axillaris, Cyperus esculenthus, Cyperus irria, Cyperus rotundus, Dactyloctenium aegyptium, Datura stramonium, Daucus carota, Digera arvensis, Digitaria sanguinalis, Dinebra retroflexa, Echinochola colonum, Echinochola crusgalli, Eclipta alba, Eichhornia crassipes, Elephantopus scaber, Eleusine indica, Eragrostis major, Euphorbia geniculata, Euphorbia hirta, Fimbristylis miliacea, Fumaria indica, Gynandropsis gynandra, Heliotropium indicum, Indigofera glandulosa, Ipomea aquatica, Lantana camara, Lathyrus aphaca, Launaea asplenifolia, Launaea nudicaulis, Leucas aspera, Ludwigia parviflora, Marsilea quadrifoliata, Medicago denticulate, Mimosa pudica, Melilotus alba, Melilotus indica, Ocimum canum, Oenothera biennis, Opuntia dillenil, Orobanche ramosa, Oryza longistaminata, Oryza sativa, Oxalis corniculata, Oxalis latifolia, Parthenium hysterophorus, Paspalum sanguinale, Phalaris minor, Phyllanthus niruri, Physalis minima, Polypogon monspeliensis, Portulaca oleracea, Prosopis juliflora, Rumex dentatus, Saccharum spontaneum, Stearia glauca, Seteria viridis, Sida spinosa, Silene antirrhina, Sisymbrium irio, Solanum nigrum, Solanum surattense, Sonchus oleraceous, Sorghum halepense, Spergula arvensis, Sphenocleazeylanica Gaertn, Striga asiatica, Tagetes minuta, Trianthema monogyna, Trianthema portulacastrum, Tribulus terrestris, Trigonelia polycerata, Vernonia cinerea, Vicia sativa and Xanthium strumarium. For example, the formulated compositions, uses and methods of the present invention can effectively control herbicide-resistant grass weeds such as, for example, Lolium species (LOLSS), Alopecurus myosuroides (ALOMY), Phalaris species (PHASS), Apera spica-venti (APESV). The formulated compositions, uses and methods of the present invention are also suitable for controlling herbicide-resistant broadleaf weeds such as, for example, Papaver rhoeas (PAPRH, corn poppy) which has evolved resistance, especially against ALS-inhibiting herbicides.

In addition, the formulated compositions, uses and methods of the present invention can effectively control weed biotypes with target-site resistance but also weed biotypes with non-target site resistance. The formulated compositions of the present invention, is effective in crops selected from Examples of the crops on which the present compositions may be used include GMO (Genetically Modified Organism) and Non GMO traits, hybrids and conventional varieties of Sugarcane (Saccharum officinarum), Soybean (Glycin max), Groundnut/Peanut (Arachis hypogaea), Green gram (Vigna radiata), Black gram (Vigna mungo), Chickpea (Cicer aritinum), Cowpea (Vigna unguiculata), Red gram (Cajanus cajan), French bean (Phaseolus vulgaris), Indian bean (Lablab purpureus), Horse gram (Macrotyloma uniflorum), Field pea (Pisum sativum), Cluster bean (Cyamopsis tetragonoloba), Lentils (Lens culinaris). Crops are to be understood as also including those crops which have been rendered tolerant to herbicides or classes of herbicides (e.g. ALS-, GS-, EPSPS-, PPO-, ACCase- and HPPD-inhibitors) by conventional methods of breeding or by genetic engineering.

Examples of crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate- and glufosinate-resistant soybean, imazethapyr tolerant paddy/rice. Crops are also to be understood to include those which are obtained by conventional methods of breeding or genetic engineering and contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavour). Other useful plants include turf grass for example in golf-courses, lawns, parks and roadsides, or grown commercially for sod, and ornamental plants such as flowers or bushes. A particular advantage is that the formulated compositions, uses and methods of the present invention also provide effective control of weed biotypes having both target-site resistance and non-target-site resistance, such as e.g. resistant populations of Alopecurus myosuroides (ALOMY) or Lolium rigidum (LOLRI).

In the formulated compositions of the present invention the herbicidal composition comprising bioactive amount of a) a herbicide A which is N-(1-Ethylpropyl)-3,4-dimethyl-2,6-dinitrobenzenamine and their salts and esters is present in the range of 15% to 50% w/w; preferably in range of 20% to 45% w/w b) a single herbicide B which is 5-ethyl-2-(4-methyl-5-oxo-4-propan-2-yl-1H-imidazol-2-yl)pyridine-3-carboxylic acid and their salts and esters is present in the range of 1% to 8 % w/w, preferably in range of 1% to 5 % w/w; c) at least one herbicide C is present in the range of 0.1% to 20% w/w, preferably in range of 0.3% to 15% w/w.

In another embodiment, the compositions of the present invention formulated combinations comprising of a herbicide A which is N-(1-Ethylpropyl)-3,4-dimethyl-2,6-dinitrobenzenamine and their salts and esters, b) a single herbicide B which is 5-ethyl-2-(4-methyl-5-oxo-4-propan-2-yl-1H-imidazol-2-yl)pyridine-3-carboxylic acid and their salts and esters, and c) at least one herbicide C which is selected from diclosulam, chlorimuron ethyl, sulfentrazone, clomazone, pyroxasulfone, oxyfluorfen, metribuzin, and at least one safener D. Exemplary safeners D include benoxacor, cloquintocet, cyometrinil, cyprosulfamide, dichlormid, dicyclonon, dietholate, fenchlorazole, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen, mefenpyr, mephenate, naphthaleneacetic acid, naphthalic anhydride, oxabetrinil, 4-(dichloroacetyl)-1 -oxa-4-azaspiro[4.5]decane, 2,2,5-trimethyl-3-(dichloroacetyl)-1 ,3-oxazolidine, N- (2-Methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide, and agriculturally acceptable salts, esters or amides thereof. Preferably, the safener is selected from the group consisting of benoxacor, cloquintocet, cyprosulfamide, dichlormid, fenclorazole, fenclorim, isoxadifen, mefenpyr, and agriculturally acceptable salts, esters or amides thereof. More preferably, the safener E is selected from the group consisting of benoxacor, cloquintocet-mexyl, cyprosulfamide, dichlormid, fenclorazole-ethyl, fenclorim, isoxadifen-ethyl, and mefenpyr-diethyl. Even more preferably, the safener is selected from the group consisting of benoxacor, cloquintocet, cyprosulfamide, isoxadifen, mefenpyr, and agriculturally acceptable salts, esters or amides thereof. In particular, the safener is selected from the group consisting of benoxacor, cloquintocet-mexyl, cyprosulfamide, isoxadifen-ethyl, and mefenpyr-diethyl.

The present herbicidal composition comprising bioactive amount of a) a herbicide A which is N-(1-Ethylpropyl)-3,4-dimethyl-2,6-dinitrobenzenamine and their salts and esters is present in the range of 15% to 50% w/w; b) a herbicide B which is 5-ethyl-2-(4-methyl-5-oxo-4-propan-2-yl-1H-imidazol-2-yl)pyridine-3-carboxylic acid and their salts and esters is present in the range of 1% to 8 % w/w; c) at least one herbicide C which is selected from diclosulam, chlorimuron ethyl, sulfentrazone, clomazone, pyroxasulfone, oxyfluorfen, metribuzin is present in the range of 0.1% to 20% w/w or combination thereof that controls harmful weeds.

The formulated combinations comprising of a herbicide A which is N-(1-Ethylpropyl)-3,4-dimethyl-2,6-dinitrobenzenamine and their salts and esters, b) a single herbicide B which is 5-ethyl-2-(4-methyl-5-oxo-4-propan-2-yl-1H-imidazol-2-yl)pyridine-3-carboxylic acid and their salts and esters, and c) at least one herbicide C which is selected from diclosulam, chlorimuron ethyl, sulfentrazone, clomazone, pyroxasulfone, oxyfluorfen, metribuzin and the optionally further at least one safener D according to the invention can, for example, be formulated as follows:

The composition of the present invention in addition to bioactive amounts of active ingredients further comprises inactive formulation excipients including but not limited to wetting agents, wetting-spreading-penetrating agent, dispersant or dispersing agent, anti-freezing agent, emulsifying agent, anti-foam agent, preservatives, solvents, co-solvents, preservative, stabilizer, diluent, carriers, suspension aid or suspending agent, thickener, and buffering agent.

Capsule suspension (CS), Dispersible concentrate (DC), Emulsifiable concentrate (EC), Emulsion, water in oil (EO), Emulsion, oil in water (EW), Jambo balls or bags (bags in water soluble pouch), Micro-emulsion (ME), Oil dispersion (OD), Oil miscible flowable concentrate (oil miscible suspension (OF), Oil miscible liquid (OL), Suspension concentrate (SC), Suspo-emulsion (SE), Soluble concentrate (SL), Water dispersible granule (WG or WDG), Water soluble granule (SG), Water soluble powder (SP), Wettable powder (WP), A mixed formulation of CS and SC (ZC), A mixed formulation of CS and SE (ZE), A mixed formulation of CS and EW (ZW), Granule for soil application (GR).

Products for Preparation of Emulsifiable concentrate (EC) formulation Lists of inactive excipients used in:

Suitable carriers include liquid carriers Solvent for Emulsifiable concentrate (EC) formulation includes: naphtha or heavy aromatic hydrocarbon is selected from the group comprising of toluene, o-, m-, p-xylene, dodecane, n- decane, n-hexane, benzene, ethylbenzene, isopropyl benzene, tert-butylbenzene, naphthalene, mono- or poly alkyl-substituted naphthalene, paraffinic hydrocarbons, n-butanol, N-methyl 2-pyrrolidine, cyclohexanone, isophorone-3, 5, ester solvents such as methyl oleate, dimethyl amide and morpholine amide derivatives of C6-C16 fatty acids, and mono-alkylene carbonates such as ethylene carbonate, propylene carbonate and butylene carbonates, dimethyl sulfoxide (DMSO), n-alkyl pyrrolidone, fatty acid dimethyl esters, fatty acid esters, dibasic esters, one or more dimethyl amides, such as C8-dimethylamide, C10-dimethylamide, C12-dimethylamide, ethylene glycol, propylene glycol, poly alkylene glycols, N-Methyl-2-Pyrrolidone (NMP); N,N-dimethylformamide (DMF); dimethyl isosorbide (DMI); isophorone; acetophenone; 1,3-dimethyl-2-imidazolidonone; lactate esters; dimethyl and diethyl carbonates; alcohols including methanol; ethanol; iso-propanol; n-propanol; n-butanol; iso-butanol; 2-ethylhexanol , methanol, tert-butanol; Methyl L-lactate, 2-Ethylhexyl L-lactate, Ethyl L-lactate, n-Butyl L-lactate, Octyl phenyl ethoxylates.

Suitable Emulsifier for Emulsifiable concentrate (EC) formulation include: Emulsifiers containing salts of dodecylbenzene sulphonate, e.g. Ca-salts or amine salts, and sulphonates of other C11-C16 alkylbenzenes, alkyl ether sulphates, alkylphenoletherphosphates and ester phosphates; non-ionic surfactants such as alkoxylated alcohols and alkylphenols, ethoxylated vegetable oils, e.g. ethoxylated castor oil, fatty acid esters, ethoxylated amines, and condensates of glycerol; and catanionic emulsifiers such as a cationic amine, optionally in combination with an alkyl sulphonate or ether sulphonate or ether phosphate, alkoxylated alcohols; alkoxylated alkylphenols; tristyrylphenol ethoxylate; fatty acid esters of sorbitol and ethoxylated derivatives thereof; sulfonated alkylbenzenes in the range C11-C16 and salts thereof; alkyl ether sulphates; alkyletherphosphates; alkylphenoletherphosphates; or combinations thereof; salts of phosphate esters of ethoxylated tristyrylphenol; salts of sulphated ethers of ethoxylated tristyrylphenol; or a catanionic system, wherein a cationic amine is present in combination with an alkyl sulphonate, an alkylethersulphonate, an ether sulphate, or an ether phosphate such as an alkyletherphosphate, nonylphenol polyethoxy ethanol, castor oil polyglycol ethers, polyadducts of ethylene oxide and polypropylene, tributyl phenoxy polyethoxy ethanol, octyl phenoxy polyethoxy ethanol, calcium alkyl benzenesulfonate, ethoxylated polysorbate and calcium salt of alkyl benzene sulfonate.
Suitable Sticker, surface tension reducer, binder for Emulsifiable concentrate (EC) formulation include: Polyvinylpyrrolidone.

Suitable Spreader, sticker, penetrant, surface tension reducer for Emulsifiable concentrate (EC) formulation include: Alkyl polyethylene glycol ether.

A Manufacturing process for preparation Oil dispersion (OD) formulation:

Part A-Preparation of the liquid premix
Step 1- Charge Vegetable oil or solvent or both into a vessel with anchor stirrer.
Step 2- Under stirring, add the emulsifier and dispersing agent and stir until all ingredients are dissolved completely.
Part B-Preparation of the slurry
Step 1- Now; charge the liquid premix into a second vessel, equipped with a cooling and heating device and a high shear stirrer.
Step 2- Add the active ingredient and homogenize thoroughly. Pre-mill this mixture and finally mill it using a bead mill to achieve a particle size distribution as required by the specification.
Part C-Preparation of the Thickener gel
Step 1- Charge the vegetable/plant/seed oil or solvent to the vessel, equipped with a high shear stirrer.
Step 2- Add gradually the thickener which is organophilic clay, maintaining high-shear mixing throughout. Stirring is continued until thoroughly mixed.
Step 3- Under stirring, the thickener activating agent is added. Allow the gel to swell whilst maintaining mixing.
Part D-Preparation of the final formulation
Step 1- Now add the thickener gel and disperse the mixture by using a high shear stirrer.
Step 2- Finally add the recommended wetting and spreading agent or adjuvants (silicone or non-silicone based) to this formulation and disperse by using high shear stirrer.
Step 3- Check the finished formulation to specification.
Step 4- After approval, material is packed in required pack sizes.

A Product for Preparation of Oil dispersion (OD) formulation Lists of inactive excipients used in:
Suitable Wetting agent includes - ethylene oxide/propylene oxide block copolymer, polyarylphenyl ether phosphate, ethoxylated fatty alcohol, sodium dioctyl sulfosuccinate, sodium lauryl sulfate and sodium dodecyl benzene sulfonate, alkyldiphenyl sulfonates, sodium isopropyl naphthalene sulfonate, alkylnaphthalene sulfonate;
Suitable Wetting-spreading-penetrating agent for Oil dispersion (OD) formulation includes - Organosilicone surfactants includes trisiloxane ethoxylate, polydimethylsiloxane, polyoxyethylene methyl polysiloxane, polyoxyalkylene methyl polysiloxane, polyether polymethyl siloxane copolymer, heptamethyl trisiloxane, Polyalkyleneoxide modified heptamethyl trisiloxane, polyether modified polysiloxane, may or may not be in modified form, may be liquid or powder form or mixture thereof etc;
Suitable Emulsifying agent for Oil dispersion (OD) formulation includes - castor oil ethoxylates, alcohol ethoxylates, fatty acid ethoxylates, sorbitan ester ethoxylates, sulphosuccinate, calcium salts of dodecylbenzene sulphonate, alkylammonium salts of alkylbenzene sulphonate, alkylsulphosuccinate salts, ethylene oxide-propylene oxide block copolymers, ethoxylated alkylamines, ethoxylated alkyl phenols,
polyoxyethylene sorbitan monolaurate etc;

Suitable Dispersing agent for Oil dispersion (OD) formulation includes -Alkyl sulfonates, alkyl benzene sulfonates, alkyl aryl sulfonates, alkylphenolalkoxylates, tristyrylphenol ethoxylates, natural or synthetic fatty ethoxylate alcohols, natural or synthetic fatty acid alkoxylates, natural or synthetic fatty alcohols alkoxylates, alkoxylated alcohols (such as n-butyl alcohol poly glycol ether), block copolymers (such as ethylene oxide-propylene oxide block copolymers and ethylene oxide-butylene oxide block copolymers), fatty acid-polyalkylene glycol condensates, polyamine-fatty acid condensates, polyester condensates, salts of polyolefin condensates, sodium ligno sulfonate, sodium ploycarboxylate, EO/PO based copolymer, phenol sulfonate, sodium methyl oleoyl taurate, styrene acrylic acid copolymer, propyleneoxide-ethyleneoxide-copolymer, polyethylene glycol 2,4,6-tristyrylphenyl ether, tristyrylphenol-polyglycolether-phosphate, tristyrylphenole with 16 moles EO, tristyrylphenol-polyglycolether-phosphate, oleyl-polyglycolether with ethylene oxide, tallow fattyamine polyethylene oxide, nonylphenol polyglycolether with 9-10 moles ethylene oxide;

Suitable Stabilizers for Oil dispersion (OD) formulation includes -hectorite clay, aluminium magnesium silicate, bentonite clay, silica, attapulgite clay;

Suitable Antifoaming agent for Oil dispersion (OD) formulation includes -silicone oil, silicone compound, C10~C20 saturated fat acid compounds or C8~C10 aliphatic alcohols compound, silicone antifoam emulsion, dimethylsiloxane, polydimethyl siloxane, vegetable oil based antifoam, tallow based fatty acids, polyalkyleneoxide modified polydimethylsiloxane etc;

Suitable Anti-freezing agent for Oil dispersion (OD) formulation includes -ethylene glycol, propane diols, glycerine or the urea, glycol (Monoethylene glycol, Diethylene glycol, Polypropylene glycol, Polyethylene glycol), glycerine, urea, magnesium sulfate heptahydrate, sodium chloride etc;
Suitable Preservative for Oil dispersion (OD) formulation includes -1,2-benzisothiazolin-3(2H)-one, sodium salt, sodium benzoate, 2-bromo-2-nitropropane-1,3-diol, formaldehyde, sodium o-phenylphenate, 5-chloro-2-methyl-4-isothiazolin-3-one & 2-methyl-4-isothiazolin-3-one;

Suitable Solvent for Oil dispersion (OD) formulation includes - solvent for the present formulation is selected from and not limited to vegetable oil (plant, seed or tree) or its alkylated or ethoxylated or esterified. The alkylated vegetable oil may be methylated vegetable oil or ethylated vegetable oil. The vegetable oils include olive oil, kapok oil, castor oil, papaya oil, camellia oil, sesame oil, corn oil, rice bran oil, cotton seed oil, soybean oil, groundnut oil, rapeseed-mustard oil, linseed oil, tung oil, sunflower oil, safflower oil, coconut oil. The alkyl ester of vegetable oils includes methyl ester, ethyl ester, propyl ester or butyl ester of vegetable oils. Some of the examples are methylated seed oil, polyalkyleneoxide modified polydimethylsiloxane alkylphenol ethoxylate, rapeseed oil methyl ester, rapeseed oil ethyl ester, rapeseed oil propyl esters, rapeseed oil butyl esters, soybean oil methyl ester, soybean oil ethyl ester, soybean oil propyl ester, soybean oil butyl ester, castor oil methyl ester, castor oil ethyl ester, castor oil propyl ester, castor oil butyl ester, cotton seed oil methyl ester, cotton seed oil ethyl ester, cotton seed oil butyl ester, cotton seed oil propyl ester, tall oil fatty acids esters-tallow methyl ester, tallow ethyl ester, tallow propyl ester, bio-diesel, mineral oil (aromatic solvents, isoparaffin, base solvent), fatty acid amides (e.g. C1 -C3 amines, alkylamines or alkanolamines with C6–C18 carboxylic acids), fatty acids, alkyl esters of fatty acids, methyl and ethyl oleate, methyl and ethyl soyate, alkyl benzenes and alkylnaphthalenes, polyalkylene glycol ethers, fatty acid diesters, fatty alkylamides and diamides, dialkylene carbonates, ketones and alcohols. The above oil based carrier/diluting agents may be used as solo or mixture of two or more if desired. Cosolvent: Cyclohexanone, Acetophenone, NMP, Dimethyl sulfoxide, Benzyl alcohol, Butanol, N-octanol, N-Propanol, 2-ethyl hexanol, Tetrahydro furfuryl alcohol, Isophorone, Fatty acid dimethyl amide, 2-hexylethyl lactate, Propylene carbonate

A Product for Preparation of Suspo Emulsion formulation is a mixture of SC + EC:
A Manufacturing process for preparation of EC part Lists of inactive excipients used:
Example of solvents used herein for the SE (Suspo Emulsion) formulation includes but not limited to naphtha or heavy aromatic hydrocarbon is selected from the group comprising of toluene, o-, m-, p-xylene, dodecane, n- decane, n-hexane, benzene, ethylbenzene, isopropyl benzene, tert-butylbenzene, naphthalene, mono- or poly alkyl-substituted naphthalene, paraffinic hydrocarbons, n-butanol, N-methyl 2-pyrrolidine, cyclohexanone, isophorone-3, 5, ester solvents such as methyl oleate, dimethyl amide and morpholine amide derivatives of C6-C16 fatty acids, and mono-alkylene carbonates such as ethylene carbonate, propylene carbonate and butylene carbonates, dimethyl sulfoxide (DMSO), n-alkyl pyrrolidone, fatty acid dimethyl esters, fatty acid esters, dibasic esters, one or more dimethyl amides, such as C8-dimethylamide, C10-dimethylamide, C12-dimethylamide, ethylene glycol, propylene glycol, poly alkylene glycols, N-Methyl-2-Pyrrolidone (NMP); N,N-dimethylformamide (DMF); dimethyl isosorbide (DMI); isophorone; acetophenone; 1,3-dimethyl-2-imidazolidonone; lactate esters; dimethyl and diethyl carbonates; alcohols including methanol; ethanol; iso-propanol; n-propanol; n-butanol; iso-butanol; 2-ethylhexanol , methanol, tert-butanol; Methyl L-lactate, 2-Ethylhexyl L-lactate, Ethyl L-lactate, n-Butyl L-lactate, Octyl phenyl ethoxylates.

Example of Emulsifier used herein for the SE (Suspo Emulsion) formulation includes but not limited to: Emulsifiers containing salts of dodecylbenzene sulphonate, e.g. Ca-salts or amine salts, and sulphonates of other C11-C16 alkylbenzenes, alkyl ether sulphates, alkylphenol ether phosphates and ester phosphates; non-ionic surfactants such as alkoxylated alcohols and alkylphenols, ethoxylated vegetable oils, e.g. ethoxylated castor oil, fatty acid esters, ethoxylated amines, and condensates of glycerol; and catanionic emulsifiers such as a cationic amine, optionally in combination with an alkyl sulphonate or ether sulphonate or ether phosphate, alkoxylated alcohols; alkoxylated alkylphenols; tristyrylphenol ethoxylate; fatty acid esters of sorbitol and ethoxylated derivatives thereof; sulfonated alkylbenzenes in the range C11-C16 and salts thereof; alkyl ether sulphates; alkyl ether phosphates; alkylphenoletherphosphates; or combinations thereof; salts of phosphate esters of ethoxylated tristyrylphenol; salts of sulphated ethers of ethoxylated tristyrylphenol; or a catanionic system, wherein a cationic amine is present in combination with an alkyl sulphonate, an alkylethersulphonate, an ether sulphate, or an ether phosphate such as an alkyletherphosphate, nonylphenol polyethoxy ethanol, castor oil polyglycol ethers, polyadducts of ethylene oxide and polypropylene, tributyl phenoxy polyethoxy ethanol, octyl phenoxy polyethoxy ethanol, calcium alkyl benzenesulfonate, ethoxylated polysorbate and calcium salt of alkyl benzene sulfonate.

Example of Sticker, surface tension reducer, binder used herein for the SE (Suspo Emulsion) formulation includes but not limited to Polyvinylpyrrolidone

Example of Spreader, sticker, penetrant, surface tension reducer used herein for the SE (Suspo Emulsion) formulation includes but not limited to Alkyl polyethylene glycol ether.

A Manufacturing process for preparation of SC part Lists of inactive excipients used:
Example of Wetting agent used herein for the SE (Suspo Emulsion) formulation includes but not limited to - ethylene oxide/propylene oxide (EO/PO) block copolymer, poly aryl phenyl ether phosphate, polyalkoxylated butyl ether, ethoxylated fatty alcohol, sodium dioctyl sulfosuccinate, sodium lauryl sulfate and sodium dodecyl benzene sulfonate, alkyl diphenyl sulfonates, sodium isopropyl naphthalene sulfonate, alkyl naphthalene sulfonate. Ethoxylated alcohol includes natural fatty alcohol (lauryl alcohol ethoxylate, lauryl alcohol alkoxylate), synthetic alcohol ethoxylate (tridecyl alcohol ethoxylate, 2-ethyl hexanol, 2-propylheptanol, isodecyl alcohol.
Example of Wetting-spreading-penetrating agent used herein for the SE (Suspo Emulsion) formulation includes but not limited to -trisiloxane ethoxylate, heptamethyl trisiloxane, modified form includes polyalkyleneoxide modified heptamethyl trisiloxane, polyether modified polysiloxane, polyalkyleneoxide modified trisiloxane, polyalkyleneoxide modified polydimethylsiloxane, may be liquid or powder form.

Example of Dispersing agent used herein for the SE (Suspo Emulsion) formulation includes but not limited to - Naphthalenesulfonic acid, sodium salt condensate with formaldehyde, alkylated naphthalene sulfonate, sodium salt, sodium salt of naphthalene sulfonate condensate, sodium ligno sulfonate, sodium polycarboxylate, EO/PO based copolymer, phenol sulfonate, sodium methyl oleoyl taurate, acrylic graft copolymer, styrene acrylic acid copolymer, propylene oxide-ethylene oxide-copolymer, polyethylene glycol 2,4,6-tristyrylphenyl ether, tristyrylphenol-polyglycol ether-phosphate, tristyrylphenole with 16 moles EO, tristyrylphenol-polyglycol ether-phosphate, oleyl-polyglycol ether with ethylene oxide, tallow fatty amine polyethylene oxide, nonylphenol polyglycol ether with 9-10 moles ethylene oxide;

Example of Suspending agent used herein for the SE (Suspo Emulsion) formulation includes but not limited to - aluminum magnesium silicate, bentonite clay, silica, attapulgite clay.

Example of Antifoaming agent used herein for the SE (Suspo Emulsion) formulation includes but not limited to - silicone antifoam emulsion, dimethyl siloxane, polydimethyl siloxane, vegetable oil based antifoam, tallow based fatty acids.

Example of Anti-freezing agent used herein for the SE (Suspo Emulsion) formulation includes but not limited to - ethylene glycol, propane diols, glycerin or the urea, glycol (monoethylene glycol, diethylene glycol, 1,2-propylene glycol, polyethylene glycol), glycerin, urea, magnesium sulfate heptahydrate, sodium chloride etc.

Example of Preservatives used herein for the SE (Suspo Emulsion) formulation includes but not limited to - 1, 2-benzisothiazolin-3(2H)-one, sodium salt, sodium benzoate, 2-bromo-2-nitropropane-1,3-diol, formaldehyde, sodium o-phenyl phenate, 5-chloro-2-methyl-4-isothiazolin-3-one & 2-methyl-4-isothiazolin-3-one

Example of Thickeners used herein for the SE (Suspo Emulsion) formulation includes but not limited to - xanthan gum, PVK, carboxymethyl celluloses, polyvinyl alcohols, gelatin, sodium carboxymethylcellulose, hydroxyethyl cellulose, sodium polyacrylate, modified starch, acacia gum.

Example of Humectant used herein for the SE (Suspo Emulsion) formulation includes but not limited to - urea, humic acid, glycerol, lactose.

Example of Diluent used herein for the SE (Suspo Emulsion) formulation includes but not limited to - water.

Lists of inactive excipient used in ZC (Zeon Concentrate) (CS+SC)
Manufacturing process for Capsule Suspension (CS):

Step 1-Aqueous Phase-Charge water to a stainless-steel vessel equipped with a high speed stirrer. Under agitation, add the wetting agent, dispersing agent 1and dispersing agent 2 into the vessel. Now add 50% quantity of antifoam to avoid foam generation in this vessel.

Step 2-Organic Phase-Charge heavy aromatic hydrocarbons solvent into second stainless-steel reactor. Then, slowly add melted active ingredient into the reactor. Afterwards, charge wall forming material 1 material to the reactor. Continue mixing. Cool the reactor contents to room temperature.

Step 3-Start the high shear disperser of aqueous phase and charge the ‘Organic Solution’ into the ‘Aqueous Phase Solution’ under gravity in specific rate so that required particle size can be achieved and continue to shear for 30 min. Then, start heating the reactor to around 50 °C and stir the formulation under slow rpm for 3-4 hours so that Polymerization reaction gets completed.

Step 4-Now add wall forming material 2 so that residual wall forming material 1 can be consumed and stir for 1 more hour at the same temperature and if required add half quantity of antifoam to remove foam generating due to CO2 during reaction.

Step 5-After the wall polymerization reaction, increase the agitator to high speed. Add the rest half quantity of antifoam to the formulation. Under slight vacuum, allow the mixture to de-gas for approximately 30 minutes to remove CO2 from the solution. Add the linear polysaccharide, preservative and in last freezing agent and mix for some minutes. Add buffering agent for pH adjustment and mix well.

Step 6-Final product is sent for QC approval.

Step 7-After approval, material is packed in required pack sizes.

Example of Wall forming material 1 used herein for the ZC (Zeon Concentrate) formulation includes but not limited to: Tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, 4,4-diphenylmethene diisocyanate (MDI), polymethylene polyphenylene isocyanate, 2,4,4’-diphenyl ether tri-isocyanate, 3,3’-dimethyl-4,4’-diphenyl diisocyanate, 3,3’-dimethoxy-4,4’-diphenyl diisocyanate, 1,5-naphthylene diisocyanate and 4,4’4"-triphenylmethane tri-isocyanate, toluene diisocyanate or polymethylene polyphenylisocyanate, polyurethane comprising of polyfunctional iso cyanate and a polyamine in polarized form;

Example of Wall forming material 2 used herein for the ZC (Zeon Concentrate) formulation includes but not limited to: Diethylene triamine, Ammonia, hexamine, ethylenediamine, propylene-1,3-diamine, tetramethylenediamine, pentamethylenediamine, 1,6-hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetra ethylene pentamine, pentaethylenehexamine, 4,9-dioxadodecane-1, 12-diamine, 1,3- phenylenediamine, 2,4- and 2,6-toluenediamine and 4,4’-diaminodiphenylmethane, 1,3-phenylenediamine, 2,4- and 2,6-toluenediamine, 4,4'-diaminodiphenylmethane, 1,5-diaminonaphthalene, 1,3,5-triaminobenzene, 2,4,6-triaminotoluene, 1,3,6-triaminonaphthalene, 2,4,4'-triaminodiphenyl ether, 3,4,5-triamino-1,2,4-triazole and 1,4,5,8-tetraminoanthraquinone;

Example of Dispersing agents used herein for the ZC (Zeon Concentrate) formulation includes but not limited to: Ethoxylated lignosulfonic acid salts, lignosulfonic acid salts, oxidized lignins, lignin salts, salts of styrenemaleic anhydride copolymers, polyvinyl alcohol, salts of partial esters of styrene-maleic anhydride copolymers, partial salts of polyacrylic acid and partial salts of polyacrylic acid terpolymers. the surfactant is lignosulfonate of calcium or sodium or mixtures thereof or a modified kraft lignin with a high sulfonic acid group , dibutylnaphthalenesulfonic acid ,fatty acids, alkyl- and alkylarylsulfonates, alkyl sulfates, lauryl ether sulfates and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols and of fatty alcohol glycol ethers, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene or of the naphthalenesulfonic acids with phenol and formaldehyde, alkyl napthalene sulfonate condensate, polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl- or nonylphenol, alkyl phenyl polyglycol ether, tributyl phenyl polyglycol ethers, alkyl aryl polyether alcohols, is tridecyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin-sulphite waste liquors, and proteins, denatured proteins, polysaccharides , ammonium salts of sulfonates, sulfates, phosphates or carboxylates, alkylarylsulfonates, diphenyl sulfonates, alpha-olefin sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of condensed naphthalene, sulfonates of dodecyl- and tridecyl benzenes, sulfonates of naphthalene and alkylnaphthalenes, sulfosuccinates or sulfosuccinates, alkoxylates, N-alkylated fatty acid amides, amine oxides, esters or sugar-based surfactants, alkylphenols, amines (e.g. tallow amine), amides, aryl phenols, fatty acids or fatty acid esters which have been alkoxylated. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide, polyethylene oxide and polypropylene oxide, polyacids or polybases;

Example of Wetting agent used herein for the ZC (Zeon Concentrate) formulation includes but not limited to: Ethylene oxide/propylene oxide block copolymer, Polyarylphenyl ether phosphate, Ethoxylated Fatty Alcohol, Sodium dioctyl sulfosuccinate, sodium lauryl sulphate and sodium dodecyl benzene sulfonate, alkyl diphenyl sulfonates, sodium isopropyl naphthalene sulfonate, Alkyl naphthalene sulfonate, Octyl phenol ethoxylate, alkyl phenol ethoxylate;

Example of Wetting-spreading-penetrating agent used herein for the ZC (Zeon Concentrate) formulation includes but not limited to: Organosilicone surfactants includes trisiloxane ethoxylate, polydimethylsiloxane, polyoxyethylene methyl polysiloxane, polyoxyalkylene methyl polysiloxane, polyether polymethyl siloxane copolymer, heptamethyl trisiloxane, Polyalkyleneoxide modified heptamethyl trisiloxane, polyether modified polysiloxane, 10 mole ethylene oxide adduct of octylphenol, may or may not be in modified form, may be liquid or powder form or mixture thereof etc;

Example of Solvent used herein for the ZC (Zeon Concentrate) formulation includes but not limited to: Hydrocarbon solvent such a an aliphatic, cyclic and aromatic hydrocarbons (e.g. toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalene or their derivatives, mineral oil fractions of medium to high boiling point (such as kerosene, diesel oil, coal tar oils)); a vegetable oil such as corn oil, rapeseed oil; a fatty acid ester such as C1-C10-alkylester of a C10-C22-fatty acid; or, methyl- or ethyl esters of vegetable oils such as rapeseed oil methyl ester or corn oil methyl ester, acetophenone, 2-Heptanon , 3-heptanone, 2-hexanone, 5-methyl-2-hexanone , 5-methyl-3-heptanone, 3-methyl-2-hexanone , 4-methyl-2-hexanone, 2-methyl-3-hexanone, 4-methyl-3-hexanone , 5-methyl-3-hexanone ,3-ethyl-2-pentanone , 3,3-dimethyl-2-pentanone , 3,4-dimethyl-2-pentanone, 4,4-dimethyl-2-pentanone , 2,2-dimethyl-3-pentanone , 2,4-dimethyl-3-pentanone, 2-octanone , 2,5-dimethyl-3-hexanone , 2,2-dimethyl-3-hexanone , 3,3-dimethyl-2-hexanone, 3,4-dimethyl-2-hexanone, 4,4-dimethyl-3-hexanone , 3-ethyl-4-methyl-2-pentanone , 2-methyl-3-heptanone, 2-methyl-4-heptanone, 3-methyl-2-heptanone, 3-methyl-4-heptanone, 5-methyl-3-heptanone, 6-methyl-2-heptanone , 6-methyl-3-heptanone, 3-octanone, 4-octanone, 2,2,4-trimethyl-3-pentanone , 3-ethyl-3-methyl-2-pentanone, 5-methyl-2-heptanone, isoprene;

Example of Thickener used herein for the ZC (Zeon Concentrate) formulation includes but not limited to: Xanthan gum, Carboxy methyl cellulose, Attapulgite clay, Bentonite clay;

Example of suspending agent used herein for the ZC (Zeon Concentrate) formulation includes but not limited to: Aluminium Magnesium Silicate, Bentonite clay, Silica, Attapulgite clay, tributyl phenyl polyglycol ether.

Example of Antifoaming agent used herein for the ZC (Zeon Concentrate) formulation includes but not limited to: silicone oil, silicone compound, C10~C20 saturated fat acid compounds or C8~C10 aliphatic alcohols compound, Silicone antifoam emulsion, Dimethyl siloxane, Polydimethyl siloxane, Vegetable oil based antifoam, tallow based fatty acids, polyalkyleneoxide modified polydimethylsiloxane etc;

Example of Antifreezing agent used herein for the ZC (Zeon Concentrate) formulation includes but not limited to: ethylene glycol, propane diols, glycerine or the urea, Glycol (Monoethylene glycol, Diethylene glycol, Polypropylene glycol, Polyethylene glycol), Glycerine, Urea, Magnesium sulphate heptahydrate, sodium chloride etc;

Example of Preservative used herein for the ZC (Zeon Concentrate) formulation includes but not limited to: 1,2-benzisothiazolin-3(2H)-one, sodium salt, Sodium benzoate, 2-bromo-2-nitropropane-1,3-diol, Formaldehyde, Sodium o-phenyl phenate, 5-chloro-2-methyl-4-isothiazolin-3-one & 2-methyl-4-isothiazolin-3-one;

Example of Buffering agent used herein for the ZC (Zeon Concentrate) formulation includes but not limited to: Sodium hydroxide, potassium hydroxide, acetic acid, sulphuric acid, hydrochloric acid, ortho phosphoric acid, ammonium hydroxide.

While the foregoing written description of the invention enables one of ordinary skill to make and use what is considered presently to be the best mode thereof, those of ordinary skill will understand and appreciate the existence of variations, combinations, and equivalents of the specific embodiment, method, and examples herein. The invention should therefore not be limited by the above described embodiment, method, and examples, but by all embodiments and methods within the scope and spirit of the invention. The invention shall now be described with reference to the following specific examples. It should be noted that the example(s) appended below illustrate rather than limit the invention, and that those skilled in the art will be able to design many alternative embodiments without departing from the scope of the present invention.
These and other aspects of the invention may become more apparent from the examples set forth herein below. These examples are provided merely as illustrations of the invention and are not intended to be construed as a limitation thereof.

EXAMPLE 1:
Chemical composition-Pendimethalin 30%+Imazethapyr 2%+Diclosulam 1% EC (Emulsifiable concentrate)
Ingredients Content(%,w/w)
Pendimethalin a.i. 30.00
Imazethapyr a.i. 2.00
Diclosulam a.i. 1.00
Vegetable oil ethoxylate (Emulsifier) 5.00
Calcium alkyl benzenesulfonate (Emulsifier) 5.00
Cyclohexanone (Co-solvent) 15.00
N,N-Dimethylformamide(Co-solvent) 12.00
Solvent naphtha (Solvent) 30.00
Total 100.00
a.i. (active ingredient/technical) on 100% purity basis

Mfg process for 100 kg of Pendimethalin 30%+Imazethapyr 2%+Diclosulam 1% EC
Step 1: Charge Solvent naphtha (30.00 kg), N, N-Dimethylformamide (12.00 kg) and Cyclohexanone (15.00 kg) into the vessel and then add Pendimethalin technical (30 kg), Imazethapyr technical (2 kg) and Diclosulam technical (1.00 kg) slowly and mix thoroughly till it get dissolved completely.
Step 2: Now add Vegetable oil ethoxylate (5 kg) and Calcium alkyl benzenesulfonate (5 kg) into this premix slowly and homogenised to get uniform solution.
Step 3: After getting the homogeneous solution give the sample for quality chech to QC and after approval from QC filter the material and pack in suitable container.
Storage stability: Pendimethalin 30%+Imazethapyr 2%+Diclosulam 1% EC

Laboratory storage stability for 14 days
Parameters Specification (in house) Initial Stability at 54±2 0C Stability at 0±2 0C
Pendimethalin a.i. (% w/w) 30% (±5%) 31.25 30.75 31.10
Imazethapyr a.i. (% w/w) 2% (-5%; +10%) 2.15 2.08 2.13
Diclosulam a.i. (% w/w) 1% (-5%; +10%) 1.08 1.05 1.07
pH (5% in DM water) 6.0 - 8.0 6.30 6.39 6.32
Emulsion stability (2 ml formulation in 98 ml 342 ppm hard water) Max. 2ml creaming or sediment after 1 hour 0 ml 0.1 ml 0 ml
Cold test (at 10ºC temperature) Any separation or creaming max. 2 ml after 1 hour Pass Pass Pass
Flash point (close cup) Above 24.5 0C Complies Complies Complies
Room temperature storage stability up to 12 months
Parameters Specification (in house) Initial 6 month 12 month
Pendimethalin a.i. (% w/w) 30% (±5%) 31.25 31.10 30.72
Imazethapyr a.i. (% w/w) 2% (-5%; +10%) 2.15 2.13 2.05
Diclosulam a.i. (% w/w) 1% (-5%; +10%) 1.08 1.07 1.05
pH (5% in DM water) 6.0 - 8.0 6.30 6.39 6.32
Emulsion stability (2 ml formulation in 98 ml 342 ppm hard water) Max. 2ml creaming or sediment after 1 hour 0 ml 0.1 ml 0.2 ml
Cold test (at 10 ºC temperatute) Any separation or creaming max. 2 ml after 1 hour Pass Pass Pass
Flash point Above 24.5 0C Complies Complies Complies

The composition of Pendimethalin 30%+Imazethapyr 2%+Diclosulam 1% EC meets the all in-house specifications for storage stability studies in laboratory (at 54±2 C & At 0±2 C for 14 days) and room temperature (for 12 months).

EXAMPLE 2:
Chemical composition: Pendimethalin 25%+Imazethapyr 2%+Clomazone 10% EC
Ingredients Content(%w/w)
Pendimethalin a.i. 25.00
Imazethapyr a.i. 2.00
Clomazone a.i. 10.00
Tristyrylphenol ethoxylate (Emulsifier) 5.00
Ethoxylated polysorbate and calcium salt of alkyl benzene sulfonate (Emulsifier) 5.00
N-Methyl-2-Pyrrolidone (Co-solvent) 10.00
Solvent naphtha (Solvent) 43.00
Total 100.00
a.i. (active ingredient/technical) on 100% purity basis.

Mfg process for 100 kg of Pendimethalin 25%+Imazethapyr 2%+Clomazone 10% EC
Step 1: Charge Solvent naphtha (43.00 kg), N-Methyl-2-Pyrrolidone (10.00 kg) into the vessel and then add Pendimethalin technical (25 kg), Imazethapyr technical (2 kg) and Clomazone technical (10.00 kg) slowly and mix thoroughly till it get dissolved completely.
Step 2: Now add Tristyrylphenol ethoxylate (5 kg) and Ethoxylated polysorbate and calcium salt of alkyl benzene sulfonate (5 kg) into this premix slowly and homogenised to get uniform solution.
Step 3: After getting the homogeneous solution give the sample for quality chech to QC and after approval from QC filter the material and pack in suitable container.
Storage stability-Pendimethalin 25%+Imazethapyr 2%+Clomazone 10% EC

Laboratory storage stability for 14 days
Parameters Specification (in house) Initial At 54±2 0C At 0±2 0C
Pendimethalin a.i. (% w/w) 25% (±5%) 26.12 25.86 26.10
Imazethapyr a.i. (% w/w) 2% (-5%;+10%) 2.05 2.01 2.04
Clomazone a.i. (% w/w) 10% (±5%) 10.12 10.05 10.10
pH (5% in DM water) 6.0 - 8.0 6.30 6.39 6.32
Emulsion stability (2 ml formulation in 98 ml 342 ppm hard water) Max. 2ml creaming or sediment after 1 hour 0 ml 0.1 ml 0 ml
Cold test (at 10 ºC temperatute) Any separation or creaming max. 2 ml after 1 hour Pass Pass Pass
Flash point (close cup) Above 24.5 0C Complies Complies Complies
Room temperature storage stability up to 12 months
Parameters Specification (in house) Initial 6 month 12 month
Pendimethalin a.i. (% w/w) 25% (±5%) 26.12 26.06 25.86
Imazethapyr a.i. (% w/w) 2% (-5%;+10%) 2.05 2.04 2.01
Clomazone a.i. (% w/w) 10% (±5%) 10.12 10.09 10.05
pH (5% in DM water) 6.0 - 8.0 6.30 6.34 6.41
Emulsion stability (2 ml formulation in 98 ml 342 ppm hard water) Max. 2ml creaming or sediment after 1 hour 0 ml 0.1 ml 0.2 ml
Cold test (at 10 ºC temperatute) Any separation or creaming max. 2 ml after 1 hour Pass Pass Pass
Flash point Above 24.5 0C Complies Complies Complies

The composition of Pendimethalin 25%+Imazethapyr 2%+Clomazone 10% EC meets the all in-house specifications for storage stability studies in laboratory (at 54±2 oC & at 0±2 oC for 14 days) and room temperature (for 12 months).

EXAMPLE 3:
Chemical composition: Pendimethalin 40%+Imazethapyr 4%+Oxyfluorfen 3% EC
Ingredients Content(%w/w)
Pendimethalin a.i. 40.00
Imazethapyr a.i. 4.00
Oxyfluorfen a.i. 3.00
Tristyrylphenol ethoxylate (Emulsifier) 5.00
Ethoxylated polysorbate and calcium salt of alkyl benzene sulfonate (Emulsifier) 5.00
N-Methyl-2-Pyrrolidone (Co-solvent) 3.00
Solvent naphtha (Solvent) 40.00
Total 100.00
a.i. (active ingredient/technical) on 100% purity basis.

Mfg process for 100 kg of Pendimethalin 40%+Imazethapyr 4%+Oxyfluorfen 3% EC
Step 1: Charge Solvent naphtha (40.00 kg), N-Methyl-2-Pyrrolidone (3.00 kg) into the vessel and then add Pendimethalin technical (40 kg), Imazethapyr technical (4 kg) and Clomazone technical (3.00 kg) slowly and mix thoroughly till it get dissolved completely.
Step 2: Now add Tristyrylphenol ethoxylate (5 kg) and Ethoxylated polysorbate and calcium salt of alkyl benzene sulfonate (5 kg) into this premix slowly and homogenised to get uniform solution.
Step 3: After getting the homogeneous solution give the sample for quality check to QC and after approval from QC filter the material and pack in suitable container.

The composition of Pendimethalin 40%+Imazethapyr 4%+Oxyfluorfen 3% EC meets the all in-house specifications for storage stability studies in laboratory (at 54±2 oC & at 0±2 oC for 14 days) and room temperature (for 12 months).

EXAMPLE 4:
Chemical composition: Pendimethalin 30%+Imazethapyr 3%+Metribuzin 5% EC
Ingredients Content(%w/w)
Pendimethalin a.i. 30.00
Imazethapyr a.i. 3.00
Metribuzin a.i. 5.00
Tristyrylphenol ethoxylate (Emulsifier) 5.00
Ethoxylated polysorbate and calcium salt of alkyl benzene sulfonate (Emulsifier) 5.00
N-Methyl-2-Pyrrolidone (Co-solvent) 6.00
Solvent naphtha (Solvent) 46.00
Total 100.00
a.i. (active ingredient/technical) on 100% purity basis.

Mfg process for 100 kg of Pendimethalin 30%+Imazethapyr 3%+Metribuzin 5% EC
Step 1: Charge Solvent naphtha (46.00 kg), N-Methyl-2-Pyrrolidone (6.00 kg) into the vessel and then add Pendimethalin technical (30 kg), Imazethapyr technical (3 kg) and Clomazone technical (5.00 kg) slowly and mix thoroughly till it get dissolved completely.
Step 2: Now add Tristyrylphenol ethoxylate (5 kg) and Ethoxylated polysorbate and calcium salt of alkyl benzene sulfonate (5 kg) into this premix slowly and homogenised to get uniform solution.
Step 3: After getting the homogeneous solution give the sample for quality check to QC and after approval from QC filter the material and pack in suitable container.

The composition of Pendimethalin 30%+Imazethapyr 3%+Metribuzin 5% EC meets the all in-house specifications for storage stability studies in laboratory (at 54±2 oC & at 0±2 oC for 14 days) and room temperature (for 12 months).

EXAMPLE 5:
Chemical composition-Pendimethalin 30%+Imazethapyr 2.4%+Diclosulam 1% SE (Suspo Emulsion)

Ingredients Content (%, w/w)
Pendimethalin a.i. 30.00
Imazethapyr a.i. 2.40
Diclosulam a.i. 1.00
EC Part
Dimethylformamide (solvent) 5.00
Octyl phenol ethoxylate (emulsifier) 10.00
Aromatic solvent (co-solvent) 10.00
Castor oil ethoxylate 40 moles (emulsifier) 5.00
SC Part
Copolymer butanol EO/PO (wetting agent) 1.50
Acrylic graft copolymer (dispersing agent I) 1.75
Tristyrylphenole with 16 moles EO (dispersing agent II) 2.80
Attapulgite clay (suspending agent) 0.70
Polydimethyl siloxane (antifoaming agent) 0.20
1,2- benzisothiazoline-3-one (preservative) 0.10
1,2-Propylene glycol (anti freezing agent) 4.00
Xanthan gum (thickener) 0.12
Water (diluent) 25.43
Total 100.00
a.i. (active ingredient/technical) on 100% purity basis

Manufacturing process for 100 kg of Pendimethalin 30%+Imazethapyr 2.4%+Diclosulam 1% SE (Suspo Emulsion):
Step 1: Gum Solution should be made 12-18 hour prior to use. Take required quantity of water (5 kg), biocide (0.1 kg) and homogenise, then slowly add gum powder (0.12 kg) to it and stir till complete mixing.
Step 2: Oil Phase: Charge aromatic solvent (10.00 kg), Dimethylformamide (5.00 kg) then add Pendimethalin technical (30.00 kg) and Imazethapyr technical (2.40 kg) and agitate till completely dissolution. Now add octyl phenol ethoxylate (10.00 kg) and castor oil ethoxylate (5.00 kg) with continuous stirring to get oil part ready.
Step 3: Aqueous phase: Charge 20.00 kg of water in a vessel.
Step 4: Add Copolymer butanol EO/PO (1.50 kg), Acrylic graft copolymer (1.75 kg) & Attapulgite clay (0.70 kg) and homogenise the contents for 45 – 60 minutes using high shear homogeniser.
Step 5: Then add diclosulam technical (1.00 kg) and homogenise to get uniform.
Step 6: Now add oil phase in aqueous phase and stirr for 30 minutes using homogeniser.
Step 7: Before grinding of step no. 6, half quantity of polydimethylsiloxane (0.10 kg) was added and then material was subjected to three cycles of grinding in bead mill.
Step 8: Half quantity of the polydimethylsiloxane (0.10 kg) was added along with 1, 2-Propylene glycol (4.00 kg) after grinding process completes and before sampling for in process analysis.
Step 9: Finally add gum solution (5.22 kg) to this formulation, mix well till homogeneous and Send to QC for quality check.

Storage stability-Pendimethalin 30%+Imazethapyr 2.4%+Diclosulam 1% SE (Suspo Emulsion)

Laboratory storage for 14 days
Parameters Specification (in house) Initial At 54±2 0C At 0±2 0C
Pendimethalin content percent by mass 30% (±5%) 31.15 30.75 31.05
Imazethapyr content percent by mass 2.4%(-5%;+10%) 2.45 2.41 2.45
Diclosulam content percent by mass 1% (-5%; +10%) 1.05 1.04 1.05
Pendimethalin suspensibility percent min. 80 96.25 95.12 96.11
Imazethapyr suspensibility percent min. 80 98.23 98.09 98.11
Diclosulam suspesnibility precent min. 80 97.25 97.00 97.22
pH range (1% aq. Suspension) 5.0 to 9.0 5.20 5.70 5.25
Pourability 95% min. 98.70 98.50 98.60
Specific gravity 1.00-1.10 1.07 1.07 1.07
Viscosity at spindle no. 62, 20 rpm 350-800 cps 425 415 430
Particle size (micron) D50<3, D90<10 5.7 6.4 5.8
Persistent foam ml (after 1 minute) max. 60 20 25 19
Room temperature storage
Parameters Specification (in house) 1 month 6 month 12 month
Pendimethalin content percent by mass 30% (±5%) 31.15 31.05 30.70
Imazethapyr content percent by mass 2.4%(-5%; +10%) 2.45 2.43 2.42
Diclosulam content percent by mass 1% (-5%; +10%) 1.06 1.03 1.02
Pendimethalin suspensibility percent min. 80 96.22 96.19 95.61
Imazethapyr suspensibility percent min. 80 98.20 98.15 97.75
Diclosulam suspesnibility precent min. 80 97.21 97.23 96.89
pH range (1% aq. Suspension) 7.0 to 10.0 5.22 5.27 5.29
Pourability 95% min. 98.69 98.77 98.61
Specific gravity 1.00-1.10 1.07 1.07 1.07
Viscosity at spindle no. 62, 20 rpm 350-800 cps 427 430 433
Particle size (micron) D50<3, D90<10 5.77 6.11 6.89
Persistent foam ml (after 1 minute) max. 60 20 20 20

The composition of Pendimethalin 30%+Imazethapyr 2.4%+Diclosulam 1% SE (Suspo Emulsion) meets the all in-house specifications for storage stability studies in laboratory (at 54±2 C & at 0±2 C for 14 days) and room temperature (for 12 months).

EXAMPLE 6:
Pendimethalin 25%+Imazethapyr 2%+Sulfentrazone 10% SE (Suspo Emulsion)
Ingredients Content (%, w/w)
Pendimethalin a.i. 25.00
Imazethapyr a.i. 2.00
Sulfentrazone a.i. 10.00
EC Part
Dimethylformamide (solvent) 5.00
Octyl phenol ethoxylate (emulsifier) 10.00
Aromatic solvent (co-solvent) 10.00
Castor oil ethoxylate 40 moles (emulsifier) 5.00
SC Part
Copolymer butanol EO/PO (wetting agent) 1.50
Acrylic graft copolymer (dispersing agent I) 1.75
Tristryphenole with 16 moles EO (dispersing agent II) 2.80
Attapulgite clay (suspending agent) 0.70
Polydimethyl siloxane (antifoaming agent) 0.20
1,2- benzisothiazoline-3-one (preservative) 0.10
1,2-Propylene glycol (anti freezing agent) 4.00
Xanthan gum (thickener) 0.12
Water (diluent) 21.83
Total 100.00
a.i. (active ingredient/technical) on 100% purity basis

Manufacturing process for 100 kg of Pendimethalin 25%+Imazethapyr 2%+Sulfentrazone 10% SE (Suspo Emulsion):
Step 1: Gum Solution should be made 12-18 hour prior to use. Take required quantity of water (5 kg), biocide (0.1 kg) and homogenise, then slowly add gum powder (0.12 kg) to it and stir till complete mixing.
Step 2: Oil Phase: Charge aromatic solvent (10.00 kg), Dimethylformamide (5.00 kg) then add Pendimethalin technical (25.00 kg) and Imazethapyr technical (2.00 kg) and agitate till completely dissolution. Now add octyl phenol ethoxylate (10.00 kg) and castor oil ethoxylate (5.00 kg) with continuous stirring to get oil part ready.
Step 3: Aqueous phase: Charge 20.00 kg of water in a vessel.
Step 4: Add Copolymer butanol EO/PO (1.50 kg), Acrylic graft copolymer (1.75 kg) & Attapulgite clay (0.70 kg) and homogenise the contents for 45 – 60 minutes using high shear homogeniser.
Step 5: Then add Sulfentrazone technical (10.00 kg) and homogenise to get uniform slurry.
Step 6: Now add oil phase in aqueous phase and stirr for 30 minutes using homogeniser.
Step 7: Before grinding of step no. 6, half quantity of polydimethylsiloxane (0.10 kg) was added and then material was subjected to three cycles of grinding in bead mill.
Step 8: Half quantity of the polydimethylsiloxane (0.10 kg) was added along with 1,2-Propylene glycol (4.00 kg) after grinding process completes and before sampling for in process analysis.
Step 9: Finally add gum solution (5.22 kg) to this formulation, mix well till homogeneous and Send to QC for quality check.

Storage stability-Pendimethalin 25%+Imazethapyr 2%+Sulfentrazone 10% SE (Suspo Emulsion)

Laboratory storage for 14 days
Parameters Specification (in house) Initial At 54±2 0C At 0±2 0C
Pendimethalin content percent by mass 20% (±5%) 20.42 20.39 20.41
Imazethapyr content percent by mass 2%(-5%; +10%) 2.15 2.11 2.15
Sulfentrazone content percent by mass 10% (±5%) 10.15 10.14 10.15
Pendimethalin suspensibility percent min. 80 95.25 94.12 95.11
Imazethapyr suspensibility percent min. 80 98.23 98.09 98.11
Sulfentrazone suspesnibility precent min. 80 97.25 97.00 97.22
pH range (1% aq. Suspension) 5.0 to 9.0 5.41 5.52 5.25
Pourability 95% min. 98.71 98.59 98.62
Specific gravity 1.10-1.20 1.15 1.15 1.15
Viscosity at spindle no. 62, 20 rpm 350-800 cps 423 419 432
Particle size (micron) D50<3, D90<10 5.81 6.42 5.79
Persistent foam ml (after 1 minute) max. 60 20 25 22
Room temperature storage
Parameters Specification (in house) 1 month 6 months 12 months
Pendimethalin content percent by mass 20% (±5%) 20.41 20.38 20.32
Imazethapyr content percent by mass 2% (-5%;+10%) 2.13 2.12 2.10
Sulfentrazone content percent by mass 10% (±5%) 10.11 10.10 10.08
Pendimethalin suspensibility percent min. 80 95.22 95.19 94.19
Imazethapyr suspensibility percent min. 80 98.19 98.16 97.23
Sulfentrazone suspesnibility precent min. 80 97.23 97.11 96.09
pH range (1% aq. Suspension) 7.0 to 10.0 5.43 5.42 5.45
Pourability 95% min. 98.69 98.61 98.59
Specific gravity 1.00-1.10 1.15 1.15 1.15
Viscosity at spindle no. 62, 20 rpm 350-800 cps 427 425 455
Particle size (micron) D50<3, D90<10 5.89 5.85 6.75
Persistent foam ml (after 1 minute) max. 60 20 20 20

The composition of Pendimethalin 25%+Imazethapyr 2%+Sulfentrazone 10% SE (Suspo Emulsion) meets the all inhouse specifications for storage stability studies in laboratory (at 54±2 0C & at 0±2 0C for 14 days) and room temperature (for 12 months).
EXAMPLE 7:
Chemical composition-Pendimethalin 30%+Imazethapyr 2.4%+Diclosulam 1% SE (Suspo Emulsion)

Ingredients Content (%, w/w)
Pendimethalin a.i. 30.00
Imazethapyr a.i. 2.40
Diclosulam a.i. 1.00
EC Part
Dimethylformamide (solvent) 5.00
Octyl phenol ethoxylate (emulsifier) 10.00
Aromatic solvent (co-solvent) 10.00
Castor oil ethoxylate 40 moles (emulsifier) 5.00
SC Part
Copolymer butanol EO/PO (wetting agent) 1.50
Acrylic graft copolymer (dispersing agent I) 1.75
Tristyrylphenole with 16 moles EO (dispersing agent II) 2.80
Attapulgite clay (suspending agent) 0.70
Polydimethyl siloxane (antifoaming agent) 0.20
1,2- benzisothiazoline-3-one (preservative) 0.10
1,2-Propylene glycol (anti freezing agent) 4.00
Xanthan gum (thickener) 0.12
Water (diluent) 25.43
Total 100.00
a.i. (active ingredient/technical) on 100% purity basis

Manufacturing process for 100 kg of Pendimethalin 30%+Imazethapyr 2.4%+Diclosulam 1% SE (Suspo Emulsion):
Step 1: Gum Solution should be made 12-18 hour prior to use. Take required quantity of water (5 kg), biocide (0.1 kg) and homogenise, then slowly add gum powder (0.12 kg) to it and stir till complete mixing.
Step 2: Oil Phase: Charge aromatic solvent (10.00 kg), Dimethylformamide (5.00 kg) then add Pendimethalin technical (30.00 kg) and Imazethapyr technical (2.40 kg) and agitate till completely dissolution. Now add octyl phenol ethoxylate (10.00 kg) and castor oil ethoxylate (5.00 kg) with continuous stirring to get oil part ready.
Step 3: Aqueous phase: Charge 20.00 kg of water in a vessel.
Step 4: Add Copolymer butanol EO/PO (1.50 kg), Acrylic graft copolymer (1.75 kg) & Attapulgite clay (0.70 kg) and homogenise the contents for 45 – 60 minutes using high shear homogeniser.
Step 5: Then add diclosulam technical (1.00 kg) and homogenise to get uniform.
Step 6: Now add oil phase in aqueous phase and stirr for 30 minutes using homogeniser.
Step 7: Before grinding of step no. 6, half quantity of polydimethylsiloxane (0.10 kg) was added and then material was subjected to three cycles of grinding in bead mill.
Step 8: Half quantity of the polydimethylsiloxane (0.10 kg) was added along with 1, 2-Propylene glycol (4.00 kg) after grinding process completes and before sampling for in process analysis.
Step 9: Finally add gum solution (5.22 kg) to this formulation, mix well till homogeneous and Send to QC for quality check.

Storage stability-Pendimethalin 30%+Imazethapyr 2.4%+Diclosulam 1% SE (Suspo Emulsion)

Laboratory storage for 14 days
Parameters Specification (in house) Initial At 54±2 0C At 0±2 0C
Pendimethalin content percent by mass 30% (±5%) 31.15 30.75 31.05
Imazethapyr content percent by mass 2.4%(-5%;+10%) 2.45 2.41 2.45
Diclosulam content percent by mass 1% (-5%; +10%) 1.05 1.04 1.05
Pendimethalin suspensibility percent min. 80 96.25 95.12 96.11
Imazethapyr suspensibility percent min. 80 98.23 98.09 98.11
Diclosulam suspesnibility precent min. 80 97.25 97.00 97.22
pH range (1% aq. Suspension) 5.0 to 9.0 5.20 5.70 5.25
Pourability 95% min. 98.70 98.50 98.60
Specific gravity 1.00-1.10 1.07 1.07 1.07
Viscosity at spindle no. 62, 20 rpm 350-800 cps 425 415 430
Particle size (micron) D50<3, D90<10 5.7 6.4 5.8
Persistent foam ml (after 1 minute) max. 60 20 25 19
Room temperature storage
Parameters Specification (in house) 1 month 6 month 12 month
Pendimethalin content percent by mass 30% (±5%) 31.15 31.05 30.70
Imazethapyr content percent by mass 2.4%(-5%; +10%) 2.45 2.43 2.42
Diclosulam content percent by mass 1% (-5%; +10%) 1.06 1.03 1.02
Pendimethalin suspensibility percent min. 80 96.22 96.19 95.61
Imazethapyr suspensibility percent min. 80 98.20 98.15 97.75
Diclosulam suspesnibility precent min. 80 97.21 97.23 96.89
pH range (1% aq. Suspension) 7.0 to 10.0 5.22 5.27 5.29
Pourability 95% min. 98.69 98.77 98.61
Specific gravity 1.00-1.10 1.07 1.07 1.07
Viscosity at spindle no. 62, 20 rpm 350-800 cps 427 430 433
Particle size (micron) D50<3, D90<10 5.77 6.11 6.89
Persistent foam ml (after 1 minute) max. 60 20 20 20

The composition of Pendimethalin 30%+Imazethapyr 2.4%+Diclosulam 1% SE (Suspo Emulsion) meets the all in-house specifications for storage stability studies in laboratory (at 54±2 C & at 0±2 C for 14 days) and room temperature (for 12 months).

EXAMPLE 8:
Pendimethalin 45%+Imazethapyr 6%+Diclosulam 1.6% SE (Suspo Emulsion)
Ingredients Content (%, w/w)
Pendimethalin a.i. 45.00
Imazethapyr a.i. 6.00
Diclosulam a.i. 1.60
EC Part
Dimethylformamide (solvent) 5.00
Octyl phenol ethoxylate (emulsifier) 10.00
Aromatic solvent (co-solvent) 10.00
Castor oil ethoxylate 40 moles (emulsifier) 5.00
SC Part
Copolymer butanol EO/PO (wetting agent) 1.50
Acrylic graft copolymer (dispersing agent I) 1.75
Tristryphenole with 16 moles EO (dispersing agent II) 2.80
Attapulgite clay (suspending agent) 0.70
Polydimethyl siloxane (antifoaming agent) 0.20
1,2- benzisothiazoline-3-one (preservative) 0.10
1,2-Propylene glycol (anti freezing agent) 4.00
Xanthan gum (thickener) 0.12
Water (diluent) 6.23
Total 100.00
a.i. (active ingredient/technical) on 100% purity basis

Manufacturing process for 100 kg of Pendimethalin 45%+Imazethapyr 6%+Diclosulam 1.6% SE (Suspo Emulsion):
Step 1: Gum Solution should be made 12-18 hour prior to use. Take required quantity of water (6.23 kg), biocide (0.1 kg) and homogenise, then slowly add gum powder (0.12 kg) to it and stir till complete mixing.
Step 2: Oil Phase: Charge aromatic solvent (10.00 kg), Dimethylformamide (5.00 kg) then add Pendimethalin technical (45.00 kg) and Imazethapyr technical (6.00 kg) and agitate till completely dissolution. Now add octyl phenol ethoxylate (10.00 kg) and castor oil ethoxylate (5.00 kg) with continuous stirring to get oil part ready.
Step 3: Aqueous phase: Charge 20.00 kg of water in a vessel.
Step 4: Add Copolymer butanol EO/PO (1.50 kg), Acrylic graft copolymer (1.75 kg) & Attapulgite clay (0.70 kg) and homogenise the contents for 45 – 60 minutes using high shear homogeniser.
Step 5: Then add Diclosulam technical (1.60 kg) and homogenise to get uniform slurry.
Step 6: Now add oil phase in aqueous phase and stirr for 30 minutes using homogeniser.
Step 7: Before grinding of step no. 6, half quantity of polydimethylsiloxane (0.10 kg) was added and then material was subjected to three cycles of grinding in bead mill.
Step 8: Half quantity of the polydimethylsiloxane (0.10 kg) was added along with 1,2-Propylene glycol (4.00 kg) after grinding process completes and before sampling for in process analysis.
Step 9: Finally add gum solution (5.22 kg) to this formulation, mix well till homogeneous and Send to QC for quality check.

The composition of Pendimethalin 45%+Imazethapyr 6%+Diclosulam 1.6% SE (Suspo Emulsion) meets the all in-house specifications for storage stability studies in laboratory (at 54±2 C & at 0±2 C for 14 days) and room temperature (for 12 months).

EXAMPLE 9:
Chemical composition-Pendimethalin 30%+Imazethapyr 2%+Chlorimuron ethyl 0.4% ZC
Ingredients Content (%, w/w)
Pendimethalin a.i. 30.00
Imazethapyr a.i. 2.00
Chlorimuron ethyl a.i. 0.40
Sodium Isopropyl Naphthalene Sulfonate (wetting agent) 2.00
Alkyl phenyl polyglycol ether (dispersing agent I) 2.50
Alkyl napthalene sulfonate condensate (dispersing agent II) 0.50
Polymethylene polyphenylene isocyanate (wall forming material I) 0.50
Diethylenetriamine (wall forming material II) 0.25
Tributyl phenyl polyglycol ether (suspending agent) 1.50
Polydimethylsiloxane (antifoaming agnet) 0.30
Sulphuric acid (buffering agent) 0.50
1,2-benzisothiazolin-3(2H)-one (preservative) 0.20
Mono ethylene glycol (antifreezing agent) 5.00
Xanthan gum (thickener) 0.15
Water (diluent) 54.20
Total 100.00
a.i. (active ingredient/technical) on 100% purity basis

Manufacturing process for 100 kg of Pendimethalin 30%+Imazethapyr 2%+Chlorimuron ethyl 0.4% ZC:
Part A: Preparation of CS (Capsule Suspension) formulation
Step 1: Aqueous Phase-Charge water to a stainless-steel vessel equipped with a high speed stirrer. Under agitation, add Sodium Isopropyl Naphthalene Sulfonate (1.00 kg), Alkyl phenyl polyglycol ether (1.25 kg) and Alkyl napthalene sulfonate condensate (0.50 kg) into the vessel. Now add 50% quantity of antifoam to avoid foam generation in this vessel.
Step 2: Organic Phase-Charge Pendimethalin technical (30.00 kg) into second stainless-steel reactor and melt it. Afterwards, charge Polymethylene polyphenylene isocyanate (0.50 kg) to the reactor. Mix well.
Step 3: Start the high shear disperser of aqueous phase and charge the ‘Organic Solution’ into the ‘Aqueous Phase Solution’ under gravity in specific rate so that required particle size can be achieved and continue to shear for 30 min. Then, start heating the reactor to around 50 °C and stir the formulation under slow rpm for 3-4 hours so that Polymerization reaction gets completed.
Step 4: Now add Diethylenetriamine (0.25 kg) so that residual wall forming material 1 can be consumed and stir for 1 more hour at the same temperature and if required add half quantity of antifoam to remove foam generating due to CO2 during reaction.
Step 5: After the wall polymerization reaction, increase the agitator to high speed. Add the rest half quantity of antifoam to the formulation. Under slight vacuum, allow the mixture to de-gas for approximately 30 minutes to remove CO2 from the solution. Add the Xanthan gum (0.15 kg), 1,2-benzisothiazolin-3(2H)-one (0.10 kg) and in last Mono ethylene glycol (5.00 kg) and mix for some minutes. Add Sulphuric acid (0.50 kg) for pH adjustment. Check the formulation to specifications.

Part B: Preparation of SC (Suspension Concentrate) formulation
Step 1: 2% Gel Preparation: Charge the required quantity of water to a vessel, equipped with a high shear stirrer and start the agitation. Add 1,2-benzisothiazolin-3(2H)-one (0.10 kg). Mix until homogenous. Add the required amount of thickener and mix vigorously until it is fully wetted.
Step 2: SC Premix- Charge the required quantity of water to a vessel, equipped with bulk agitator and a high shear homogenizer and start agitation. Add Mono ethylene glycol (2.50 kg) and mix until uniform. Add the antifoaming agent and ensure that it is well dispersed. Add Sodium Isopropyl Naphthalene Sulfonate (1.00 kg) and Alkyl phenyl polyglycol ether (1.25 kg) and mix until uniform.
Step 3: Now add the Imazethapyr (2.00 kg) and Chlorimuron ethyl (0.40 kg) and continue agitating the vessel contents until all components get homogenized. Mill this pre-mix through a Colloid mill and subsequently through a Dyno mill to meet the specified particle size.
Now add remaining antifoaming agent to this SC mill base to a vessel, equipped with bulk agitator. Mix until uniform. Add the required amount of 2% aqueous pre-gel and continue agitation until the formulation is homogeneous and has the target viscosity. Mix well.

Part C: Preparation of ZC Formulation
Step 1: Charge the required quantity of SC formulation into a vessel, equipped with bulk agitator and start agitation. Add the CS Premix to this slurry and mix slowly until uniform. Add the required amount of 2% pre-gel and continue agitation until the formulation is homogeneous and a target viscosity of around 600-800 m cPs is reached. Mix well.
Step 2: Final product is sent for QC approval.
Step 3: After approval, material is packed in required pack sizes.
Storage stability-Pendimethalin 30%+Imazethapyr 2%+Chlorimuron ethyl 0.4% ZC

Laboratory storage for 14 days
Parameters Specification (in house) Initial At 54±2 0C At 0±2 0C
Pendimethalin content percent by mass 30% (±5%) 31.27 31.23 31.26
Imazethapyr content percent by mass 2% (-5%;+10%) 2.16 2.11 2.15
Chlorimuron ethyl content percent by mass 0.4% (-5%;+10%) 0.44 0.43 0.44
Pendimethalin suspensibility percent min. 80 94.8 93.72 94.71
Imazethapyr suspensibility percent min. 80 97.12 96.6 97.2
Chlorimuron ethyl suspensibility precent min. 80 95.05 94.5 95.2
pH range (1% aq. Suspension) 5 to 9 7.20 7.25 7.21
Pourability 95% min. 97.52 97.11 97.43
Specific gravity 1.05-1.10 1.07 1.07 1.07
Viscosity at spindle no. 62, 20 rpm 350-800 cps 480 475 492
Particle size (micron) D50<3, D90<10 2.2,8.1 2.4,8.7 2.1,8.2
Persistent foam ml (after 1 minute) max. 60 10 15 10
Room temperature storage
Parameters Specification (in house) 1 month 6 month 12 month
Pendimethalin content percent by mass 30% (±5%) 31.27 31.20 31.05
Imazethapyr content percent by mass 2% (-5%;+10%) 2.16 2.14 2.13
Chlorimuron ethyl content percent by mass 0.4% (-5%;+10%) 0.44 0.43 0.42
Pendimethalin suspensibility percent min. 80 94.78 94.7 94.1
Imazethapyr suspensibility percent min. 80 96.98 96.9 95.3
Chlorimuron ethyl suspensibility precent min. 80 95.02 94.8 94.5
pH range (1% aq. Suspension) 5 to 9 7.23 7.2 7.4
Pourability 95% min. 97.49 97.4 97.1
Specific gravity 1.05-1.10 1.07 1.07 1.07
Viscosity at spindle no. 62, 20 rpm 350-800 cps 483 480 492
Particle size (micron) D50<3, D90<10 2.3,8.2 2.2, 8.3 2.3, 8.5
Persistent foam ml (after 1 minute) max. 60 10 10 10

The composition of Pendimethalin 30%+Imazethapyr 2%+Chlorimuron ethyl 0.4% ZC meets the all in-house specifications for storage stability studies in laboratory (at 54±2 0C & At 0±2 0C for 14 days) and room temperature (for 12 months).

EXAMPLE 10:
Chemical composition- Pendimethalin 20%+Imazethapyr 5%+Sulfentrazone 15% ZC
Ingredients Content (%, w/w)
Pendimethalin a.i. 20.00
Imazethapyr a.i. 5.00
Sulfentrazone a.i. 15.00
Sodium Isopropyl Naphthalene Sulfonate (wetting agent) 2.00
Alkyl phenyl polyglycol ether (dispersing agent I) 2.50
Alkyl napthalene sulfonate condensate (dispersing agent II) 0.50
Polymethylene polyphenylene isocyanate (wall forming material I) 0.50
Diethylenetriamine (wall forming material II) 0.25
Tributyl phenyl polyglycol ether (suspending agent) 1.50
Polydimethylsiloxane (antifoaming agnet) 0.30
Sulphuric acid (buffering agent) 0.50
1,2-benzisothiazolin-3(2H)-one (preservative) 0.20
Mono ethylene glycol (antifreezing agent) 5.00
Xanthan gum (thickener) 0.15
Water (diluent) 46.60
Total 100.00
a.i. (active ingredient/technical) on 100% purity basis

Manufacturing process for 100 kg of Pendimethalin 20%+Imazethapyr 5%+Sulfentrazone 15% ZC:
Part A: Preparation of CS (Capsule Suspension) formulation
Step 1: Aqueous Phase-Charge water to a stainless-steel vessel equipped with a high speed stirrer. Under agitation, add Sodium Isopropyl Naphthalene Sulfonate (1.00 kg), Alkyl phenyl polyglycol ether (1.25 kg) and Alkyl napthalene sulfonate condensate (0.50 kg) into the vessel. Now add 50% quantity of antifoam to avoid foam generation in this vessel.
Step 2: Organic Phase-Charge Pendimethalin technical (20.00 kg) into second stainless-steel reactor and melt it. Afterwards, charge Polymethylene polyphenylene isocyanate (0.50 kg) to the reactor. Mix well.
Step 3: Start the high shear disperser of aqueous phase and charge the ‘Organic Solution’ into the ‘Aqueous Phase Solution’ under gravity in specific rate so that required particle size can be achieved and continue to shear for 30 min. Then, start heating the reactor to around 50 °C and stir the formulation under slow rpm for 3-4 hours so that Polymerization reaction gets completed.
Step 4: Now add Diethylenetriamine (0.25 kg) so that residual wall forming material 1 can be consumed and stir for 1 more hour at the same temperature and if required add half quantity of antifoam to remove foam generating due to CO2 during reaction.
Step 5: After the wall polymerization reaction, increase the agitator to high speed. Add the rest half quantity of antifoam to the formulation. Under slight vacuum, allow the mixture to de-gas for approximately 30 minutes to remove CO2 from the solution. Add the Xanthan gum (0.15 kg), 1,2-benzisothiazolin-3(2H)-one (0.10 kg) and in last Mono ethylene glycol (5.00 kg) and mix for some minutes. Add Sulphuric acid (0.50 kg) for pH adjustment. Check the formulation to specifications.

Part B: Preparation of SC (Suspension Concentrate) formulation
Step 1: 2% Gel Preparation: Charge the required quantity of water to a vessel, equipped with a high shear stirrer and start the agitation. Add 1,2-benzisothiazolin-3(2H)-one (0.10 kg). Mix until homogenous. Add the required amount of thickener and mix vigorously until it is fully wetted.
Step 2: SC Premix- Charge the required quantity of water to a vessel, equipped with bulk agitator and a high shear homogenizer and start agitation. Add Mono ethylene glycol (2.50 kg) and mix until uniform. Add the antifoaming agent and ensure that it is well dispersed. Add Sodium Isopropyl Naphthalene Sulfonate (1.00 kg) and Alkyl phenyl polyglycol ether (1.25 kg) and mix until uniform.
Step 3: Now add the Imazethapyr (5.00 kg) and Sulfentrazone (15.00 kg) and continue agitating the vessel contents until all components get homogenized. Mill this pre-mix through a Colloid mill and subsequently through a Dyno mill to meet the specified particle size.
Now add remaining antifoaming agent to this SC mill base to a vessel, equipped with bulk agitator. Mix until uniform. Add the required amount of 2% aqueous pre-gel and continue agitation until the formulation is homogeneous and has the target viscosity. Mix well.

Part C: Preparation of ZC Formulation
Step 1: Charge the required quantity of SC formulation into a vessel, equipped with bulk agitator and start agitation. Add the CS Premix to this slurry and mix slowly until uniform. Add the required amount of 2% pre-gel and continue agitation until the formulation is homogeneous and a target viscosity of around 600-800 m cPs is reached. Mix well.
Step 2: Final product is sent for QC approval.
Step 3: After approval, material is packed in required pack sizes.

The composition of Pendimethalin 20%+Imazethapyr 5%+Sulfentrazone 15% ZC meets the all in-house specifications for storage stability studies in laboratory (at 54±2 0C & At 0±2 0C for 14 days) and room temperature (for 12 months).

EXAMPLE 11:
Chemical composition-Pendimethalin 24%+Imazethapyr 2.4%+Pyroxasulfone 6% OD
Ingredients Content (%, w/w)
Pendimethalin a.i. 24.00
Imazethapyr a.i. 2.40
Pyroxasulfone a.i. 6.00
Tristyrylphenol-polyglycolether-phosphate (dispersing agent) 4.50
Calcium salts of dodecylbenzene sulphonate (emulsifying agent) 8.00
Organo clay (stabilizer) 2.00
Polydimethyl siloxane (antifoaming agent) 0.30
Polypropylene glycol (antifreezing agent) 5.00
Polyalkyleneoxide modified Heptamethyltrisiloxane (wetting agent) 5.00
Methyl ester of Palm oil or soybean oil (carrier or solvent) 42.80
Total 100.00
a.i. (active ingredient/technical) on 100% purity basis

Manufacturing process for 100 kg of Pendimethalin 24%+Imazethapyr 2.4%+Pyroxasulfone 6% OD:
Step 1: Charge 42.80 kg of Methyl ester of Palm oil or soyabean oil into a designated vessel for OD production.
Step 2: Now add Tristyrylphenol-polyglycolether-phosphate (4.50 kg), Calcium salts of dodecylbenzene sulphonate (8.00 kg), Polypropylene glycol (5.00 kg), and Polydimethyl siloxane (0.30 kg) homogenise the contents for 45 – 60 minutes using high shear homogeniser.
Step 3: Add Pendimethalin technical (24.00 kg), Imazethapyr technical (2.40 kg) and Pyroxasulfone technical (6.00 kg) into above premix and homogenized for 30-45 minutes.
Step 4: Now, mill the above prepared slurry using a suitable colloidal mill or using dyno mill till the required particle size achieved.
Step 5: After achieving the required particle size discharge the material into final vessel and add organo clay (2.00 kg) and mix till homogeneous.
Step 6: Send this final formulation to QC for quality check.

Storage stability- Pendimethalin 24%+Imazethapyr 2.4%+Pyroxasulfone 6% OD

Laboratory storage for 14 days
Parameters Specification (in house) Initial At 54±2 0C At 0±2 0C
Pendimethalin content percent by mass 24% (±5%) 24.30 24.28 24.31
Imazethapyr content percent by mass 2.4% (-5%;+10%) 2.45 2.42 2.44
Pyroxasulfone content percent by mass 6% (-5%;+10%) 6.10 6.08 6.11
Pendimethalin suspensibility percent min. 80 97.53 96.72 97.49
Imazethapyr suspensibility percent min. 80 98.21 97.36 98.19
Pyroxasulfone suspensibility percent min. 80 97.86 97.12 97.79
pH range (1% aq. Suspension) 5.0 to 7.5 6.00 6.05 6.00
Pourability (Rinsed Residue) 4% Max. 9.87 98.60 99.80
Specific gravity 0.97-1.05 1.01 1.01 1.01
Viscosity at spindle no. 62, 20 rpm 350-800 cps 570 590 610
Particle size (micron) D50<3, D90<10 2.2,8.7 2.4,8.9 2.5,8.9
Persistent foam ml (after 1 minute) max. 60 nil 2 nil
Room temperature storage
Parameters Specification (in house) 1 month 6 months 12 months
Pendimethalin content percent by mass 24% (±5%) 24.29 24.27 24.25
Imazethapyr content percent by mass 2.4% (-5%;+10%) 2.44 2.44 2.42
Pyroxasulfone content percent by mass 6% (-5%;+10%) 6.09 6.06 6.02
Pendimethalin suspensibility percent min. 80 97.59 96.69 95.12
Imazethapyr suspensibility percent min. 80 98.18 97.10 96.02
Pyroxasulfone suspensibility percent min. 80 97.45 96.74 95.79
pH range (1% aq. Suspension) 5.0 to 7.5 6.05 6.08 6.12
Pourability (Rinsed Residue) 4% Max. 9.87 98.60 99.80
Specific gravity 0.97-1.05 1.01 1.01 1.01
Viscosity at spindle no. 62, 20 rpm 350-800 cps 570 590 610
Particle size (micron) D50<3, D90<10 2.2,8.7 2.4,8.9 2.5,8.9
Persistent foam ml (after 1 minute) max. 60 nil 2 nil

The composition of Pendimethalin 24%+Imazethapyr 2.4%+Pyroxasulfone 6% OD meets the all in-house specifications for storage stability studies in laboratory (at 54±2 C & at 0±2 C for 14 days) and room temperature (for 12 months).

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) or tank 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 or three active components can be calculated as follows:

Field studies have been carried out to judge synergism and its effect on crops.

Example 1: Weed control in Groundnut crop.
Crop : Groundnut
Location : Junagadh, Gujarat
Number of Treatments: 11 including untreated check.
Plot size : 40 sq.m. (m2)
Application time : 1 day after sowing (pre-emergence)
Method of application: Blanket spray over the soil with backpack sprayer fitted with 2 nozzle booms.
Water volume : 500 liter per hectare
Observation Methods:
Phytotoxicity: The observations on crop safety i.e. phytotoxicity or adverse effect of treatments were recorded for symptoms visible. All the visual phytotoxicity symptoms like plant yellowing, leaf scorching, bleaching, necrosis, stunting, crinkling, epinasty, hyponasty recorded on the basis of entire plot in comparison with untreated control (UTC) plot. Each individual visual symptom were recorded on the basis severity of injury i.e. from 0 to 100%.

Weed count: Species wise count of weed was recorded using a quadrat of size 50cm x 50 cm (0.25 m2). Observations were recorded by placing the quadrat randomly in the experimental plots at 15 and 30 DAS (Days after sowing). Recorded the observations from 5 spots per plot. Calculated total weed control (grasses, broad leaf and sedges) as per give formula;

Table 1: Treatment details
Treatment number Treatment details Application Rate (gai/h)
T1 pendimethalin 30%+imazethapyr 2.4%+diclosulam 1% SE 750+60+25
T2 pendimethalin 30%+imazethapyr 2%+diclosulam 1% EC 750+50+25
T3 pendimethalin 30%+imazethapyr 2% EC (ready mix) 750+60
T4 pendimethalin 30%+diclosulam 1% SE (ready mix) 750+25
T5 imazethapyr 2.4%+diclosulam 1% SE (ready mix) 60+25
T6 imazethapyr 2%+diclosulam 1% EC (ready mix) 50+25
T7 pendimethalin 30% EC 750
T8 Imazethapyr 70% WG 60
T9 Imazethapyr 70% WG 50
T10 diclosulam 84% WG 25
T11 Untreated Control (UTC) 0

SE suspo emulsion, EC emulsifiable concentrate, WG water dispersible granule/wettable granule. T1 & T2: present compositions, T3-T6: known composition/prior art.

Table 2: Weed control in ground nut.
Treatment number % Weed control
15 DAS 30 DAS
Observed Expected Colby's ratio Synergism (Y/N) OV EV Colby's ratio Synergism (Y/N)
T1 100.0 94.05 1.06 Y 99.0 89.26 1.11 Y
T2 100.0 93.51 1.07 Y 97.8 87.63 1.12 Y
T3 88.4 87.50 1.01 Y 74.8 81.23 0.92 N
T4 87.2 85.05 1.03 Y 73.8 77.35 0.95 N
T5 81.8 81.06 1.01 Y 68.6 72.89 0.94 N
T6 80.6 79.34 1.02 Y 67.4 68.77 0.98 N
T7 68.6 60.4
T8 60.2 52.6
T9 56.6 45.4
T10 52.4 42.8
T11 0.0 0.0

Weed flora composition: Grassy weeds (approx.60%)-Echinochloa colonum, Eragrostis minor, Dactyloctenium aegyptium; Broad leaf weeds (approx. 35%)-Trainthema portulacastrum, Digera arvensis, Phyllanthus niruri; Sedges (approx. 5%) - Cyperus rotundus.

Both the present compositions (T1 & T2) provide synergistic control as well as residual control up to 30 DAS as compared to all known compositions (T3-T6) and market products (T7-T10). Both the present compositions (T1 & T2) depict Colby’s ratio >1 which means stronger synergism.
All the treatments (T1-T10) found safe to groundnut crop and does not cause any adverse effects on growth.

Example 2: Weed control in soybean crop.
Crop : Soybean
Location : Ujjain, Madhya Pradesh
Number of Treatments: 12, including untreated check.
Plot size : 50 m2
Application time : Immediately after seed sowing (pre-emergence)
Method of application: Blanket spray over the soil with backpack sprayer fitted with 2 nozzle boom.
Water volume : 500 liter per hectare
Observation Methods: as per Example 1.

Table 3: Treatment details.
Treatment number Treatment details Application Rate (gai/h)
T1 pendimethalin 25%+imazethapyr 2%+sulfentrazone 10% SE 625+50+250
T2 pendimethalin 25%+imazethapyr 2%+clomazone 10% EC 625+50+250
T3 pendimethalin 30%+imazethapyr 2% EC (ready mix) 625+50
T4 pendimethalin 30% EC+sulfentrazone 39.6% SC (tank mix) 625+250
T5 pendimethalin 30% EC+clomazone 50% EC (tank mix) 625+250
T6 imazethapyr 70% WG+sulfentrazone 39.6% SC (tank mix) 625+250
T7 imazethapyr 70% WG+clomazone 50% EC (tank mix) 625+250
T8 pendimethalin 30% EC 625
T9 Imazethapyr 70% WG 50
T10 sulfentrazone 39.6% SC 250
T11 clomazone 50% EC 250
T12 Untreated Control (UTC) 0
T1 & T2: present compositions, T3: known composition, T4-T7: tank mixes

Table 4: Weed control in soybean crop.
Treatment number % Weed control at
15 DAS 30 DAS
Observed Expected Colby's ratio Observed Expected Colby's ratio
T1 99.2 94.02 1.06 97.8 86.81 1.13
T2 98.6 93.54 1.05 95.6 85.46 1.12
T3 86.2 85.19 1.01 65.4 71.82 0.91
T4 85.4 84.97 1.01 70.6 75.76 0.93
T5 84.4 83.78 1.01 68.2 73.27 0.93
T6 85.0 83.92 1.01 78.4 74.54 1.05
T7 83.2 82.65 1.01 73.0 71.93 1.01
T8 62.8 48.2
T9 60.2 45.6
T10 59.6 53.2
T11 56.4 48.4
T12 0.0 0.0

Weed flora composition: Grassy weeds (approx.30%)-Echinochloa colonum, Ischaemum rugosuam, Dinebra ratroflexa,; Broad leaf weeds (approx.70%)-Commelina benghalensis, Commelina communis, Acalypha indica, Digera arvensis.

Both the present compositions (T1 & T2) provide synergistic weed control on 15 and 30 DAS.as well as residual control up to 30 DAA. Both, T1 & T2 founds highly effective (>95% control on 30) against all type of weeds, especially broad leaf weeds, which are dominating the trial plot.
The visual observations show all the treatments (T1-T10) found safe to soybean crop and does not cause any adverse effects on growth.

Example 3: Weed control in soybean crop.
Crop : Soybean
Location : Amaravati, Maharashtra
Number of Treatments: 12 including untreated check.
Plot size : 50 m2
Application time : Immediately after seed sowing (pre-emergence)
Method of application: Blanket spray over the soil with backpack sprayer fitted with 2 nozzle booms.
Water volume : 500 liter per hectare
Observation Methods: as per Example 1.

Table 5: Treatment details
Treatment number Treatment details Application Rate (gai/h)
T1 pendimethalin 24%+imazethapyr 2.4%+pyroxasulfone 6% OD 600+60+150
T2 pendimethalin 30%+imazethapyr 2%+chlorimuron ethyl 0.4% ZC 600+40+8
T3 pendimethalin 24%+imazethapyr 2.4% EC (ready mix) 600+60
T4 pendimethalin 30%+imazethapyr 2% EC (ready mix) 600+40
T5 imazethapyr 70% WG+pyroxasulfone 85% WG (tank mix) 60+25
T6 imazethapyr 70% WG+chlorimuron ethyl 25% WP (tank mix) 50+25
T7 pendimethalin 30% EC 600
T8 Imazethapyr 70% WG 60
T9 Imazethapyr 70% WG 40
T10 pyroxasulfone 85% WG 150
T11 chlorimuron ethyl 25% WP 8
T12 Untreated Control (UTC) 0
OD-oil dispersion, ZC-zeon concentrate, T1-T2: present compositions, T3-T4: known compositions, T5-T6: tank mixes.

Table 6: Weed control in soybean.
Treatment number % Weed control
15 DAS 30 DAS
Observed Expected Colby's ratio Synergism (Y/N) Observed Expected Colby's ratio Synergism (Y/N)
T1 98.6 93.99 1.05 Y 96.4 90.16 1.07 Y
T2 96.8 92.95 1.04 Y 93.8 88.66 1.06 Y
T3 86.8 84.90 1.02 79.2 78.41 1.01
T4 84.6 83.84 1.01 76.4 77.93 0.98
T5 86.2 85.19 1.01 77.8 79.66 0.98
T6 83.4 82.65 1.01 75.6 76.56 0.99
T7 59.4 51.6
T8 62.8 55.4
T9 56.4 48.6
T10 60.2 54.4
T11 48.6 42.8
T12 0.0 0.0
Weed flora composition: Grassy weeds (approx. 65%)- Brachiaria erusiformis, Eleusine indica, Echinochloa colonum, Cloris barbata; Broad leaf weeds (approx. 30%)-Euphorbia hirta, Amaranthus viridis, Sedges (approx. 5%)-Cyperus rotundus.

Field study shows that both the present compositions (T1 & T2) provide synergistic and residual control of mixed weed flora in soybean crop.

Example 4: Weed control in green gram.
Crop : Green gram
Location : Umreth, Gujarat
Number of Treatments: 12 including untreated check.
Plot size : 40 m2
Application time : 2 days after sowing (pre-emergence)
Method of application: Blanket spray over the soil with backpack sprayer fitted with 2 nozzle boom.
Water volume : 500 litre per hectare
Observation Methods: as per Example 1.

Table 7: Treatment details
Treatment number Treatment details Application Rate (gai/h)
T1 pendimethalin 40%+imazethapyr 4%+oxyfluorfen 3% EC 600+60+45
T2 pendimethalin 30%+imazethapyr 3%+metribuzin 5% EC 600+60+100
T3 pendimethalin 30%+imazethapyr 3% EC 600+60
T4 pendimethalin 40%+oxyfluorfen 3% EC 600+45
T5 pendimethalin 30%+metribuzin 5% EC 600+100
T6 imazethapyr 70% WG+oxyfluorfen 23.5% EC (tank mix) 600+45
T7 imazethapyr 70% WG+metribuzin 70% WP (tank mix) 600+100
T8 pendimethalin 30% EC 600
T9 imazethapyr 70% WG 60
T10 oxyfluorfen 23.5% EC 45
T11 metribuzin 70% WP 100
T12 Untreated Control (UTC) 0
T1-T2: present compositions, T3-T5: known compositions, T6-T7: tank mixes.

Table 8: Weed control in green gram.
Treatment number % Weed control
15 DAS 30 DAS
Observed Expected Colby's ratio Synergism (Y/N) Observed Expected Colby's ratio Synergism (Y/N)
T1 97.8 92.40 1.06 Y 95.6 87.11 1.10 Y
T2 98.4 93.47 1.05 Y 96.0 87.76 1.09 Y
T3 85.6 84.37 74.4 76.82
T4 83.4 82.89 73.8 75.31
T5 86.8 85.29 72.4 76.56
T6 79.4 78.42 67.8 70.98
T7 82.4 81.44 69.6 72.44
T8 64.8 55.6
T9 55.6 47.8
T10 51.4 44.4
T11 58.2 47.2
T12 0.0 0.0

Weed flora composition: Grassy weeds (approx. 50%) - Echinochloa colonum, Dactyloctenium spp. Broad leaf weeds (approx. 50%)-Digera arvensis, Parthenium spp., Amaranthus spinosus.

The present compositions (T1 & T2) provide synergistic and residual control of mixed weed flora in green gram crop.

Example 5: Weed control in Sugarcane crop.
Crop : Sugarcane
Location : Sangamner, Maharashtra
Number of Treatments: 5 including untreated check.
Plot size : 100 sq.m. (m2)
Application time : 2 days after planting.
Method of application: Blanket spray over the soil with backpack sprayer fitted with 2 nozzle booms.
Water volume : 500 liter per hectare
Observation Methods: as per example 1.

Table 9: Treatment details
Treatment number Treatment details Application Rate (gai/h)
T1 pendimethalin 45%+imazethapyr 6%+diclosulam 1.6% SE 675+90+24
T2 pendimethalin 20%+imazethapyr 5%+sulfentrazone 15% ZC 400+100+300
T3 pendimethalin 30% EC+imazethapyr 10% SL+diclosulam 84% WG (tank mix) 675+90+24
T4 pendimethalin 38.7% CS+imazethapyr 10% SL+sulfentrazone 39.6% SC (tank mix) 400+100+300
T5 Untreated Control (UTC) 0

T1 & T2: present compositions, T3 & T4: on farm tank mixes.

Table 10: Weed control in Sugarcane.
Treatment number % Weed control
15 DAA 30 DAA 45 DAA 60 DAA
T1 100.00 100.00 98.40 94.60
T2 100.00 99.60 96.20 93.20
T3 100.00 94.20 88.80 81.60
T4 100.00 92.60 85.40 77.40
T5 0.00 0.00 0.00 0.00

Weed flora composition: Grassy weed flora includes Echinochloa colonum, Dactyloctenium spp., Eleusine indica. Broad leaf weed flora includes Trianthema portulacastranum, Physalis minima, Amaranthus viridis, Parthenium hysterophorus.

Both the present compositions (T1 & T2) provide excellent residual control of both the grasses and broad leaf weeds in sugarcane as compared with their on farm tank mixes.

Summary of field trials:
• The compositions comprising of Pendimethalin+ Imazethapyr+ at least one herbicide provides synergistic and broad spectrum control of mixed weed flora (grassy, broad leaf weeds and sedges).
• Provides desirable residual control of weeds.
• Excellent control of tough to control weeds in single shot application. Farmers do not need to apply frequently.
• Provides excellent tools as delaying resistance development in weeds against specific herbicide.
• Does not shows phytotoxicity symptoms and does not have any kind of impact on crop growth and yield.
• Due to excellent weed control, crops were observed with increase tillers, shoot counts which are directly contributing to the crop yield.

Claims:CLAIMS
We claim;

1. A synergistic herbicidal composition comprising:
a. a herbicide A is N-(1-Ethylpropyl)-3,4-dimethyl-2,6-dinitrobenzenamine and their salts and esters;
b. a herbicide B is 5-ethyl-2-(4-methyl-5-oxo-4-propan-2-yl-1H-imidazol-2-yl)pyridine-3-carboxylic acid and their salts and esters;
c. at least one herbicide C which is selected from diclosulam, chlorimuron ethyl, sulfentrazone, clomazone, pyroxasulfone, oxyfluorfen, metribuzin;
d. formulation excipients.

2. The synergistic herbicidal composition as claimed in claim 1, wherein a herbicide A is present in the range of 15% to 50% w/w; b) a herbicide B is present in the range of 1% to 8 % w/w; and c) a herbicide C is present in the range of 0.1% to 20% w/w.

3. The synergistic herbicidal composition as claimed in claim 1, wherein formulation for the said composition is selected from Capsule suspension (CS), Dispersible concentrate (DC), Emulsifiable concentrate (EC), Emulsion, water in oil (EO), Emulsion, oil in water (EW), Jambo balls or bags (bags in water soluble pouch), Micro-emulsion (ME), Oil dispersion (OD), Oil miscible flowable concentrate (oil miscible suspension (OF), Oil miscible liquid (OL), Suspension concentrate (SC), Suspo-emulsion (SE), Soluble concentrate (SL), Water dispersible granule (WG or WDG), Water soluble granule (SG), Water soluble powder (SP), Wettable powder (WP), A mixed formulation of CS and SC (ZC), A mixed formulation of CS and SE (ZE), A mixed formulation of CS and EW (ZW), Granule for soil application (GR).

4. The synergistic herbicidal composition as claimed in claim 3, wherein the composition for suspo-emulsion (SE) formulation comprises:
a. a herbicide A is N-(1-Ethylpropyl)-3,4-dimethyl-2,6-dinitrobenzenamine and their salts and esters is in the range of 15% to 50% w/w;
b. a herbicide B is 5-ethyl-2-(4-methyl-5-oxo-4-propan-2-yl-1H-imidazol-2-yl)pyridine-3-carboxylic acid and their salts and esters is in the range of 1% to 8 % w/w;
c. at least one herbicide C which is selected from diclosulam, chlorimuron ethyl, sulfentrazone, clomazone, pyroxasulfone, oxyfluorfen, metribuzin is present in the range of 0.1% to 20% w/w of the composition;
d. wetting agent present in an amount of 2.0-4.0%w/w;
e. dispersing agent I present in an amount of 2.0-4.0%w/w;
f. dispersing agent II present in an amount of 2.0-4.0%w/w;
g. suspending agent present in an amount of 0.1-2.0 %w/w;
h. anti foaming agent present in an amount of 0.05-0.5%w/w;
i. anti freezing agent present in an amount of 0.05-0.5%w/w.

5. The synergistic herbicidal composition as claimed in claim 4, wherein dispersing agent is selected from Naphthalenesulfonic acid, sodium salt condensate with formaldehyde, alkylated naphthalene sulfonate, sodium salt, sodium salt of naphthalene sulfonate condensate, sodium ligno sulfonate, sodium polycarboxylate, EO/PO based copolymer, phenol sulfonate, sodium methyl oleoyl taurate, acrylic graft copolymer, styrene acrylic acid copolymer, propylene oxide-ethylene oxide-copolymer, polyethylene glycol 2,4,6-tristyrylphenyl ether, tristyrylphenol-polyglycol ether-phosphate, tristyrylphenole with 16 moles EO, tristyrylphenol-polyglycol ether-phosphate, oleyl-polyglycol ether with ethylene oxide, tallow fatty amine polyethylene oxide, nonylphenol polyglycol ether with 9-10 moles ethylene oxide.

6. The synergistic herbicidal composition as claimed in claim 4, wherein wetting agent is selected from ethylene oxide/propylene oxide (EO/PO) block copolymer, poly aryl phenyl ether phosphate, polyalkoxylated butyl ether, ethoxylated fatty alcohol, sodium dioctyl sulfosuccinate, sodium lauryl sulfate and sodium dodecyl benzene sulfonate, alkyl diphenyl sulfonates, sodium isopropyl naphthalene sulfonate, alkyl naphthalene sulfonate. Ethoxylated alcohol includes natural fatty alcohol (lauryl alcohol ethoxylate, lauryl alcohol alkoxylate), synthetic alcohol ethoxylate (tridecyl alcohol ethoxylate, 2-ethyl hexanol, 2-propylheptanol, isodecyl alcohol.

7. The synergistic herbicidal composition as claimed in claim 4, wherein Suspending agent is selected from aluminum magnesium silicate, bentonite clay, silica, attapulgite clay.

8. The synergistic herbicidal composition as claimed in claim 4, wherein Antifoaming agent is selected from silicone antifoam emulsion, dimethyl siloxane, polydimethyl siloxane, vegetable oil based antifoam, tallow based fatty acids.

9. The synergistic herbicidal composition as claimed in claim 4, wherein Anti-freezing agent is selected from ethylene glycol, propane diols, glycerin or the urea, glycol (monoethylene glycol, diethylene glycol, 1,2-propylene glycol, polyethylene glycol), glycerin, urea, magnesium sulfate heptahydrate, sodium chloride.

10. The synergistic herbicidal composition as claimed in claim 3, wherein the composition for Zeon Concentrate (ZC) formulation comprises:
a. a herbicide A is N-(1-Ethylpropyl)-3,4-dimethyl-2,6-dinitrobenzenamine and their salts and esters is in the range of 15% to 50% w/w of the composition;
b. a herbicide B is 5-ethyl-2-(4-methyl-5-oxo-4-propan-2-yl-1H-imidazol-2-yl)pyridine-3-carboxylic acid and their salts and esters is in the range of 1% to 8 % w/w of the composition;
c. at least one herbicide C which is selected from diclosulam, chlorimuron ethyl, sulfentrazone, clomazone, pyroxasulfone, oxyfluorfen, metribuzin is present in the range of 0.1% to 20% w/w of the composition;
d. Wall forming material 1 present in an amount of 0.1-2.0 %w/w;
e. Wall forming material 2 present in an amount of 0.1-2.0 %w/w;
f. dispersing agent I present in an amount of 0.1% to 5.0% w/w;
g. dispersing agent II present in an amount of 0.1% to 2.0% w/w;
h. wetting agent present in an amount of 0.5% to 4.0% w/w;
i. suspending agent present in an amount of 0.1-2.0 %w/w;
j. anti foaming agent present in an amount of 0.05-0.5%w/w;
k. anti freezing agent present in an amount of 3.0-6.0%w/w.

11. The synergistic herbicidal composition as claimed in claim 10, wherein Wall forming material 1 is selected from Tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, 4,4-diphenylmethene diisocyanate (MDI), polymethylene polyphenylene isocyanate, 2,4,4’-diphenyl ether tri-isocyanate, 3,3’-dimethyl-4,4’-diphenyl diisocyanate, 3,3’-dimethoxy-4,4’-diphenyl diisocyanate, 1,5-naphthylene diisocyanate and 4,4’4"-triphenylmethane tri-isocyanate, toluene diisocyanate or polymethylene polyphenylisocyanate, polyurethane comprising of polyfunctional iso cyanate and a polyamine in polarized form.

12. The synergistic herbicidal composition as claimed in claim 10, wherein Wall forming material 2 is selected from Diethylene triamine, Ammonia, hexamine, ethylenediamine, propylene-1,3-diamine, tetramethylenediamine, pentamethylenediamine, 1,6-hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetra ethylene pentamine, pentaethylenehexamine, 4,9-dioxadodecane-1, 12-diamine, 1,3- phenylenediamine, 2,4- and 2,6-toluenediamine and 4,4’-diaminodiphenylmethane, 1,3-phenylenediamine, 2,4- and 2,6-toluenediamine, 4,4'-diaminodiphenylmethane, 1,5-diaminonaphthalene, 1,3,5-triaminobenzene, 2,4,6-triaminotoluene, 1,3,6-triaminonaphthalene, 2,4,4'-triaminodiphenyl ether, 3,4,5-triamino-1,2,4-triazole and 1,4,5,8-tetraminoanthraquinone.

13. The synergistic herbicidal composition as claimed in claim 10, wherein a Antifoaming agent is selected from silicone oil, silicone compound, C10~C20 saturated fat acid compounds or C8~C10 aliphatic alcohols compound, Silicone antifoam emulsion, Dimethyl siloxane, Polydimethyl siloxane, Vegetable oil based antifoam, tallow based fatty acids, polyalkyleneoxide modified polydimethylsiloxane.

14. The synergistic herbicidal composition as claimed in claim 10, wherein dispersing agent 1 is selected from sodium polycarboxylate, EO/PO based copolymer, phenol sulfonate, sodium methyl oleoyl taurate, styrene acrylic acid copolymer, propylene oxide-ethylene oxide-copolymer, polyethylene glycol 2,4,6-tristyrylphenyl ether, tristyrylphenol-polyglycol ether-phosphate, tristyrylphenole with 16 moles EO, tristyrylphenol-polyglycol ether-phosphate, oleyl-polyglycol ether with ethylene oxide, tallow fatty amine polyethylene oxide, nonylphenol polyglycol ether with 9-10 moles ethylene oxide, alkyl phenyl polyglycol ether, tributyl phenyl polyglycol ethers, alkyl aryl polyether alcohols, is tridecyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate,.

15. The synergistic herbicidal composition as claimed in claim 10, wherein dispersing agent 2 is selected from Ethoxylated lignosulfonic acid salts, lignosulfonic acid salts, oxidized lignins, lignin salts, salts of styrenemaleic anhydride copolymers, polyvinyl alcohol, salts of partial esters of styrene-maleic anhydride copolymers, partial salts of polyacrylic acid and partial salts of polyacrylic acid terpolymers, lignosulfonate of calcium or sodium or mixtures thereof or a modified kraft lignin with a high sulfonic acid group, dibutylnaphthalenesulfonic acid, fatty acids, alkyl- and alkylarylsulfonates, alkyl sulfates, lauryl ether sulfates and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols and of fatty alcohol glycol ethers, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene or of the naphthalenesulfonic acids with phenol and formaldehyde, alkyl napthalene sulfonate condensate, polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl- or nonylphenol, sorbitol esters, lignin-sulphite waste liquors, and proteins, denatured proteins, polysaccharides , ammonium salts of sulfonates, sulfates, phosphates or carboxylates, alkylarylsulfonates, diphenyl sulfonates, alpha-olefin sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of condensed naphthalene, sulfonates of dodecyl- and tridecyl benzenes, sulfonates of naphthalene and alkylnaphthalenes, sulfosuccinates or sulfosuccinates, alkoxylates, N-alkylated fatty acid amides, amine oxides, esters or sugar-based surfactants, alkylphenols, amines (e.g. tallow amine), amides, aryl phenols, fatty acids or fatty acid esters which have been alkoxylated. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide, polyethylene oxide and polypropylene oxide, polyacids or polybases.

16. The synergistic herbicidal composition as claimed in claim 10, wherein wetting agent is selected from Ethylene oxide/propylene oxide block copolymer, Polyarylphenyl ether phosphate, Ethoxylated Fatty Alcohol, Polycondensate of polypropylene glycol with ethylene oxide, Sodium dioctyl sulfosuccinate, sodium lauryl sulphate and sodium dodecyl benzene sulfonate, alkyl diphenyl sulfonates, sodium isopropyl naphthalene sulfonate, Alkyl naphthalene sulfonate, Octyl phenol ethoxylate, alkyl phenol ethoxylate.

17. The synergistic herbicidal composition as claimed in claim 10, wherein Antifreezing agent is selected from ethylene glycol, propane diols, glycerine or the urea, Glycol (Monoethylene glycol, Diethylene glycol, Polypropylene glycol, Polyethylene glycol), Glycerine, Urea, Magnesium sulphate heptahydrate, sodium chloride

18. The synergistic herbicidal composition as claimed in claim 10, wherein Suspending agent is selected from Aluminium Magnesium Silicate, Bentonite clay, Silica, Attapulgite clay, tributyl phenyl polyglycol ether

19. The synergistic herbicidal composition as claimed in claim 3, wherein the composition for Oil dispersion (OD) formulation comprises:
a. A herbicide A is N-(1-Ethylpropyl)-3,4-dimethyl-2,6-dinitrobenzenamine and their salts and esters is in the range of 15% to 50% w/w of the composition;
b. A herbicide B is 5-ethyl-2-(4-methyl-5-oxo-4-propan-2-yl-1H-imidazol-2-yl)pyridine-3-carboxylic acid and their salts and esters is in the range of 1% to 8 % w/w of the composition;
c. at least one herbicide C which is selected from diclosulam, chlorimuron ethyl, sulfentrazone, clomazone, pyroxasulfone, oxyfluorfen, metribuzin is present in the range of 0.1% to 20% w/w of the composition;
d. dispersing agent present in an amount of 2.0% to 8.0% w/w;
e. wetting agent present in an amount of 3.0% to 8.0% w/w;
f. anti foaming agent present in an amount of 0.1-2.0%w/w;
g. antifreezing agent present in an amount of 2.0-7.0%w/w

20. The synergistic herbicidal composition as claimed in claim 19, wherein dispersing agent is selected from Alkyl sulfonates, alkyl benzene sulfonates, alkyl aryl sulfonates, alkylphenolalkoxylates, tristyrylphenol ethoxylates, natural or synthetic fatty ethoxylate alcohols, natural or synthetic fatty acid alkoxylates, natural or synthetic fatty alcohols alkoxylates, alkoxylated alcohols (such as n-butyl alcohol poly glycol ether), block copolymers (such as ethylene oxide-propylene oxide block copolymers and ethylene oxide-butylene oxide block copolymers), fatty acid-polyalkylene glycol condensates, polyamine-fatty acid condensates, polyester condensates, salts of polyolefin condensates, sodium ligno sulfonate, sodium ploycarboxylate, EO/PO based copolymer, phenol sulfonate, sodium methyl oleoyl taurate, styrene acrylic acid copolymer, propyleneoxide-ethyleneoxide-copolymer, polyethylene glycol 2,4,6-tristyrylphenyl ether, tristyrylphenol-polyglycolether-phosphate, tristyrylphenole with 16 moles EO, tristyrylphenol-polyglycolether-phosphate, oleyl-polyglycolether with ethylene oxide, tallow fattyamine polyethylene oxide, nonylphenol polyglycolether with 9-10 moles ethylene oxide.

21. The synergistic herbicidal composition as claimed in claim 19, wherein wetting agent is selected form ethylene oxide/propylene oxide block copolymer, polyarylphenyl ether phosphate, ethoxylated fatty alcohol, sodium dioctyl sulfosuccinate, sodium lauryl sulfate and sodium dodecyl benzene sulfonate, alkyldiphenyl sulfonates, sodium isopropyl naphthalene sulfonate, alkylnaphthalene sulfonate.

22. The synergistic herbicidal composition as claimed in claim 19, wherein Emulsifying agent is selected form castor oil ethoxylates, alcohol ethoxylates, fatty acid ethoxylates, sorbitan ester ethoxylates, sulphosuccinate, calcium salts of dodecylbenzene sulphonate, alkylammonium salts of alkylbenzene sulphonate, alkylsulphosuccinate salts, ethylene oxide-propylene oxide block copolymers, ethoxylated alkylamines, ethoxylated alkyl phenols, polyoxyethylene sorbitan monolaurate.

23. The synergistic herbicidal composition as claimed in claim 19, wherein Antifoaming agent is selected from silicone oil, silicone compound, C10~C20 saturated fat acid compounds or C8~C10 aliphatic alcohols compound, silicone antifoam emulsion, dimethylsiloxane, polydimethyl siloxane, vegetable oil-based antifoam, tallow based fatty acids, polyalkyleneoxide modified polydimethylsiloxane.

24. The synergistic herbicidal composition as claimed in claim 19, wherein Antifoaming agent is selected from ethylene glycol, propane diols, glycerine, urea, Monoethylene glycol, Diethylene glycol, Polypropylene glycol, Polyethylene glycol, glycerine, magnesium sulfate heptahydrate, sodium chloride.

25. The synergistic herbicidal composition as claimed in claim 3, wherein the composition for Emulsifiable concentrate (EC) formulation comprises:
a. a herbicide A is N-(1-Ethylpropyl)-3,4-dimethyl-2,6-dinitrobenzenamine and their salts and esters is in the range of 15% to 50% w/w of the composition;
b. a herbicide B is 5-ethyl-2-(4-methyl-5-oxo-4-propan-2-yl-1H-imidazol-2-yl)pyridine-3-carboxylic acid and their salts and esters is in the range of 1% to 8 % w/w of the composition;
c. at least one herbicide C which is selected from diclosulam, chlorimuron ethyl, sulfentrazone, clomazone, pyroxasulfone, oxyfluorfen, metribuzin is present in the range of 0.1% to 20% w/w of the composition;
d. Solvent present in an amount of 4.0% to 6.0% w/w;
e. Emulsifier present in an amount of 2.0% to 5.0% w/w;
f. Sticker, surface tension reducer, binder present in an amount of 0.1-2.0 %w/w;
g. Spreader, sticker, penetrant, surface tension reducer present in an amount of 0.05-0.5%w/w.

26. The synergistic herbicidal composition as claimed claim in 25, wherein Solvent is selected from naphtha or heavy aromatic hydrocarbon is selected from the group comprising of toluene, o-, m-, p-xylene, dodecane, n- decane, n-hexane, benzene, ethylbenzene, isopropyl benzene, tert-butylbenzene, naphthalene, mono- or poly alkyl-substituted naphthalene, paraffinic hydrocarbons, n-butanol, N-methyl 2-pyrrolidine, cyclohexanone, isophorone-3, 5, ester solvents such as methyl oleate, dimethyl amide and morpholine amide derivatives of C6-C16 fatty acids, mono-alkylene carbonates, ethylene carbonate, propylene carbonate, butylene carbonates, dimethyl sulfoxide (DMSO), n-alkyl pyrrolidone, fatty acid dimethyl esters, fatty acid esters, dibasic esters, one or more dimethyl amides, C8-dimethylamide, C10-dimethylamide, C12-dimethylamide, ethylene glycol, propylene glycol, poly alkylene glycols, N-Methyl-2-Pyrrolidone (NMP); N,N-dimethylformamide (DMF); dimethyl isosorbide (DMI); isophorone; acetophenone; 1,3-dimethyl-2-imidazolidonone; lactate esters; dimethyl, diethyl carbonates; methanol; ethanol; iso-propanol; n-propanol; n-butanol; iso-butanol; 2-ethylhexanol , methanol, tert-butanol; Methyl L-lactate, 2-Ethylhexyl L-lactate, Ethyl L-lactate, n-Butyl L-lactate, Octyl phenyl ethoxylates.

27. The synergistic herbicidal composition as claimed in claim 25, wherein Emulsifiers selected from salts of dodecylbenzene sulphonate, sulphonates of other C11-C16 alkylbenzenes, alkyl ether sulphates, alkylphenoletherphosphates, ester phosphates, alkoxylated alcohols and alkylphenols, ethoxylated vegetable oils, ethoxylated castor oil, fatty acid esters, ethoxylated amines, and condensates of glycerol; and catanionic emulsifiers such as a cationic amine, optionally in combination with an alkyl sulphonate or ether sulphonate or ether phosphate, alkoxylated alcohols; alkoxylated alkylphenols; tristyrylphenol ethoxylate; fatty acid esters of sorbitol and ethoxylated derivatives thereof; sulfonated alkylbenzenes in the range C11-C16 and salts thereof; alkyl ether sulphates; alkyletherphosphates; alkylphenoletherphosphates; or combinations thereof; salts of phosphate esters of ethoxylated tristyrylphenol; salts of sulphated ethers of ethoxylated tristyrylphenol; or a catanionic system, wherein a cationic amine is present in combination with an alkyl sulphonate, an alkylethersulphonate, an ether sulphate, or an ether phosphate such as an alkyletherphosphate, nonylphenol polyethoxy ethanol, castor oil polyglycol ethers, polyadducts of ethylene oxide and polypropylene, tributyl phenoxy polyethoxy ethanol, octyl phenoxy polyethoxy ethanol, calcium alkyl benzenesulfonate, ethoxylated polysorbate and calcium salt of alkyl benzene sulfonate.

28. The synergistic herbicidal composition as claimed in claim 25, wherein Sticker, surface tension reducer, binder is selected from Polyvinylpyrrolidone.

29. The synergistic herbicidal composition as claimed in claim 25, wherein Spreader, sticker, penetrant, surface tension reducer is selected from Alkyl polyethylene glycol ether.

Dated this 16th day of July 2024