DESC:FIELD OF THE INVENTION:
The present invention relates to synergistic herbicidal composition comprising A) Topramezone B) at least one herbicide selected from Atrazine and Metribuzin C) at least one more herbicide selected from Nicosulfuron, Rimsulfuron, Halosulfuron methyl, Mesotrione, Tembotrione, Sulcotrione, 2,4-D and salts thereof with one or more inactive excipients. The present invention also relates to process for preparing the said composition and its use as herbicide.

BACKGROUND OF THE INVENTION
Topramezone was first disclosed in WO 98/31681. Chemically known as 3-(4,5-dihydro-3-isoxazolyI)-2-methyl-4-(methylsulfonyl)phenyl]-(5-hydroxy-1-methyl-1H-pyrazol-4-yl)methanone and chemical structure is as below formula I and also the tautomer of the formula I;

Topramezone is a selective herbicide in the phenyl pyrazolyl ketone chemical family used for post-emergence control mainly of broadleaf weeds as well as some grasses in field maize, sweet maize, and popcorn (IMPACT(r) herbicide, 2007). It has a low use rate with a wide post-emergence application window in field maize. Topramezone can be safely applied to maize at the 2- to 8-leaf growth stage, indicating no difference in selectivity, thus providing flexibility in application window (Gitsopoulos et al., 2010). This herbicide inhibits the activity of 4-hydroxyphenylpyruvate dioxygenase (4-HPPD, EC 1.13.11.27), an enzyme catalyzing the catabolism of the common to essentially all aerobic forms of life amino acid tyrosine (Moran, 2005). Inhibition of the activity of 4-HPPD disrupts the biosynthesis of carotenoid pigments in susceptible plants, thus resulting in bleaching (chlorophyll loss) of the foliage, cessation of growth, and ultimately death of the treated plants.

Atrazine is a selective triazine herbicide used to control broadleaf and grassy weeds in corn, sorghum, sugarcane, pineapple, Christmas trees and other crops, and in conifer reforestation plantings. It is also used as a non-selective herbicide on non-cropped industrial lands and on fallow lands. It is available as dry flowable, flowable liquid, liquid, water dispersible granular, and wettable powder formulations. Atrazine is slightly mild to moderately toxic to humans and other animals. It can be absorbed into the bloodstream through oral, dermal and inhalation exposure. Symptoms of poisoning include abdominal pain, diarrhea and vomiting, eye irritation, irritation of mucous membranes, and possible skin reactions. At very high doses, rats showed excitation followed by depression, slowed breathing, incoordination, muscle spasms, and hypothermia.

Metribuzin is a selective herbicide of the chemical classes the triazines. Metribuzin can be applied as a foliar spray or soil treatment in order to control pre-emergence and post-emergence broadleaf weeds and annual grasses. Metribuzin also has a residual effect on the soil. Metribuzin is primarily absorbed by the roots, but also by the leaves to a lesser extent. It is translocated acropetally in the xylem to the leaves where it has its effect. The mode of action of metribuzin is that it acts by inhibiting photosystem II of photosynthesis by disrupting electron transfer. This results in death due to starvation in the target plant. Selectivity is due to differing metabolism of the compound within the plant.

Nicosulfuron is a sulfonylurea herbicide which was originally discovered by ISK. It controls a wide range of weeds covering both annual and perennial species. Nicosulfuron is a herbicide for maize, and forage maize in particular, which has been in use since the early 1990s. Nicosulfuron is a broad spectrum herbicide that controls a wide range of maize weeds, both annual weeds and perennial weeds. Nicosulfuron is a systemic selective herbicide, displaying genera-selectivity, therefore ensuring it is effective at killing other plants growing near the maize – even those grasses closely related to maize. This selectivity is achieved by the maize plants ability to metabolise nicosulfuron into harmless compounds. This compound works by being absorbed through the leaves (it is a foliar application) and travelling through the xylem to the meristematic regions. Here it inhibits the activity of acetolactase synthase, a key enzyme required for cell division and plant growth. Application will result in the post emergence growth of weeds within a few hours and death will result within 20 – 25 days. It will thereby be effective at controlling post-emergent weeds such as annual and perennial grass weeds, sedges and broad-leaved weeds such as Sorghum halepense and Agropyron repens. This compound is easy to use, requires no adjuvant and does no wash into the soil. It is harmless to birds, fish, bees and insects.

Rimsulfuron is a herbicide of certain grasses, annual broadleaf weeds and perennial broadleaf weeds and is also particularly effective for the management of glyphosate-resistant weed species such as ryegrass and marestail/horseweed. It is applied as a foliar spray and absorbed through the plants leaves and translocated to the growing point of the plant. Rimsulphuron acts by inhibiting the action of acetolactate synthase (ALS), also known as acetohydroxyacid synthase (AHAS). Without this enzyme the plant cannot produce specific amino acids (isoleucine, leucine and valine) thereby preventing protein formation. This effectively prevents growth at the growing points of the plant, namely the apical meristem and root tip. This enzyme is only found in plants – making them have a very low toxicity for animals and man. Rimsulfuron can be applied to cropland for potatoes and forage maize. It is effective on grasses including barnyard grass, quackgrass and crab grass as well as other weeds such as marestail/horseweed, fleabane, filaree, foxtail and dandelion. The speed at which plans metabolise rimsulfuron differs, meaning some plants are more sensitive to this compound than others. It is not selective and rotation crops can be sensitive to the product.

Halosulfuron-methyl is a new post-emergence sulfonylurea herbicide for control of broad-leaf weeds and sedges in rice and maize. On rice, it can be used on submerged field as well as on dry seeded one with a dosage between 22.5 and 37.5 g/ha a.i.. It has proved to be particularly effective against Bolboschoenus spp., Schoenoplectus spp., Cyperus spp., Alisma spp., Bidens spp., Typha spp., Ammannia spp. and Lindernia spp. It can be applied from the stage of 2-4 leaves up to the end of tillering, also in combination with special products for control of grass weeds, such as Echinochloa spp. Halosulfuron-methyl shows excellent selectivity to both rice groups (indica and japonica varieties). On maize, it is applied in post-emergence conditions starting from the stage of 1-2 leaves with a dose between 22.5 and 37.5 g/ha of a.i. It is particularly effective against Cyperus spp., Abutilon theophrasti, Xanthium spp., Bidens spp., Polygonum spp., Amaranthus ssp. It shows also an excellent selectivity to maize.

Mesotrione is a relatively new herbicide that inhibits pigment development by blocking production of the HPPD enzyme in susceptible plants. It is also the only herbicide with this mode of action that is currently registered for use in Kentucky bluegrass (Poa pratensis) grown for seed. The product label lists control of numerous broadleaf weeds. Anecdotal evidence suggests that mesotrione has some activity on grassy weeds. If this were the case mesotrione would be extremely useful in Kentucky bluegrass seed production.

Tembotrione is a novel HPPD maize herbicide effective against a wide range of broadleaf and grass weeds. Some characteristics of this compound are described in this paper linking weed and crop responses following tembotrione applications to environmental parameters or use conditions. The activity of HPPD herbicides is very much dependant on the availability of light. Increasing illumination intensities following application augmented the activity levels of several comparable HPPD compounds in a growth chamber experiment. Tembotrione was shown to be more efficacious at low and high illumination intensities compared to standard herbicides applied at the same rate. At the high intensity, tembotrione retained its high efficacy from two up to four weeks after application showing a rapid and strong herbicidal activity.

The activity following post-emergent treatments of tembotrione against broadleaf weeds was influenced by soil characteristics such as soil texture and organic matter content in a glasshouse test. The level of weed suppression clearly declined stronger on heavier soils than on lighter soils at a rather low application rate of 12.5 g a.i./ha and lower. This is a clear indication of residual efficacy of tembotrione.

Sulcotrione is primarily a systemic, post-emergence herbicide. However, it also has some residual soil activity, remaining in the top layer of the soil to be activated by rainfall. Grass weeds are best controlled with early post-emergence applications. Plant death occurs within ten days of treatment. The product has shown no cross-resistance to atrazine-resistant species. Sulcotrione may be used for pre-emergence applications in flax. No visible injury or negative effects on yield have been noted.

CN103181391A relates to herbicide composition used for controlling farmland weeds, and a purpose thereof, and specifically relates to a herbicide used for controlling corn field grass weeds and broadleaf weeds. The invention provides a binary herbicide composition with topramezone and atrazine as active components. In the composition, the weight ratio of topramezone to atrazine is 1:180-1:1. The composition can be prepared into any agriculturally acceptable preparations. When the composition is used in corn field weed controlling, a substantial synergetic effect compared with single applications of the components is provided. With the composition, herbicidal spectrum can be widened, controlling cost can be reduced, appearance of weed resistance can be retarded, and good safety upon crops is provided.

CN103518739A relates to a herbicide containing topramezone and atrazine. The herbicide is a two-member herbicide composition with topramezone and atrazine as effective components, wherein the weight ratio of the effective component topramezone to the effective component atrazine is 1:15; the herbicide can be prepared into any allowed dosage forms in agriculture. The herbicide is used for preventing and removing weeds in corn fields, has significant synergic effect compared with alone application of the components, can broaden weed killing spectrum, reduces preventing and removing cost, retards generation of weed resistance, and has good safety to crops.

CN105104388B discloses a corn post-emergent herbicide containing complex topramezone, clopyralid and atrazine, which is characterized in that: the compound of the active ingredient is a herbicide topramezone, dichloro pyridine atrazine and acid weight ratio of 0.1 to 70: 0.1 to 70: 0.1 to 80 components. The herbicide of the present invention is not only complex cornfield controlling annual grass weeds, broadleaf weeds and sedges can herbicidal effect is significant, significant synergism, and a pesticide capable of controlling crop entire i.e. weed growth period, no effect on the crop, is an ideal herbicide.

CN105191949A discloses a pesticide composition containing tembotrione, topramezone and atrazine. The effective ingredients of the pesticide composition comprise the tembotrione, the topramezone and the atrazine, wherein the weight percent of the tembotrione in the pesticide composition is 1%-40%; the weight percent of the topramezone in the pesticide composition is 1%-40%; the weight percent of the atrazine in the pesticide composition is 1%-60%; and the rest is the pesticide auxiliaries. The components of the pesticide composition provided by the invention are reasonable; the pesticide composition has synergies response to the weeds in the corn field and especially has obvious synergies effects on barnyard grass, crab grasses and wild cotton; the weeding spectrum of single agent is expanded; the risk of weed resistance is reduced; and the pesticide composition is fit for preventing and killing the annual weeds in the corn field.

CN107047579A relates to a maize after-seedling weeding composition containing topramezone, florasulam and atrazine. Three effective constituents, including topramezone, florasulam and atrazine, are taken as the main effective constituents of the weeding composition, wherein the mass ratio of topramezone to florasulam to atrazine is (0.1-70):(0.1-70):(0.1-80). The weeding composition disclosed by the invention not only can prevent and weed annual gramineous weeds in maize fields but also can prevent and weed broad leaf weeds and nutgrass flatsedge, has an obvious weeding effect and an obvious synergic effect, can prevent and weed the weeds in the whole duration period by once application, has no influence on succession crops, and is an ideal weeding agent.

CN107279166A discloses a complex suspending agent of topramezone and nicosulfuron and a preparation method of the complex suspending agent and relates to the technical field of annual weed control of a corn field. A 36% complex suspending agent of the topramezone and the nicosulfuron mixed at the ratio of 1:2 is capable of playing an obvious synergistic effect, and the preparation mixed at other ratios cannot reach the obvious synergistic effect range.

CN105409999A relates to corn field annual weed control, the invention provides a topramezone, nicosulfuron and atrazine compounded dispersible oil-based suspension agent and a preparation method thereof. The compounded dispersible oil-based suspension agent is prepared from 1.5 parts of topramezone, 4.5 parts of nicosulfuron, 22 parts of atrazine, 3 parts of fatty alcohol polyoxyethylene ether, 5 parts of styrylphenol polyoxyethylene ether, 0.5 part of xanthan gum, 0.3 part of sodium benzoate, 0.5 part of a defoaming agent and 62.7 parts of deionized water.

CN103636647A discloses a topramezone-rimsulfuron-containing weeding composition. The topramezone-rimsulfuron-containing weeding composition comprises topramezone and rimsulfuron as active ingredients and the balance an herbicide assistant. A mass part ratio of topramezone to rimsulfuron in the topramezone-rimsulfuron-containing weeding composition is in a range of 1: 5 to 5: 1, and the total mass of topramezone and rimsulfuron is 3-75% that of the topramezone-rimsulfuron-containing weeding composition. According to application demands, the topramezone-rimsulfuron-containing weeding composition can be processed to form a dispersible oil suspending agent, a suspending agent, wettable powder or water dispersible granules suitable for agricultural application, can be used for preventing and removing annual weeds in the corn field, has prevention and control effects superior to those of various single-component agents, reduces a herbicide use amount and delays production of herbicide resistance of weeds.

CN105532701A provides a mixed herbicide containing topramezone and rimsulfuron and application of the mixed herbicide. The mixed herbicide employs topramezone and rimsulfuron as major effective ingredients, wherein the mass ratio of topramezone to rimsulfuron is (1: 15) to (900: 1). The mixed herbicide provided by the invention is applied to the weeding of corn fields and particularly has a remarkable effect in application of preventing and weeding emerged or forthcoming various Gramineae, Cyperaceae and broad-leaf weeds. Compared with single agents, the herbicide provided by the invention has the advantages that the resistance to the weeds is retarded on the premise of improving drug effect, the weeding spectrum is broad, the effect duration is long, and the herbicide has safety to corn.

CN104012562B discloses a weed control composition containing atrazine. The weed control composition comprises the following ingredients by weight percent: 0.1-50% of topramezone, 1-40% of halosulfuron-methyl,1-60% of atrazine and the balance of pesticide adjuvants, wherein the topramezone, the halosulfuron-methyl and the atrazine are active ingredients. The weed control composition is used for controlling annual weeds in the corn fields, has obviously effects better than the corresponding single agent, expands the weed control spectrum, also reduces the dosage, delays the drug resistance of weeds and reduces environmental pollution.

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

Inventors of the present invention have surprisingly found that the synergistic herbicidal composition comprising A) Topramezone B) at least one herbicide selected from Atrazine and Metribuzin C) at least one more herbicide selected from Nicosulfuron, Rimsulfuron, Halosulfuron methyl, Mesotrione, Tembotrione, Sulcotrione, 2,4-D and salts thereof with one or more inactive excipients described herein in can provide solution to the above mentioned problems.

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

We have accordingly found that this object is achieved by synergistic herbicidal composition comprising A) Topramezone B) at least one herbicide selected from Atrazine and Metribuzin C) at least one more herbicide selected from Nicosulfuron, Rimsulfuron, Halosulfuron methyl, Mesotrione, Tembotrione, Sulcotrione, 2,4-D and salts thereof with one or more inactive excipients.

Accordingly, in a second aspect, the present invention provides a method of preparing the synergistic herbicidal composition comprising A) Topramezone B) at least one herbicide selected from Atrazine and Metribuzin C) at least one more herbicide selected from Nicosulfuron, Rimsulfuron, Halosulfuron methyl, Mesotrione, Tembotrione, Sulcotrione, 2,4-D and salts thereof with one or more inactive excipients.

DETAILED DESCRIPTION OF THE INVENTION
The present invention provides solution to all the problems mentioned above by providing the synergistic herbicidal composition.

The present invention provides a synergistic herbicidal composition comprising A) Topramezone B) at least one herbicide selected from Atrazine and Metribuzin C) at least one more herbicide selected from Nicosulfuron, Rimsulfuron, Halosulfuron methyl, Mesotrione, Tembotrione, Sulcotrione, 2,4-D and salts thereof with one or more inactive excipients.

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

The term “formulation” and “composition” as used herein conveys the same meaning and can be used interchangeably.

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

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

In a preferred embodiment, the composition of present invention is selected from Suspension Concentrate (SC), Suspo emulsion (SE), Capsule Suspension (CS), Oil Dispersion (OD), mixed formulation of CS and SC (ZC), a mixed formulation of CS and SE (ZE), a mixed formulation of CS and EW (ZW), Granules (Soil Applied Granules), Controlled Release Granules (CR Granules), Slow release and Fast release microsphere Granules (MS Granules), Water Soluble Granules (SG), Water dispersible granule (WDG or WG), Jumbo ball formulation, Water soluble bag formulation, Wettable Powder (WP), Soluble Powder (SP).

As per one embodiment, the synergistic herbicidal composition comprising A) Topramezone B) at least one herbicide selected from Atrazine and Metribuzin C) at least one more herbicide selected from Nicosulfuron, Rimsulfuron, Halosulfuron methyl, Mesotrione, Tembotrione, Sulcotrione, 2,4-D and salts thereof with one or more inactive excipients, wherein active ingredients are present in concentration as described below;

Compound A Compound B Compound C
Active Ingredient Topramezone Atrazine
Metribuzin Nicosulfuron, Rimsulfuron, Halosulfuron methyl, Mesotrione, Tembotrione, Sulcotrione, 2,4-D
Concentration 0.1-40% 0.1-30% 0.1-30%

In another embodiment of the present invention the synergistic herbicidal composition comprising A) Topramezone B) at least one herbicide selected from Atrazine and Metribuzin C) at least one more herbicide selected from Nicosulfuron, Rimsulfuron, Halosulfuron methyl, Mesotrione, Tembotrione, Sulcotrione, 2,4-D and salts thereof with one or more inactive excipients effective for controlling or killing of resistant and tough to control weeds.

A herbicidal synergistic composition of present invention controls all kind of monocots, dicots and sedges weeds. The most common weeds controlled are selected from 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, Convolvulus arvensis, Conyza canadensis, Corchorus acutangulus, Coronopus didymus, Crotalaria serice, Cucumis callosus, Cuscuta campestris, Cuscuta chinensis, Cynodon dactylon, Cyanotis axillaris, Cyperus esculenthus, Cyperus iria, 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, 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.

In one embodiment of the present invention, the synergistic herbicidal composition of present invention is effective in controlling the growth of undesirable vegetation, e.g., in monocot and dicot crops including genetically modified and conventional or non-genetically modified varieties of sugarcane (Saccharum officinarum), corn/maize (Zea mays), Sorghum (Sorghum bicolor), Pearl millet (Pennisetum glaucum), Soybean (Glycin max), Peanut (Arachis hypogaea), Sunflower (Helianthus annuus), Green gram (Vigna radiata), Black gram (Vigna mungo), Chickpea (Cicer aritinum), Cowpea (Vigna unguiculata), Redgram (Cajanus cajan), Frenchbean (Phaseolus vulgaris), Indian bean (Lablab purpureus), Horse gram (Macrotyloma uniflorum), Field pea (Pisum sativum), Cluster bean (Cyamopsis tetragonoloba), Lentils (Lens culinaris), Apple (Melus domestica), Banana (Musa spp.), Citrus groups (Citrus spp.), Grape (Vitis vinifera), Guava (Psidium guajava), Litchi (Litchi chinensis), Mango (Mangifera indica), Papaya (Carica papaya), Pineapple (Ananas comosus), Pomegranate (Punica granatum) , Sapota (Manilkara zapota), Tea (Camellia sinensis), Coffea (Coffea Arabica), Coconut (Coco nucifera).

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

In one embodiment of the present invention, the synergistic herbicidal composition of present invention is effective against monocots, dicots and sedges weeds and are selected from 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, Convolvulus arvensis, Conyza canadensis, Corchorus acutangulus, Coronopus didymus, Crotalaria serice, Cucumis callosus, Cuscuta campestris, Cuscuta chinensis, Cynodon dactylon, Cyanotis axillaris, Cyperus esculenthus, Cyperus iria, 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, 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.

The present invention of synergistic herbicidal composition comprising A) Topramezone B) at least one herbicide selected from Atrazine and Metribuzin C) at least one more herbicide selected from Nicosulfuron, Rimsulfuron, Halosulfuron methyl, Mesotrione, Tembotrione, Sulcotrione, 2,4-D and salts thereof with one or more inactive excipients has advantages as mentioned below;
1. Synergism between three active ingredients in comparison to activity of single ingredients,
2. Covers broad spectrum of weeds
3. Synergism will be useful for control/kill of resistant and tough to control weeds.
4. Offer longer residual control

Application Time and Method:
The synergistic herbicidal composition can be applied as foliar spray pre emergence, early post emergence or late post emergence. It can be also applied as blanket spray over the crop and weed or in between the rows as directed application. The present compositions can be applied to weeds or their locus by the use of conventional ground or aerial duster, sprayers, and granules applicators by addition to irrigation and by other conventional means known to those skilled in art.

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

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

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

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

A wetting agent is a substance that when added to a liquid increases the spreading or penetration power of the liquid by reducing the interfacial tension between the liquid and the surface on which it is spreading. Wetting agents are used for two main functions in agrochemical formulations: during processing and manufacture to increase the rate of wetting of powders in water to make concentrates for soluble liquids or suspension concentrates; and during mixing of a product with water in a spray tank or other vessel to reduce the wetting time of wettable powders and to improve the penetration of water into water-dispersible granules. Examples of wetting agents used in wettable powder, suspension concentrate, and water-dispersible granule formulations include but not limited to sodium lauryl sulphate; sodium dioctylsulphosuccinate; alkyl phenol ethoxylates; and aliphatic alcohol ethoxylates and the salts thereof which are standard in agricultureor mixtures thereof.
Suspension aid in the present description denotes a natural or synthetic, organic or inorganic material with which the active substance is combined in order to facilitate its application to the plant, to the seeds or to the soil. This carrier is hence generally inert, and it must be agriculturally acceptable, in particular to the plant being treated. The carrier may be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, and the like or mixtures thereof) or liquid (water, alcohols, ketones, petroleum fractions, aromatic or paraffinic hydrocarbons, chlorinated hydrocarbons, liquefied gases, and the like or mixtures thereof).

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

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

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

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

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

Biological Examples:
Field experiments of tank mix combinations of topramezone+atrazine+mesotrione, topramezone+atrazine+2,4-D amine salt, topramezone+metribuzin+mesotrione and topramezone+metribuzin+halosulfuron methyl were carried out in sugarcane crop to evaluate their phytotoxicity and bioefficacy against different weed flora existing in the field.
A synergistic effect exists wherever the action of a combination of active ingredient is greater than the sum of the action of each of the components alone. Therefore a synergistically effective amount or an effective amount of a synergistic composition or combination is an amount that exhibits greater herbicidal activity than the sum of the herbicidal activities of the individual components.
In the field of agriculture, it is often understood that the term “synergy” is as defined by Colby S.R. in an article entitled “ Calculation of the synergistic and antagonistic responses of herbicide combinations” published in the journal Weeds, 1967, 15, p.20-22, incorporated herein by reference in its entirety. The action expected for a given combination of two active components can be calculated as follows:


The synergistic herbicidal action of the inventive mixtures can be demonstrated by the experiments below.
Example 1 Bioefficacy and phytotoxicity to sugarcane
The field experiment was conducted on sugarcane crop and experimental details as below:
Crop & Variety : Maize, Ganaga Kaveri
Experimental design : Randomized block design (R.B.D)
Replications : Three
No. of Treatments : Twelve (12)
Plot size : 50 sq. mt.
Application Time : 45 DAS (Days after planting), 2 to 6 leaf stage of weeds
Observations : at 10 and 20 DAA (days after application) for phytotoxicity and 15 and 30 DAA (Days after Application) for bioefficacy against mixed weed flora
Spray Volume : 375 liter water per hectare
Application Equipment : Manually operated knap sack sprayer fitted with flat fat nozzle
Experimental Methodology:
Sugarcane crop was raised as per the standard agronomic practices in the field to conduct a trial to assess phytotoxicity of different inventive synergistic mixtures. The trial was laid out in Randomized Block Design (RBD) with twelve treatments including untreated check (UTC), replicated three times. For each treatment plot size of 50 sq. mt was maintained. The application of different treatments with prescribed doses was done with manually operated knapsack sprayer fitted with flat fan nozzle. The spray volume was used at 375 l/h for spraying. The Untreated check plot was sprayed with water alone. Observations on phytotoxicity viz., yellowing, stunting, epinasty and hyponasty was recorded at 10 and 20 days after spraying, by adopting 0-10 rating scale as below:
0= No phytotoxicity, 1 =1-10%, 2=11-20%, 3=21-30%, 4=31-40%, 5=41-50%, 6=51-60%, 7=61-70%, 8=71-80%, 9=81-90% and 10=91-100% phytotoxicity
Percent phytotoxicity was calculated by following formula:

Sum of all scores
% Phytotoxicity = ------------------------------------------------------------- X 100
Number of samples x highest rating scale

Species wise weed count recorded at 15 and 30 DAA (Days After Application) by using 0.25 m2 quadrant treatment wise in minimum 4 places randomly selected in the plot per replication. The average of each variable was used together with the sum of all the variables per plot to calculate the percentage of control.
% Weed Control =

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

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

Table 1: Treatment details
Treatment Details Formulation (ml or g per h) Active Ingredient (g/h)

T1-Topramezone 33.6% SC+Atrazine 50% WP+Mesotrione 10% SC + 2 ml/l MSO 89.29+600+250 30+300+25
T2-Topramezone 33.6% SC+Atrazine 50% WP+2,4-D Amine Salt 58% SL+ 2ml/l MSO 89.29+600+517.24 30+300+300
T3-Topramezone 33.6% SC+Atrazine 50% WP+ 2 ml/l MSO 89.29+600 30+300
T4-Topramezone 33.6% SC+Mesotrione 10% SC+ 2 ml/l MSO 89.29+250 30+25
T5-Topramezone 33.6% SC+2,4-D Amine Salt 58% SL + 2 ml/l MSO 89.29+517.24 30+300
T6-Atrazine 50% WP+Mesotrione 10% SC 600+250 300+25
T7-Atrazine 50% WP+2,4-D Amine Salt 58% SL 600+517.24 300+300
T8-Topramezone 33.6% SC + 2 ml/l MSO 89.29 30
T9-Atrazine 50% WP 600.0 300
T10-Mesotrione 10% SC 250.0 25
T11-2,4-D Amine Salt 58% SL 517.24 300
T12-Unweeded control 0 0
ml- milli liter, g- gram, h-hectare, DAA- Days After Application, SC- Suspension Concentrate, WP Wettable Powder, SL Soluble liquid, MSO Modified seed oil as adjuvant
Table 2: Phytotoxicity on sugarcane crop
Treatment Details Yellowing (%) Stunting (%) Epinasty (%) Hyponasty (%)
10 DAA 20 DAA 10 DAA 20 DAA 10 DAA 20 DAA 10 DAA 20 DAA
T1 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
T2 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
T3 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
T4 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
T5 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
T6 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
T7 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
T8 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
T9 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
T10 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
T11 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
T12 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0

The results of the field trial on crop phytotoxicity presented in table 2 indicates that the inventive tank mix combination of topramezone+atrazine+mesotrione and topramezone+atrazine+2,4-D amine salt did not cause any significant damage to crop and crop vigor and growth. Overall all tested combinations were found safe to the sugarcane crop.

Table 3: Bioefficacy against mixed weed flora in sugarcane crop
Treatment Details % Weed Control Observed % Weed Control Expected Colby Ratio o/e
15 DAA 30 DAA 15 DAA 30 DAA 15 DAA 30 DAA
T1 99.2 95.6 84.81 74.59 1.17 1.28
T2 98.6 93.6 81.87 71.96 1.20 1.30
T3 70.4 56.8 71.76 61.27 0.98 0.93
T4 74.2 63.4 76.11 65.76 0.97 0.96
T5 68.4 60.2 71.50 62.21 0.96 0.97
T6 62.6 46.8 65.78 51.32 0.95 0.91
T7 56.8 42.6 59.17 46.28 0.96 0.92
T8 55.6 47.8
T9 36.4 25.8
T10 46.2 34.4
T11 35.8 27.6
T12 0.0 0.0

The field trials results presented in table 3 shows that inventive synergistic tank mix combination of topramezone+atrazine+mesotrione and topramezone+atrazine+2,4-D amine salt shows synergistic effect in terms of total weed control i.e. grasses, broadleaf weeds and sedges.

Example 2 Bioefficacy and phytotoxicity to sugarcane
Experimental details and method for observations were same as in example 1.
Table 4: Treatment details
Treatment Details Formulation (ml or g per h) Active Ingredient (g/h)

T1-Topramezone 33.6% SC+Metribuzin 70% WP+Mesotrione 10% SC + 2 ml/l MSO 89.29+429+250 30+300+25
T2-Topramezone 33.6% SC+Metribuzin 70% WP+Halosulfuron methyl 75% WG+ 2ml/l MSO 89.29+429+66.67 30+300+50
T3-Topramezone 33.6% SC+Metribuzin 70% WP+ 2 ml/l MSO 89.29+429 30+300
T4-Topramezone 33.6% SC+Mesotrione 10% SC+ 2 ml/l MSO 89.29+250 30+25
T5-Topramezone 33.6% SC+Halosulfuron methyl 75% WG + 2 ml/l MSO 89.29+66.67 30+50
T6-Metribuzin 70% WP+Mesotrione 10% SC 429+250 300+25
T7-Metribuzin 70% WP+Halosulfuron methyl 75% WG 429+66.67 300+50
T8-Topramezone 33.6% SC + 2 ml/l MSO 89.29 30
T9-Metribuzin 70% WP 429.0 300
T10-Mesotrione 10% SC 250.0 25
T11-Halosulfuron methyl 75% WG 66.67 50
T12-Unweeded control 0 0
ml- milli liter, g- gram, h-hectare, DAA- Days After Application, SC- Suspension Concentrate, WP Wettable Powder, WG Wettable Granule, MSO Modified seed oil as adjuvant

Table 5: Phytotoxicity on Sugarcane crop
Treatment Details Yellowing (%) Stunting (%) Epinasty (%) Hyponasty (%)
10 DAA 20 DAA 10 DAA 20 DAA 10 DAA 20 DAA 10 DAA 20 DAA
T1 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
T2 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
T3 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
T4 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
T5 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
T6 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
T7 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
T8 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
T9 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
T10 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
T11 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
T12 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0

The results of the field trial on crop phytotoxicity presented in table 5 indicates that the inventive tank mix combination of topramezone+metribuzin+mesotrione and topramezone+metribuzin+halosulfuron methyl did not cause any significant damage to crop and crop vigor and growth. Overall all tested combinations were found safe to the sugarcane crop.

Table 6: Bioefficacy against mixed weed flora in sugarcane crop
Treatment Details % Weed Control Observed % Weed Control Expected Colby Ratio o/e
15 DAA 30 DAA 15 DAA 30 DAA 15 DAA 30 DAA
T1 99.8 96.4 88.68 82.68 1.13 1.17
T2 98.4 94.2 88.36 82.02 1.11 1.15
T3 78.4 70.2 79.65 72.68 0.98 0.97
T4 74.2 70.4 77.98 69.82 0.95 1.01
T5 70.2 63.6 77.35 68.68 0.91 0.93
T6 67.6 56.2 71.42 63.61 0.95 0.88
T7 66.2 53.2 70.60 62.23 0.94 0.85
T8 60.4 52.4
T9 48.6 42.6
T10 44.4 36.6
T11 42.8 34.2
T12 0.0 0.0

The field trials results presented in table 6 shows that inventive synergistic tank mix combination of topramezone+metribuzin+mesotrione and topramezone+metribuzin+halosulfuron methyl shows synergistic effect in terms of total weed control i.e. grasses, broadleaf weeds and sedges.

The present disclosure is based in part on the discovery that A) topramezone B) at least one herbicide selected from atrazine and metrizubin C) at least one more herbicide selected from
Nicosulfuron, Rimsulfuron, Halosulfuron methyl, Mesotrione, Tembotrione, Sulcotrione, 2,4-D and salts thereof with one or more inactive excipients,already known individually for their herbicidal efficacy, display a synergistic effect when applied in a three-way combination.

EXAMPLES

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

Example 1: Suspension Concentrate (SC) formulation of Topramezone 2.4% + Atrazine 24% + Mesotrione 2%

Ingredients %
Topramezone a.i. 2.40
Cloquintocet mexyl safener a.i. 2.40
Atrazine a.i. 24.00
Mesotrione a.i. 2.00
Ethoxylated Fatty Alcohol 2.00
Acrylic graft copolymer 3.00
Alkylated naphtalene sulfonate, sodium salt 0.50
Silicone antifoam 0.50
1,2-benzisothiazolin-3-one 0.20
Mono Ethylene Glycol 5.00
Xanthan powder 0.15
D.M Water Q.S
Total 100.00

Manufacturing Process of Suspension Concentrate (SC) formulation:

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

Storage Stability of Suspension Concentrate (SC) formulation of Topramezone 2.4% + Atrazine 24% + Mesotrione 2% SC

Laboratory storage stability for 14 days
Parameters Specification (In house) Initial Stability (for 14 days)
At 54±2 0C At 0±2 0C
Description Off white colour flowable liquid Complies Complies Complies
Topramezone content percent by mass 2.28 to 2.64 2.43 2.44 2.47
Cloquintocet mexyl safener percent by mass 2.28 to 2.64 2.42 2.43 2.46
Atrazine contnet percent by mass 22.8 to 25.20 24.52 24.56 24.61
Mesotrione content percent by mass 1.90 to 2.20 2.07 2.10 2.11
Topramezone suspensibility percent mini. 80 98.55 95.65 96.25
Atrazine suspensibility percent mini. 80 98.14 94.56 97.91
Mesotrione suspensibility percent mini. 80 97.13 94.25 96.10
pH range (1% aq. Suspension) 5.5 to7.5 7.30 7.25 7.18
Pourability 95 % min 98.70 97.70 97.60
Specific gravity 1.14 – 1.60 1.14 1.14 1.15
Viscosity at spindle no.62, 20 rpm 350 -800 cps 510 520 530
Particle size (micron) D50 <3, D90 <10 2.2, 7.9 2.6, 8.5 2.7, 8.5
Persistent foam ml (after 1 minute) max. 60 nil nil nil

Room temperature storage data
Parameters Specification (In house) Study Duration
1 month 6 month 12 months
Description Off white colour flowable liquid Complies Complies Complies
Topramezone content percent by mass 2.28 to 2.64 2.43 2.46 2.49
Cloquintocet mexyl safener percent by mass 2.28 to 2.64 2.42 2.44 2.47
Atrazine contnet percent by mass 22.8 to 25.20 24.55 24.59 24.67
Mesotrione content percent by mass 1.90 to 2.20 2.08 2.10 2.12
Topramezone suspensibility percent mini. 80 97.85 97.61 97.19
Atrazine suspensibility percent mini. 80 97.62 97.14 96.33
Mesotrione suspensibility percent mini. 80 96.15 96.56 95.65
pH range (1% aq. Suspension) 5.5 to7.5 7.28 7.21 7.15
Pourability 95 % min 98.70 98.50 98.30
Specific gravity 1.14 – 1.60 1.14 1.15 1.16
Viscosity at spindle no.62, 20 rpm 350 -800 cps 510 515 522
Particle size (micron) D50 <3, D90 <10 2.2, 8 2.2, 8.1 2.3, 8.2
Persistent foam ml (after 1 minute) max. 60 nil nil nil

Example 2: Suspension Concentrate (SC) formulation of Topramezone 2.4% + Metribuzin 24 % + Mesotrione 2%

Ingredients %
Topramezone a.i. 2.40
Cloquintocet mexyl safener a.i. 2.40
Metribuzin a.i. 24.00
Mesotrione a.i. 2.00
Ethoxylated Fatty Alcohol 2.00
Acrylic graft copolymer 3.00
Alkylated naphtalene sulfonate, sodium salt 0.50
Silicone antifoam 0.50
1,2-benzisothiazolin-3-one 0.20
Mono Ethylene Glycol 5.00
Xanthan powder 0.20
D.M Water Q.S
Total 100.00

Manufacturing Process of Suspension Concentrate (SC) formulation as per Example 1

Example 3: Water Dispersible Granules (WG) formulation of Topramezone 6% + Metribuzin 60 % + Halosulfuron Methyl 10%

Ingredients %
Topramezone a.i. 6.00
Cloquintocet mexyl safener a.i. 6.00
Halosulfuron methyl a.i. 10.00
Metribuzin a.i. 60.00
Alkyl sulfonate 6.00
sodium salt of sulphonate napthalene formaldehyde condensate 3.00
Silicon Antifoam 0.50
Silicon Dioxide 2.00
China clay Q.S
Total 100.00

Manufacturing Process of Water Dispersible Granules (WG) by extrusion method

Step 1 Charge the required quantity of filler, wetting agent, dispersing agent, and suspending agent, & technical in premixing blender for homogenization for 30 minutes.
Step 2 Pre-blended material is then grinded through Jet mill/ air classifier mills. Finely grinded material is blended in post blender till it becomes homogeneous. (for approx.. 1.5 hr)
Step 3 Finely grinded powder is mixed with required quantity of water to form extrudable dough.
Step 4 Dough is passed through extruder to get granules of required size.
Step 5 Wet granules are passed through Fluidized bed drier and further graded using vibrating screens.
Step 6 Final product is sent for QC approval.
Step 7 After approval material is packed in required pack sizes.

Storage Stability of Water Dispersible Granules (WG) formulation of Topramezone 6% + Metribuzin 60 % + Halosulfuron Methyl 10%

Laboratory storage stability for 14 days
parameters specification (in house) initial heat stability study at 54±2 0C cold storage stability at 0±2 0C
Topramezone content percent by mass 5.70 to 6.60 6.13 6.17 6.21
Cloquintocet mexyl safener percent by mass 5.70 to 6.60 6.15 6.17 6.20
Metribuzin contnet percent by mass 58.20 to 63.00 60.72 60.81 60.92
Halosulfuron Methyl content percent by mass 9.50 to 10.50 10.13 10.14 10.17
Topramezone suspensibility percent min. 70 97.18 96.98 96.87
Metribuzin suspensibility percent min. 70 96.15 95.97 96.01
Halosulfuron Methyl suspensibility percent min. 70 97.15 96.89 96.78
pH range (1% aq. Suspension) 5.5 to 7.5 7.35 7.28 7.16
wettability sec. max. 60 10 12 13
wet sieve (45 micron) percent by mass min. 99.5 99.4 99.4 99.3
bulk density (g/ml) 0.45 to 0.75 0.61 0.61 0.62
moisture content percent by mass max. max. 2% 1.4 1.2 1.1

Room temperature storage stability up to 12 months
Parameters specification (in house) Study Duration
1 month 6 month 12 months
Description Off white colour granules Complies Complies Complies
Topramezone content percent by mass 5.70 to 6.60 6.14 6.16 6.18
Cloquintocet mexyl safener percent by mass 5.70 to 6.60 6.13 6.18 6.22
Metribuzin contnet percent by mass 58.20 to 63.00 60.72 60.8 61.1
Halosulfuron Methyl content percent by mass 9.50 to 10.50 10.12 10.13 10.15
Topramezone suspensibility percent min. 70 97.20 96.98 96.97
Metribuzin suspensibility percent min. 70 96.56 95.89 95.9
Halosulfuron Methyl suspensibility percent min. 70 97.18 96.89 96.88
pH range (1% aq. Suspension) 5.5 to 7.5 7.33 7.19 7.16
wettability sec. max. 60 12 14 15
wet sieve (45 micron) percent by mass min. 99.6 99.5 99.3 99.3
bulk density (g/ml) 0.45 to 0.75 0.61 0.61 0.62
moisture content percent by mass max. max. 2% 1.15 1.1 1.02

Example 4: Wettable Powder (WP) formulation of Topramezone 6% + Metribuzin 60 % + Halosulfuron Methyl 10%

Ingredients %
Topramezone a.i. 6.00
Cloquintocet mexyl safener a.i. 6.00
Halosulfuron methyl a.i. 10.00
Metribuzin a.i. 60.00
Alkylated naphthalene sulfonate, sodium salt 7.00
Sodium lauryl sulphate 4.00
Silicon Antifoam 0.50
Silicon Dioxide 3.50
China clay Q.S
Total 100.00

Manufacturing Process of Wettable Powder (WP) formulation

Step 1 Charge the required quantity of filler, wetting agent, dispersing agent, and suspending agent, & technical in premixing blender for homogenization for 30 minutes.
Step 2 Pre-blended material is then grinded through Jet mill/ air classifier mills. Finely grinded material is blended in post blender till it becomes homogeneous. (for approx.. 1.5 hr)
Step 6 Final product is sent for QC approval.
Step 7 After approval material is packed in required pack sizes.

Storage Stability of Wettable Powder (WP) formulation of Topramezone 6% + Metribuzin 60 % + Halosulfuron Methyl 10%

Laboratory storage stability for 14 days
Parameters Specification (In house) Initial Stability (for 14 days)
At 54±2 0C At 0±2 0C
Description Off white colour flowable liquid Complies Complies Complies
Topramezone content percent by mass 5.70 to 6.60 6.18 6.21 6.23
Cloquintocet mexyl safener percent by mass 5.70 to 6.60 6.20 6.22 6.25
Metribuzin contnet percent by mass 58.20 to 63.00 60.80 60.86 60.97
Halosulfuron Methyl content percent by mass 9.50 to 10.50 10.27 10.30 10.32
Topramezone suspensibility percent mini. 70 96.89 96.54 96.25
Metribuzin suspensibility percent mini. 70 95.16 94.25 93.56
Halosulfuron Methyl suspensibility percent mini. 70 97.23 97.86 97.23
pH range (1% aq. Suspension) 5.5 to7.5 7.35 7.28 7.21
wettability sec. max. 60 11 12 12
wet sieve (45 micron) percent by mass min. 99.5 99.30 99.10 99.00
bulk density (g/ml) 0.3 to .60 0.40 0.41 0.41
moisture content percent by mass max. 2% max 1.2 1.1 1.02

Example 5: Wettable Powder (WP) formulation of Topramezone 3% + Atrazine 30% + 2,4-D Amine Salt 30%

Ingredients %
Topramezone a.i. 3.00
Cloquintocet mexyl safener a.i. 3.00
Atrazine a.i. 30.00
2,4 D Amine a.i. 30.00
Alkylated naphthalene sulfonate, sodium salt 7.00
Sodium lauryl sulphate 4.00
Silicon Antifoam 0.50
Silicon Dioxide 8.00
China clay Q.S
Total 100.00

Room temperature storage data
Parameters Specification (In house) Study Duration
1 month 6 month 12 months
Description Off white colour flowable liquid Complies Complies Complies
Topramezone content percent by mass 5.70 to 6.60 6.22 6.23 6.28
Cloquintocet mexyl safener percent by mass 5.70 to 6.60 6.21 6.25 6.28
Metribuzin contnet percent by mass 58.20 to 63.00 60.85 60.88 60.96
Halosulfuron Methyl content percent by mass 9.50 to 10.50 10.28 10.35 10.40
Topramezone suspensibility percent mini. 70 96.90 96.67 96.35
Metribuzin suspensibility percent mini. 70 95.18 94.35 94.05
Halosulfuron Methyl suspensibility percent mini. 70 98.20 97.85 97.63
pH range (1% aq. Suspension) 5.5 to 7.5 7.33 7.25 7.15
wettability sec. max. 60 15 15 16
wet sieve (45 micron) percent by mass min. 99.5 99.4 99.3 99.3
bulk density (g/ml) 0.3 to 0.6 0.40 0.41 0.41
moisture content percent by mass max. 2 1.6 1.4 1.3

Manufacturing Process of Wettable Powder (WP) formulation as per Example 4

Example 6: Wettable Powder (WP) formulation of Topramezone 3% + Metribuzin 30% + 2,4-D Amine Salt 30%

Ingredients %
Topramezone a.i. 3.00
Cloquintocet mexyl safener a.i. 3.00
Metribuzin a.i. 30.00
2,4 D Amine a.i. 30.00
Alkylated naphthalene sulfonate, sodium salt 6.00
Sodium lauryl sulphate 5.00
Silicon Antifoam 0.50
Silicon Dioxide 8.00
China clay Q.S
Total 100.00

Manufacturing Process of Wettable Powder (WP) formulation as per Example 4
,CLAIMS:CLAIMS
We claim;
[CLAIM 1]. An synergistic herbicidal composition comprising
A) topramezone;
B) at least one herbicide selected from Atrazine and Metribuzin;
C) at least one more herbicide selected from Nicosulfuron, Rimsulfuron, Halosulfuron methyl, Mesotrione, Tembotrione, Sulcotrione, 2,4-D; and
D) one or more other inactive excipients.

[CLAIM 2]. The synergistic herbicidal composition as claimed in claim 1 wherein the component (A) Topramezone is in ratio of 0.1 to 40%, component (B) at least one herbicide selected from Atrazine and Metribuzin is in ratio of 0.1 to 30% and component (C) at least one more herbicide selected from Nicosulfuron, Rimsulfuron, Halosulfuron methyl, Mesotrione, Tembotrione, Sulcotrione, 2,4-D is in ratio of 0.1 to 30%.

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

[CLAIM 4]. The synergistic herbicidal composition as claimed in claim 1-3, wherein the formulations comprises of Suspension Concentrate (SC), Water dispersible granule (WDG or WG), Wettable Powder (WP).

[CLAIM 5]. The synergistic herbicidal composition as claimed in claim 1 or 4, wherein the Suspension Concentrate (SC) formulation comprises:
a) component (A) Topramezone is in ratio of 0.1 to 40% with Cloquintocet mexyl safener a.i., component (B) at least one herbicide selected from Atrazine and Metribuzin is in ratio of 0.1 to 30% and component (C) at least one more herbicide selected from Nicosulfuron, Rimsulfuron, Halosulfuron methyl, Mesotrione, Tembotrione, Sulcotrione, 2,4-D is in ratio of 0.1 to 30%;
b) Ethoxylated Fatty Alcohol
c) Acrylic graft copolymer
d) Alkylated naphtalene sulfonate, sodium salt
e) Silicone antifoam
f) 1,2-benzisothiazolin-3-one
g) Mono Ethylene Glycol
h) Xanthan powder
i) D.M Water.

[CLAIM 6]. The synergistic herbicidal composition as claimed in claim 1 or 4, wherein the Wettable Powder (WP) formulation comprises:
a) component (A) Topramezone is in ratio of 0.1 to 40% with Cloquintocet mexyl safener a.i., component (B) at least one herbicide selected from Atrazine and Metribuzin is in ratio of 0.1 to 30% and component (C) at least one more herbicide selected from Nicosulfuron, Rimsulfuron, Halosulfuron methyl, Mesotrione, Tembotrione, Sulcotrione, 2,4-D is in ratio of 0.1 to 30%;
b) Alkylated naphthalene sulfonate, sodium salt
c) Sodium lauryl sulphate
d) Silicon Antifoam
e) Silicon Dioxide
f) China clay.

[CLAIM 7]. The synergistic herbicidal composition as claimed in claim 1 or 4, wherein the Wettable Granule (WDG/WG) formulation comprises:
a) component (A) Topramezone is in ratio of 0.1 to 40% with Cloquintocet mexyl safener a.i., component (B) at least one herbicide selected from Atrazine and Metribuzin is in ratio of 0.1 to 30% and component (C) at least one more herbicide selected from Nicosulfuron, Rimsulfuron, Halosulfuron methyl, Mesotrione, Tembotrione, Sulcotrione, 2,4-D is in ratio of 0.1 to 30%;
b) Alkyl sulfonate
c) sodium salt of sulphonate napthalene formaldehyde condensate
d) Silicon Antifoam
e) Silicon Dioxide
f) China clay.

[CLAIM 8]. The synergistic herbicidal composition as claimed in any of the preceding claims, wherein the said composition is to be used to manage or control weeds selected from 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, Convolvulus arvensis, Conyza canadensis, Corchorus acutangulus, Coronopus didymus, Crotalaria serice, Cucumis callosus, Cuscuta campestris, Cuscuta chinensis, Cynodon dactylon, Cyanotis axillaris, Cyperus esculenthus, Cyperus iria, 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, 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.

[CLAIM 9]. The synergistic herbicidal composition as claimed in any of the preceding claims, wherein the said composition controlling the growth of undesirable vegetation, in monocot and dicot crops including genetically modified and conventional or non genetically modified varieties of sugarcane (Saccharum officinarum), corn/maize (Zea mays), Sorghum (Sorghum bicolor), Pearl millet (Pennisetum glaucum), Soybean (Glycin max), Peanut (Arachis hypogaea), Sunflower (Helianthus annuus), Green gram (Vigna radiata), Black gram (Vigna mungo), Chickpea (Cicer aritinum), Cowpea (Vigna unguiculata), Redgram (Cajanus cajan), Frenchbean (Phaseolus vulgaris), Indian bean (Lablab purpureus), Horse gram (Macrotyloma uniflorum), Field pea (Pisum sativum), Cluster bean (Cyamopsis tetragonoloba), Lentils (Lens culinaris), Apple (Melus domestica), Banana (Musa spp.), Citrus groups (Citrus spp.), Grape (Vitis vinifera), Guava (Psidium guajava), Litchi (Litchi chinensis), Mango (Mangifera indica), Papaya (Carica papaya), Pineapple (Ananas comosus), Pomegranate (Punica granatum) , Sapota (Manilkara zapota), Tea (Camellia sinensis), Coffea (Coffea Arabica), Coconut (Coco nucifera).