DESC:FIELD OF THE INVENTION:

The present invention relates to novel synergistic herbicide composition comprising Pendimethalin, Pyrazosulfuron- ethyl and Zinc. The present invention also relates to process for preparing the said composition comprising of synergistic bioactive amounts of Pendimethalin, Pyrazosulfuron - ethyl and Zinc along with one or more inactive excipients.

BACKGROUND OF THE INVENTION

Pesticides are chemicals that may be used to kill fungus, bacteria, insects, plant diseases, snails, slugs, or weeds among others. These chemicals can work by ingestion or by touch and death may occur immediately or over a long period of time.

Herbicides are type of pesticides also commonly known as weed killers, which are chemical substances used to control unwanted plants. Selective herbicides control specific weed species, while leaving the desired crop relatively unharmed, while non-selective herbicides sometimes called "total weed killers" can be used to clear waste ground, industrial and construction sites, railways and railway embankments as they kill all plant material with which they come into contact.

There are many different types of herbicides containing different chemicals and having different modes of actions. The different types of herbicides are all designed to kill plant tissue. However, they accomplish it by two basic methods, Contact Herbicides and Systemic Herbicides.

Contact herbicides: Contact is a word that means the chemical in that specific type of herbicide will kill the parts of the plant it contacts. For broadleaf weeds this means it will kill the above ground leafy part of the plants. It will not directly kill the below ground plants parts, such as roots, bulbs, tubers, or rhizomes. Contact herbicides are popular because they work quickly by killing the tissue in as fast as one day. Some herbicides will combine contact with systemic chemicals for a faster effect.

Systemic Herbicides: For systemic types of herbicides, the word "Systemic" means the plant absorbs through the leaves or stems and transports it internally throughout the plant. The chemical travels with the sap so it usually doesn't have the quick "knockdown" effect. The greatest benefit of a systemic type of herbicide is that it will kill the entire plant, roots and all. The speed of chemical movement in the plant is largely dependent on soil and air temperature. A chemical sprayed in early spring may take a couple weeks longer to work than the same chemical sprayed in mid-summer. The speed of kill is also dependent on the "mode of action" of the chemical (how the chemical works inside the plant).

Pendimethalin was first disclosed in DE 2232263.Pendimethalin is chemically known as N-(1-Ethylpropyl)-3, 4-dimethyl-2, 6-dinitrobenzenamineand having chemical structure as below;

Pendimethalin is an herbicide of the dinitroaniline class used in pre-emergence and post-emergence applications to control annual grasses and certain broadleaf weeds. It inhibits cell division and cell elongation. Pendimethalin protects crops like wheat, corn, soybeans potatoes, cabbage, peas, carrots and asparagus. It is used to control annual grasses and certain broadleaf weeds which interfere with growth, development, yield and quality of agricultural and horticultural crops by competing on nutrients, water and light.

Pyrazosulfuron-ethyl is a chemical compound from the group of the sulfonylureas, and an herbicide which discovered in 1982 and 1990 by Nissan Chemical was put on the market. Pyrazosulfuron-ethyl is chemically known as
Ethyl-5-[({[(4,6-dimethoxypyrimidin-2-yl)amino]carbonyl}amino)sulfonyl]-1-methyl-1 H -pyrazol-4-carboxylatand having chemical structure as below

Pyrazosulfuron-ethyl is under the tradenames AGREEN and Sirius used as systemic herbicide in rice cultivation. It acts by inhibiting acetolactate synthase.

Zinc is a chemical element. Zinc deficiency is crop plants most common micronutrient deficiency; it is particularly common in high-pH soils. Plants that grow in soils that are zinc-deficient are more susceptible to disease. Zinc is primarily added to the soil through the weathering of rocks, but humans have added zinc through fossil fuel combustion, mine waste, phosphate fertilizers, pesticide (zinc phosphide), limestone, manure, sewage sludge, and particles from galvanized surfaces. Excess zinc is toxic to plants, although zinc toxicity is far less widespread.

The main concern with the use of herbicide is the development of resistance by the weeds for that particular herbicide and at the end one has to apply more concentrated formulation of the herbicide. The high amount of herbicide may results in the toxicity to human beings as well as has bad effect on environment. Further the most of the herbicides lacks with multiple actuation on different types of weeds.

Previously people have tried many alternatives and option to overcome this problem and as a result developed poly mixture of pesticide, use of non-toxic ingredients and developing novel formulations which provides effective amount of the pesticide and at the required part only.

However the use of poly mixture containing large number of pesticides poses a problem in many was like preparing formulation of multiple pesticides with different chemical properties and behavior and physical properties. It also creates challenge for formulator in term of compatibility and stability of all the pesticide along with used excipients in the formulation.

CN 104222131 A discloses herbicidal composition comprising Pyrazosulfuron-ethyl, oxadiazon, Pendimethalin and a synergist, wherein the mass ratio of Pyrazosulfuron-ethyl to oxadiazon to Pendimethalin to the synergist is (1-20) :( 5-25) :( 5-45) :( 1-5).

CN 101856031 A discloses herbicidal composition comprising cyhalofop-butyl and Pyrazosulfuron-ethyl into three types of water dispersing granules, a suspending agent and a wettable powder. The said herbicides are also compounded with Pendimethalin.

The development of such products is relatively simple providing that the active ingredients to be combined are physically, chemically and biologically compatible. In these situations the active ingredients can be combined in a broad range of formulation types well known in the art. Where the active ingredients are not physically, chemically and/or biologically compatible, it has been necessary to develop novel formulations to overcome the problems associated with such incompatibilities. One example of a formulation type is the so-called ‘Soil Applied Granules’ (SAG).

Inventors of the present invention have surprisingly found that the novel synergistic composition of Pendimethalin in combination with Pyrazosulfuron-ethyl and Zinc as described herein in can provide solution to the above mentioned problems. Further the present invention the novel synergistic composition provides multisite action of different weeds in results with delay resistance development the combination is also effective on broad spectrum weeds it is also easy to apply as only one formulation controls broad spectrum weeds.

SUMMARY OF THE INVENTION

The present invention relates to a novel herbicide composition which comprises synergistic bioactive amounts of Pendimethalin in combination with Pyrazosulfuron-ethyl and Zinc and at least one more inactive excipients.

Further the present invention also relates to process for preparing novel herbicide composition which comprises synergistic bioactive amounts of Pendimethalin in range of 1-40%, Pyrazosulfuron-ethyl in range of 0.01-20% and Zinc in range of 1-40% and excipients.

Accordingly, in a third aspect, the present invention provides a method of protecting a plant propagation material, a plant, parts of a plant and/or plant organs that grow at a later point in time against pathogenic damage or pest damage by applying to the plant propagation material a composition comprising a formulated mixture defined in the first aspect.

Accordingly, in a fourth aspect of the present invention is to be develop suitable formulations selected from Soil Applied Granules (SAG), Water Dispersible Granules (WDG), ZC formulation (ZC).

Accordingly, in a another aspect the said composition is to be developed in suitable formulations selected from Soil Applied Granules (SAG), Water Dispersible Granules (WDG), ZC formulation (ZC) powder & liquid formulation comprising Pendimethalin in combination with Pyrazosulfuron-ethyl and zinc and the salts thereof which are standard in agriculture or mixture thereof; and optionally one or more customary formulation adjuvants such as a) dispersant b) wetting agent c) anti-foaming agent d) biocides e) anti freezing agent f) suspending agent g) thickener h) coating agent and i) buffering agent.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides a novel herbicide composition which comprises synergistic bioactive amounts of Pendimethalin in combination with Pyrazosulfuron-ethyl and Zinc and optionally one or more inactive excipients.

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

As used herein “Pyrazosulfuron” or “Pyrazosulfuron-ethyl” to be considered as synonym and can be used interchangeably.

The novel herbicidal synergistic compositions comprising the formulation of the present invention can be classified as below:

The formulation can be in various physical forms, for example in the form of a Soil Applied Granules (SAG), Water Dispersible Granules (WDG), ZC formulation (ZC), dustable powder (DP), a gel, a wettable powder (WP), a granule (GR) (such as an emulsifiable granule (EG) or more particularly a water-dispersible granule (WG)), a water-dispersible tablet (WT), an emulsifiable concentrate (EC), a micro- emulsifiable concentrate, an oil-in-water emulsion (EW), an oil flowable (e.g. a spreading oil (SO)), an aqueous dispersion (e.g. aqueous suspension concentrate (SC)), an oily dispersion (OD), a suspo-emulsion (SE), a capsule suspension (CS), a soluble liquid, a water-soluble concentrate (with water or a water-miscible organic solvent as carrier), an impregnated polymer film, or jumbo formulation.

Preferably, the formulation is in the form of a Soil Applied Granules (SAG), Water Dispersible Granules (WDG), ZC formulation (ZC).

The term “Granular formulation” and “Soil Applied Granules’ (SAG)” are interchangeable and are similar to each other both have the same meaning.

It is of substantial importance to increase the amounts of active ingredients in specific formulations since it enables the reduction in amounts of formulation to be applied, the storage volume during distribution as well as the production costs thereof. Another prerequisite for a successful formulation is a satisfactorily large spreadability, which together with the sufficient active ingredient content contributes to the above effects. Without sufficient spreadability, the amount of application cannot be reduced, eventually leading to the necessity in large storage amounts and high production costs. Therefore, sufficiently high active ingredient content and a satisfactorily large spreadability are the most important factors for the production of advantageous formulation. In addition to these factors, it is also important to consider environmental aspects.

Surfactants are non-ionic and anionic surfactants. The non-ionic surfactants are polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylenestyryl aryl ethers, polyoxyethylenepolyoxypropylene block polymers, sorbitan fatty acid esters, polyoxyethylenesorbitan fatty acid esters, glyceric fatty acid esters, polyoxyethyleneglyceric fatty acid esters, acetylene glycols, and acetylene alcohols. The anionic surfactants are calcium alkylbenzenesulfonates, sodium alkyl sulfosuccinates, and sodium polyoxyethylene alkyl aryl ether sulfate esters. In addition to the above illustrated surfactants, no particular limitation is imposed on the surfactants being used in the present formulation, if they can be used for either emulsifiable concentrates or spreadable oil formulations. The surfactants added in the liquid pesticide mixtures are in the range of 5 to 15% of the total weight, but more preferably 10%.

Thickeners or gelling agents are selected from but not limited to ethyl cellulose, methyl cellulose; sodium carboxymethyl cellulose (SCMC); hydroxyethyl cellulose (HEC) or mixtures thereof can be added for controlling the viscosity of the liquid pesticide mixture.

Anti-decomposition agents or stabilizers such as epichlorohydrin, soybean oil, phosphoric acid, can also be added to the liquid pesticide mixture for stabilizing the physico-chemical properties of the formulations during the prolonged storage. When the formulations are applied to the paddy water, Pendimethalin in combination with Pyrazosulfuron-ethyl and Zinc and excipients from the formulations should be released within a day.

In one of the embodiment of the present invention the method of application of the formulation comprising of Pendimethalin in combination with Pyrazosulfuron-ethyl and Zinc are by broadcasting in standing water by manual or by machine. Broadcasting can be done as direct granules broadcasting or mixing with sand or mixing with fertilizer, spraying with manual or machine operated knapsack sprayer, back pack sprayer, jumbo ball application, and Shaker bottle application. The formulation of the present invention can be in any of the form described above.

In one of the embodiment of the present invention on method of application of the formulation comprising of Pendimethalin in combination with Pyrazosulfuron-ethyl and Zinc the time of application or formulations are applied before or after paddy sowing or transplanting, or before weed germination or after weed germination.

Formulation of the present invention can be in any of the form described above.

As per embodiment the novel herbicide formulation comprises Pendimethalin in combination with Pyrazosulfuron-ethyl and Zinc.

As per embodiment Zinc is present with Pendimethalin and Pyrazosulfuron-ethyl as per below range of % w/w:

Pendimethalin Pyrazosulfuron-ethyl Zinc
1-40% 0.01-20% 1-40%

The term “zinc” relates to any one of the form Zinc Sulfate Monohydrate (ZnSO4,H2O), Zinc Sulfate Heptahydrate (ZnSO4,7H2O ), Zinc Oxysulphate (ZnSO4xZnO), Zinc Oxide (ZnO), Zinc carbonate (ZnCO3), Zinc Chloride (ZnCl2), Zinc EDTA/Zinc chelate, Zinc Gluconate, Zinc Lactate Gluconate, Zinc Polyflavonoid, Zinc lignosulphate. The various forms of zinc in the present formulation optionally may be used in nanoparticles form.

Zinc (Zn) is one of the eight essential micronutrients. It is needed by plants in small amounts, but yet crucial to plant development. In plants, zinc is a key constituent of many enzymes and proteins. It plays an important role in a wide range of processes, such as growth hormone production and inter-node elongation.

Zinc deficiency is probably the most common micronutrient deficiency in crops worldwide, resulting in substantial losses in crop yields and human nutritional health problems. Deficiency in zinc might result in significant reduction in crop yields and quality. In fact, yield can even be reduced by over 20% before any visual symptoms of the deficiency occur. The cost to the farmer, associated with loss of production, is by far higher than the cost of testing the soil and plant tissue and applying zinc fertilizers.

The mobility of zinc in plants varies, depending on its availability in the soil or growing media. When zinc availability is adequate, it is easily translocated from older to younger leaves, while when zinc is deficient, movement of zinc from older leaves to younger ones is delayed.

Therefore, zinc deficiency will initially appear in middle leaves. Symptoms of zinc deficiency include one or some of the symptoms are: Stunting - reduced height, Interveinal chlorosis, Brown spots on upper leaves, distorted leaves, reduced tillering, reduction in leaf size.

As mentioned above, the visual symptoms usually appear in severely affected plants. When the deficiency is marginal, crop yields can be reduced by 20% or more without any visible symptoms.

Zinc deficiency is common in many crops and on a wide range of soil types. It affects the main cereal crops: rice, wheat and maize as well as different fruit crops, vegetables and other types of crops. Zinc (Zn) deficiency affects several biochemical processes in the rice plant, thus severely affecting plant growth. It is important to prevent zinc deficiency than to correct it.

As per another embodiment Zinc deficiency is corrected or prevented by application of zinc combination with Pendimethalin and Pyrazosulfuron-ethyl formulation. It is applied as soil application as well as foliar application. Application of zinc in combination with Pendimethalin and Pyrazosulfuron-ethyl formulation on early stage of the crop is very essential for normal plant growth. In rice, it can be applied before crop sowing or transplanting to grain filling stage.

As per another embodiment Zinc in combination with Pendimethalin and Pyrazosulfuron-ethyl formulation is formulated as various forms of Zinc. Various sources or salts of zinc are Zinc Sulfate Monohydrate (ZnSO4,H2O), Zinc Sulfate Heptahydrate (ZnSO4,7H2O ), Zinc Oxysulphate (ZnSO4xZnO), Zinc Oxide (ZnO), Zinc carbonate (ZnCO3), Zinc Chloride (ZnCl2), Zinc EDTA/Zinc chelate, Zinc Gluconate, Zinc Lactate Gluconate, Zinc Polyflavonoid, Zinc lignosulphate. The various forms of zinc in the present formulation optionally may be used in nanoparticles form.

The rate of application of zinc varies from 100 g to 10 kilogram per hectare depending upon soil texture, soil pH, organic matter, redox potential, temperature, C: N ratio, nutrient interaction, cropping pattern etc. In India soil with cropping pattern of rice-wheat rotation is highly deficient in zinc, red soil, deep cotton black soil and calcareous soil are highly deficient in zinc.

The novel herbicide composition of the present invention is effective for control or management of weeds in Crops like Paddy (Oryza sativa L.) including Indica, Japonica and Javanica race. GMO Paddy. It can be applied in nursery as well as main field after sowing or transplanting. Sugarcane (Saccharumofficinarum), Cotton (Gossypium spp.), Jute (Corchorusoliotorus), Wheat (Triticumaestavum), Barley (Hordeumvulgare), Maize (Zea mays), Sorghum (Sorghum bicolor), Ragi (Eleusinecoracana), Pearl millet (Pennisetumglaucum), Brinjal (Solanummelongena), Onion (Allium cepa L.), Tomato (Solanumlycopersicun) , Potato (Solanumtuberosum) , Sweet potato (Ipomoea batatas), Chilly (Capsicum annum), Garlic (Allium sativum)

The novel herbicide composition of the present invention can be used to control the weed Aeschynomeneaspera, Aeschynomeneindica, Ageratum conyzoides, Alternantherasessilis, Alternantheraphiloxeroides, Amaranthusspinosus, Amaranthusviridis, Ammaniabaccifera, Cynodondactylon, Dactylocteniumaegyptium, Digitariaciliaris, Digitariasetigera, Ischaemumrugosum, Echinochloacolona, Echinochloa crus-galli, Echinochloaglabrescens, Echinochloa crus-pavonis, Echinochloaesculenta, Echinochloafrumentacea, Echinochloamuricata, Echinochloaoryzoides, Echinochloapaludigena, Eleochariskuruguwai, Laptochloachinensis, Eleusineindica, Eclipta alba, Eclipta prostate, Imperata cylindrical, Leersiahexandra, Leptochloachinensis, Oryza sativa, Panicumrepens, Paspalumdistichum, Paspalumscrobiculatum, Rottboelliacochinchinensis, Setariaglauca, Bolboschoenusmaritimus, Bergiacapensis, Commelinabenghalensis, Commelinadiffusa, Cyanotisaxillaris, Eclipta alba, Eclipta prostrate, Eichhorniacrassipes, Ipomoea aquatic, Ludwigiaadscendens, Ludwigiahyssopifolia, Ludwigiaoctovalvis, Ludwigiaparviflora, Marsileaminuta, Marsileaquadrifoliata, Mimosa diplotricha, Monochoriavaginalis, Pistiastratiotes, Polygonumhydropiper, Portulacaoleracea, Sagittariamilliacea, Sagittariasagittifolia, Sphenocleazeylanica, Trianthemaportulacastrum, Typha spp., Isachneglobosa, Paspalumdistichum, Cyperusdifformis, Cyperushaspen, Cyperusiria, Cyperusrotundus, Fimbristylisdichotoma, Fimbristylismiliacea, Scirpusjuncoides, Scirpusnipponicus, Scirpusplaniculmis, Scirpurroyelei, Scirpusjuncoides

The novel herbicide composition comprising of formulation of the present invention in addition to Pendimethalin in combination with Pyrazosulfuron-ethyl and Zinc further optionally comprises inactive excipients 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.

In further embodiment of the invention was to provide a nanoparticles of various forms of Zinc with combination of Pendimethalin and Pyrazosulfuron-ethyl.

The mean particle size of the nanoparticles of various forms of Zinc is in the range from 1 to 1000 nm, preferably 1 to 100, more preferably 1 to 50 nm, determined by means of X-ray diffraction spectroscopy.

The term “nanoparticles” relates to one type or a mixture of different types of said compounds. Suitable zinc in any one of the form of various forms of Zinc are Zinc Sulfate Monohydrate (ZnSO4,H2O), Zinc Sulfate Heptahydrate (ZnSO4,7H2O ), Zinc Oxysulphate (ZnSO4xZnO), Zinc Oxide (ZnO), Zinc carbonate (ZnCO3), Zinc Chloride (ZnCl2), Zinc EDTA/Zinc chelate, Zinc Gluconate, Zinc Lactate Gluconate, Zinc Polyflavonoid, Zinc lignosulphate.

A dispersant is a substance which adsorbs onto the surface of particles and helps to preserve the state of dispersion of the particles and prevents them from re-aggregating. Dispersants are added to agrochemical formulations to facilitate dispersion and suspension during manufacture, and to ensure the particles re-disperse into water in a spray tank. They are widely used in wettable powders, suspension concentrates and water-dispersible granules. Surfactants that are used as dispersants have the ability to adsorb strongly onto a particle surface and provide a charged or steric 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 or mixtures thereof.

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

Thickeners or gelling agents are used mainly in the formulation of suspension concentrates, emulsions and suspoemulsions 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, e.g. 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, e.g., 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.

In further embodiment of the invention provide novel herbicide composition which comprises a dye therein. The dye is beneficially a drain tracing dye, and beneficially comprises one or more food grade ingredients. Such food grade ingredients are beneficially used as they are not harmful to a person if ingested.

The dye is beneficially in a granulated form. This provides the benefit that it can be pre-mixed with the herbicide and the capsule filled with both dye and herbicide ready for use. Examples of suitable dyes which are commercially available and their colours are green (acid yellow 73), red (food amaranth), blue (food blue FCF), orange (food sunset yellow), yellow (food tartrazine), purple (food P/N). Such dye materials are beneficially in powdered form and are beneficially water soluble.

The wettable dry granules (WDG) can be applied after disintegration and dispersion in water. Water dispersible granules can be formed by a) agglomeration, b) spray drying, or c) extrusion techniques.

WDG formulations offer a number of advantages in packaging, ease of handling and safety. The WDG are preferably of uniform size and which are free flowing, low dusting and readily disperse in water to form a homogenous solution of very small particles which may pass through conventional spray nozzles. Ideally WDG formulations when dispersed in water under gentle agitation for five minutes have residues of less than 0.01% on a 150 µm sieve screen and less than 0.5% on a 53 µm screen. The granules can usually be measured accurately by volume which is convenient for the end user.

The SC formulation can be prepared by below described method;
STEP-I: Adding anti-microbial agent and gum in water under continuous stirring followed by slow addition. Continuing stirring until homogeneous dispersion is formed.
STEP-II: Mixing anti-freezing agent, dispersant, wetting agent, anti-microbial agentand anti-foaming agent in water for 30 minute until homogeneous solution is formed. Finally Pendimethalin, Pyrazosulfuron-ethyl and Zinc are added slowly under continuous stirring at 30 minutes till homogeneous dispersion is obtained. Milling the slurry through bead mill until required particle size is achieved.
Step-III: Adding rest of water, anti-foaming agent and gum solution under continuous stirring to get desired viscosity of the suspension. Continue stirring for about 4 hr. to obtain homogeneous formulation.

The process for preparing the present novel synergistic composition can be modified accordingly by any person skilled in the art based on the knowledge of the manufacturing the formulation. However all such variation and modification is still covered by the scope of present invention.

In a preferred embodiment of this aspect of the invention, said herbicidally effective amount of Pendimethalin in combination with Pyrazosulfuron-ethyl and Zinc and excipients mixture effective amount are dissolved in solvent and along with excipients effective amount are emulsified; and said emulsion is co-extruded or sprayed with a carrier selected from soapstone, kaolin, talc, titanium dioxide and mixtures thereof or sprayed on provided blank granules' selected from the group comprising bentonite, attapulgite, ceramic, montmorillonite, pumice, sepiolite, diatomaceous earth, clay, sand, dolomite and calcite.

In this embodiment, the pre-formed emulsion comprising Pendimethalin in combination with Pyrazosulfuron-ethyl and Zinc be either (i) admixed with an inert carrier selected from soapstone, kaolin, talc and mixtures thereof and prepared a dough therefrom, the dough being extruded and dried to afford the target granules; or (ii) sprayed on blank granules selected from the group comprising bentonite, attapulgite, ceramic, montmorillonite, pumice, sepiolite, diatomaceous earth, clay, sand, dolomite and calcite and dried to afford the target granules. It has been found that irrespective of the process used to granulate the pre-formed emulsion, whether by extrusion or spraying, the resultant granules always displayed enhanced stability of Pendimethalin in combination with Pyrazosulfuron-ethyl and Zinc when the solution presented for granulation was an emulsion comprising either Pyrazosulfuron ethyl or Pendimethalin or both.

Process for Preparation of Pendimethalin and Pyrazosulfuron -ethyl Granules (GR):
1. Herbicidally effective amount of Pendimethalin in combination with Pyrazosulfuron-ethyl are dissolved in solvent and along with excipients effective amount to produce emulsion concentrate for coating.
2. Blank granules are charged in booth mixture and sprayed with emulsion concentrate from step 1. Booth mixture operates continuously during addition of liquid.
3. After addition of liquid on blank granules, material is homogenized for 20 minutes.
4. After completion of homogenization, various form of Zinc powder is added to coat granules.

In preferred embodiment, the soil applied granules comprising Pendimethalin in combination with Pyrazosulfuron-ethyl and zinc are prefeblayy prepared by any one of the process:
Process (A): Manufacturing process of Granules by Coating Method
Step 1 Take required quantity of bentonite in booth mixer.
Step 2 Take required quantity Pendimethalin technical (melted/liquid) and emulsifiers and spray on bentonite.
Step 3 After completion of step 2 spray Pyrazosulfuron tech. on bentonite. Mix well till homogenized.
Step 4 Now take remaining fillers Zinc and China clay and mix well till homogenized.
Step 5 Final product is sent for QC department approval.
Step 6 After approval material is packed in required pack sizes.

Process (B): Manufacturing process of Granules by Impregnation method
Step 1 Charge the required quantity of filler, wetting agent, dispersing agent, emulsifiers and technical in high shear granulator. Mix it well, till it becomes homogeneous.
Step 2 Final product is sent for QC department approval.
Step 3 After approval material is packed in required pack sizes.

Process (C): Manufacturing process of Granules by extrusion method
Step 1 Charge the required quantity of filler, wetting agent, dispersing agent, suspending agent and 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 extricable 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.

The process for preparing the present novel synergistic herbicide formulation can be modified accordingly by any person skilled in the art based on the knowledge of the manufacturing the formulation. However all such variation and modification is still covered by the scope of present invention.

List of inactive agent which may be used in the present invention are listed below but not limited to:

Inactive excipients used in Granules (Ready to use) formulation
Excipients Function
Zinc Sulfate Monohydrate (ZnSO4,H2O), Zinc Sulfate Heptahydrate (ZnSO4,7H2O ), Zinc Oxysulphate (ZnSO4xZnO), Zinc Oxide (ZnO), Zinc carbonate (ZnCO3), Zinc Chloride (ZnCl2), Zinc EDTA/Zinc chelate, Zinc Gluconate, Zinc Lactate Gluconate, Zinc Polyflavonoid, Zinc lignosulphate. Filler
China clay, Vermiculite, Quartz sand, Silica, River sand, Diatomaceous earth, Corn cob grits, Montmorillonite, Kaolin, Talc, Calcium carbonate Filler
Aluminium phyllosilicate clay (bentonite clay) Filler,Absorbent
Polyaryl Phenol Ethoxylate Emulsifier, Wetting agents, Dispersants & Stabilizers
Calcium Dodecyl Benzene Sulphonate, Isopropyl alcohol phosphate, Polyoxy ethylene ethanoxy ether & dihydroxy diethyl ether blend Emulsifiers
Precipitated Silica Anti-caking and Free-flow agent
Urea formaldehyde Resin
Sodium montmorillonite (Bentonite)

Inactive excipients used in WG formulation

Excipients Function
Sodium salt of naphthalene sulfonate condensate, Modified polyacrylate copolymer, Sodium polycarboxylate, Sodium Ligno sulfonate, Alkyl naphthalene sulfonate condensate, sodium salt, Dispersing Agent
Polyacrylate co-polymer Dispersing Agent, Stabilizer, Emulsifier
Alcohol block co-polymer Co-dispersant
Blend of naphthalene sulfonate condensate & phenol sulfonate condensate Wetting Agent & Dispersing Agent
blend of naphthalene sulfonate condensate, Sodium dodecylbenzene sulfonate, Sodium lauryl sulfate, Blend of alkyl naphthalene sulfonate and anionic wetting agent, Sodium n-butyl naphthalene sulfonate, Sodium isopropyl naphthalene sulfonate, Blend of sodium alkyl aryl sulfonates Wetting Agent
Corn starch Binder, Filler
Silicon dioxide Suspending agent, Anti-caking Agent, Filler
Urea formaldehyde resin / Urea-methanol Anti-caking agent
Lactose, China clay/ Kaolin, Titanium dioxide, Talcum powder, Diatomaceous earth Filler
Polyvinylpyrrolidone Binder
Silicone antifoam emulsion Defoaming agent
Fatty amine ethoxylate Wetting agent, Dispersing agent, Stabilizers, Sanitizers, Defoaming agent

Inactive excipients used in ZC formulation

Excipients Function
Acrylic graft copolymer, Alkylated naphthalene sulfonate, sodium salt, Sodium salt of naphthalene sulfonate condensate, Sodium ligno sulfonate Dispersing agent
Polyalkoxy alkyl ether, Ethylene oxide/propylene oxide block copolymer Dispersing agent, Emulsifier
Polyarylphenyl ether phosphate, Ethoxylated Fatty Alcohol Dispersing agent & Wetting agent
Trisiloxane ethoxylate Wetting agent & Spreader
Sodium dioctyl sulfosuccinate Wetting agent & Emulsifier
Silicone antifoam emulsion Antifoam
Polysaccharide Rheology Modifier,Thickner
Glycol (Monoethylene glycol, Diethylene glycol, Polypropylene glycol, Polyethylene glycol), Glycerene Antifreezing Agent
1,2-benzisothiazolin-3-one, 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 Biocide/Preservative
Aluminum Magnesium Silicate Suspending aid
Silicon dioxide Suspending aid, Anticaking agent
Polydimethyl siloxane Antifoaming agent
Organo modified Trisiloxane Spreader
Poly glycerol ester Sticker, Penetrant
Poly ether Deposition aid

The process for preparing the present agrochemical composition can be modified accordingly by any person skilled in the art based on the knowledge of the manufacturing the composition. However all such variation and modification is still covered by the scope of present invention.

EXAMPLES

Example 1 (Recipe-1) Pendimethalin 15% + Pyrazosulfuron Ethyl 0.15% Granule

Chemical Composition Percent (% w/w)
Pendimethalin a.i. 15.00
Pyrazosulfuron ethyl a.i. 0.15
Polyaryl phenol ethoxylate 3.00
Calcium dodecyl benzene sulfonate 2.00
China Clay 3.00
Zinc 20.00
Sodium montmorillonite (Bentonite) Q.S.
Total 100.00

Process: Manufacturing process of Granules by Coating Method

Step 1 Take required quantity of bentonite in booth mixer.
Step 2 Take required quantity Pendimethalin technical (melted/liquid) and emulsifiers and spray on bentonite.
Step 3 After completion of step 2 spray Pyrazosulfuron tech. on bentonite. Mix well till homogenized.
Step 4 Now take remaining fillers Zinc and China clay and mix well till homogenized.
Step 5 Final product is sent for QC department approval.
Step 6 After approval material is packed in required pack sizes.

Storage stability-Pendimethalin 15% + Pyrazosulfuron Ethyl 0.15% Granule
Parameters Specification Initial Heat stability at 54+2 0C for 14 days
In house
Description Green color Granules Complies Complies
Pendimethalin content percent by mass 14.25-15.75 15.35 15.30
Pyrazosulfuron Ethyl content percent by mass 0.14-0.17 0.16 0.15
pH range (1% aq. Suspension) 5.5-7.5 7.13 7.12
Moisture content (%) 3 1.50 0.80
Bulk Density 0.80 - 1.20 0.99 0.99

Room temperature storage data
Parameters Specification Study Duration
In house 1 month 6 month 12 months
Description Green color Granuals Complies Complies Complies
Pendimethalin content percent by mass 14.25-15.75 15.35 15.34 15.33
Pyrazosulfuron Ethyl content percent by mass 0.14-0.17 0.16 0.16 0.15
pH range (1% aq. Suspension) 5.5-7.5 7.13 7.12 7.12
Moisture content (%) 3 1.7 1.2 1
Bulk Density 0.80 - 1.20 0.99 0.99 0.99

Example 2-Recipe-2-Pendimethalin 15% + Pyrazosulfuron Ethyl 0.15% Granule
Chemical Composition Percent (% w/w)
Pendimethalin a.i. 15.00
Pyrazosulfuron ethyl a.i. 0.15
Polyaryl phenol ethoxylate 3.00
Calcium dodecyl benzene sulfonate 2.00
China clay 3.00
Urea formaldehyde Resin 3.00
Sodium montmorillonite (Bentonite) Q.S.
Total 100.00

Process As per Example 1
Storage stability-Pendimethalin 15% + Pyrazosulfuron Ethyl 0.15% Granule
Parameters Specification Initial Heat stability at 54+2 0C for 14 days
In House
Description Green color Granules Complies Complies
Pendimethalin content percent by mass 14.25-15.75 15.25 15.15
Pyrazosulfuron Ethyl content percent by mass 0.14-0.17 0.16 0.15
pH range (1% aq. Suspension) 5.5-7.5 7.15 7.13
Moisture content (%) 3 1.50 0.80
Bulk Density 0.80 - 1.20 0.99 0.99

Room temperature storage data
Parameters Specification Study Duration
In house 1 month 6 month 12 months
Description Green color Granules Complies Complies Complies
Pendimethalin content percent by mass 14.25-15.75 15.25 15.25 15.22
Pyrazosulfuron Ethyl content percent by mass 0.14-0.17 0.16 0.15 0.15
pH range (1% aq. Suspension) 5.5.-7.5 7.15 7.15 7.14
Moisture content (%) 3 1.7 1.2 1
Bulk Density 0.80-1.20 0.99 0.99 0.99

Example 3: Pendimethalin 15% + Pyrazosulfuron Ethyl 0.15% Granule
Chemical Composition Percent (% w/w)
Pendimethalin 38.7% *CS 39.30
Pyrazosulfuron ethyl a.i. 0.15
Polyaryl phenol ethoxylate 3.00
Calcium dodecyl benzene sulfonate 2.00
China Clay 3.00
Zinc 20.00
Sodium montmorillonite (Bentonite) Q.S.
Total 100.00
*capsule suspension
Process: Manufacturing process of Granules by Coating Method
Step 1 Take required quantity of bentonite in booth mixer.
Step 2 Take required quantity Pendimethalin technical (melted/liquid) and emulsifiers and spray on bentonite.
Step 3 After completion of step 2 spray Pyrazosulfuron -ethyl tech. on bentonite. Mix well till homogenized.
Step 4 Now take remaining fillers Zinc and China clay and mix well till homogenized.
Step 5 Final product is sent for QC department approval.
Step 6 After approval material is packed in required pack sizes.

Storage stability-Pendimethalin 15% + Pyrazosulfuron Ethyl 0.15% Granule
Parameters Specification Initial Heat stability at 54+2 0C for 14 days
In house
Description Green color Granules Complies Complies
Pendimethalin content percent by mass 14.25-15.75 15.35 15.30
Pyrazosulfuron Ethyl content percent by mass 0.14-0.17 0.16 0.15
pH range (1% aq. Suspension) 5.5-7.5 7.13 7.12
Moisture content (%) 3 1.50 0.80
Bulk Density 0.80 - 1.20 0.99 0.99

Room temperature storage data
Parameters Specification Study Duration
In house 1 month 6 month 12 months
Description Green color Granuals Complies Complies Complies
Pendimethalin content percent by mass 14.25-15.75 15.35 15.34 15.33
Pyrazosulfuron Ethyl content percent by mass 0.14-0.17 0.16 0.16 0.15
pH range (1% aq. Suspension) 5.5-7.5 7.13 7.12 7.12
Moisture content (%) 3 1.7 1.2 1
Bulk Density 0.80 - 1.20 0.99 0.99 0.99

Example 4 Pendimethalin 30% + Pyrazosulfuron Ethyl 0.3% WG
Chemical Composition Percent (% w/w)
Pendimethalin a.i. 30.00
Pyrazosulfuron Ethyl a.i. 0.30
Alkylated naphtalene sulfonate, sodium salt 5.00
Polyacrylate co-polymer 2.00
Sodium alkyl naphthalene sulfonate blend 2.00
PPT silica 3.00
Silicone antifoam 0.50
Zinc 10.00
Lactose 20.00
Corn Starch 20.00
China Clay QS
Total 100.00

Process manufacturing process of Granules by extrusion method
Step 1 Charge the required quantity of filler, wetting agent, dispersing agent, suspending agent and 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 extricable 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 study- Pendimethalin 30%+Pyrazosulfuron Ethyl 0.3% WG
Parameters Specification (In house) Initial Stability (for 14 days)
At 54±2 0C At 0±2 0C
Description Off white color granules Complies Complies Complies
Pendimethalin content percent by mass 28.5 to 31.5 30.35 30.12 30.33
Pyrazosulfuron Ethyl content percent by mass 0.27 to 36 0.33 0.31 0.32
Pendimethalin suspensibility percent min. 70 94.78 92.93 94.75
Pyrazosulfuron Ethyl suspensibility percent min. 70 93.97 91.88 93.47
pH range (1% aq. Suspension) 5.5 to7.5 7.15 7.11 7.15
Wettability sec. max. 60 10 11 11
Wet Sieve(45 micron ) percent by mass min. 98.5 99.4 99 99.2
Bulk density (g/ml) 0.45 to 0.75 0.42 0.42 0.42
Moisture content percent by mass max. Max. 2.0% 1.8 0.8 1.4

Room temperature storage data
Parameters Specification (In house) Study Duration
1 month 6 month 12 months
Description Off white colour granules Complies Complies Complies
Pendimethalin content percent by mass 28.5 to 31.5 30.35 30.12 30.33
Pyrazosulfuron Ethyl content percent by mass 0.27 to 36 0.33 0.31 0.32
Pendimethalin suspensibility percent min. 70 94.61 94.26 93.39
Pyrazosulfuron Ethyl suspensibility percent min. 70 93.75 93.41 92.69
pH range (1% aq. Suspension) 5.5 to7.5 7.15 7.15 7.13
Wettability sec. max. 60 10 10 11
Wet Sieve(45 micron ) percent by mass min. 98.5 99.4 99.3 99.2
Bulk density (g/ml) 0.45 to 0.75 0.42 0.42 0.42
Moisture content percent by mass max. Max. 2.0% 1.8 1.4 1.2

Example 5: Pendimethalin 38%+Pyrazosulfuron -ethyl 0.5% ZC
Chemical Composition Percent (% w/w)
Pendimethalin a.i. 38.00
Pyrazosulfuron Ethyl a.i. 0.50
Polyurea capsule wall 1.50
Ligno Sulfonic Acid Na salt Sulfomethylated 1.00
Magnesium heptahydrate 8.00
Diethylenetriamine 0.80
Acrylic graft polymer 0.18
Fatty alcohol Ethoxylated 0.12
MonoEthyleneGlycol 3.00
Hydrochloric Acid 0.80
Zinc 10.00
Silicon Antifoam 0.50
1,2-benzisothiazolin-3-one 0.10
Modified sodium lignosulphonate 0.40
Xanthan powder 0.02
Water Q.S.
TOTAL 100.00

Manufacturing Process- ZC
Part 1 Preparation of Pendimethalin CS (Capsule Suspension)
Step1 Oil Phase: Take required quantity of melted pendimethalin technical and add Polymethalene polyphenyl isocynate (PMPI) and stir till proper mixing maintaining temperature 65-70 °C.
Step2 Aqueous Phase: Add required quantity of Wetting agent, antifreeze, dispersing agent & suspending agents and homogenize the contents for 45 – 60 minutes using high shear homogenizer with maintaining temperature 62-67 °C.
step3 Now transfer oil phase in aqueous phase slowly and continue to high shear for 30 minutes. When particle size is achieved (less than 20 micron) add DETA and stir it for another 90 to 120 minutes.
step4 Now cool the vessel at room temperature (25-35 °C).
Step 5 Add required quantity of biocide, antifoam and 2% xanthan gum and mix well for 30 minutes.
Step 6 Adjust the pH by adding potassium hydroxide solution or Hydrochloric acid until a target pH of around 7.5-8.0 is reached. Mix well.
Step 7 Final product is sent for QC approval.
Part 2 Preparation of Pyrazosulfuron Ethyl SC (Suspension Concentrate)
Step 1 Charge required quantity of DM water need to be taken in designated vessel for Suspension concentrate production.
Step 2 Add required quantity of Wetting agent, antifreezing agent,dispersing agent & suspending agents and homogenize the contents for 45 – 60 minutes using high shear homogenizer.
Step 3 Then add technical and other remaining adjuvant excluding ‘thickener’ are added to it and homogenized to get uniform slurry ready for grinding.
Step 4 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 5 After grinding material is transferred in CS Vessel.
Step 6 Final product is sent for QC approval.
Part 3 Mixing Pendimethalin CS and Pyrazosulfuron Ethyl SC
Step 1 After getting approval from QC department SC part is added in CS Vessel and homogenized for 30 minutes.
Step 2 Finally remaining 2% Xanthum Gum is added to it and homogenized for 20 minutes.
step 3 Now Final Formulation is sent for quality check.
Step 4 After approval material is packed in required pack sizes.

Storage stability Study of Pendimethalin 38%+Pyrazosulfuron -ethyl 0.5% ZC
Parameters Specification (In house) Initial Stability (for 14 days)
At 54±2 0C At 0±2 0C
Description Yellow to Brown color liquid Complies Complies Complies
Pendimethalin content percent by mass 36.10 to 39.9 38.18 38.11 38.18
Pyrazosulfuron Ethyl content percent by mass 0.475 to 0.550 0.52 0.5 0.52
Pendimethalin suspensibility percent mini. 80 95.65 93.07 95.14
Pyrazosulfuron Ethyl suspensibility percent mini. 80 96.07 94.88 96.5
pH range (1% aq. Suspension) 5.5 to7.5 7.31 7.28 7.31
Pourability 95 % min 98.5 97.4 97.3
Specific gravity 1.14 to 1.22 1.18 1.18 1.18
Viscosity at spindle no.62, 20 rpm 350 to 800 cps 480 530 535
Particle size (micron) D50 <3, D90 <10 2.4, 7.9 2.5, 8.6 2.7, 8.9

Room temperature storage data
Parameters Specification (In house) Study Duration
1 month 6 month 12 months
Description Yellow to Brown color liquid Complies Complies Complies
Pendimethalin content percent by mass 36.10 to 39.9 38.17 38.16 38..15
Pyrazosulfuron Ethyl content percent by mass 0.475 to 0.550 0.52 0.52 0.51
Pendimethalin suspensibility percent mini. 80 95.25 95.21 95.17
Pyrazosulfuron Ethyl suspensibility percent mini. 80 96.01 95.87 95.19
pH range (1% aq. Suspension) 5.5 to7.5 7.31 7.31 7.29
Pourability 95 % min 98.5 98.4 98.2
Specific gravity 1.14 to 1.22 1.18 1.18 1.18
Viscosity at spindle no.62, 20 rpm 350 to 800 cps 480 485 500
Particle size (micron) D50 <3, D90 <10 2.4, 7.9 2.4, 8.0 2.4, 8.2

Example 6: Biological Examples:
Field experiments of inventive mixture of Pendimethalin+ Pyrazosulfuron Ethyl and Zinc were carried on Rice crop to evaluate their phytotoxicity, Bioefficacy against different weed flora existing in Rice field and their impact on yield.
Trial 1 Phytotoxicity and Bioefficacy in transplanted Rice (Oryza sativa L.) crop
Experiment 1
The field experiment was conducted on transplanted Rice and experimental details as below:
Crop & Variety: Rice, MTU 1010
Experimental design: Randomized block design (R.B.D)
Replications: Four
No. of Treatments: Six (including untreated check)
Plot size: 30 sq. mt.
Application Time: 1 DATP (Days after Transplanting)
Application Method: Broadcasting manually
Experimental Method:
Rice crop nursery was raised in the field by using seed rate 10 kg per acre. The rice seedling (25 days old) was transplanted in to the main field by planting 2 seedlings per hill. The main field was puddle and flooded with water before transplanting. The plots were prepared by manual bunding. The bunds were covered with plastic. Each plot of 5 m X 6 m and such 24 plots were prepared considering 6 treatments with 4 replications. All standard agronomic practices were followed to raise the crop in the main field including fertilizer application and protecting the crop from insect pests and fungal diseases up to the harvest.

The treatments were applied as per the details given in the Table 1.
Observations Method:
1) Phytotoxicity: The phytotoxicity observations were recorded at 5, 10, 15, 20 and 25 DAA (Days after Application). The observations were recorded for crop stunting, yellowing, tiller count or any other visual observations by adopting 0-10 rating scale on entire plot basis as below:
0= No phytotoxicity, 1 =1-10% phytotoxicity, 2=11-20% phytotoxicity, 10=91-100% phytotoxicity symptoms appear.
Percent phytotoxicity was calculated by following formula:
Sum of all scores
% Phytotoxicity = ------------------------------------------------------------- X 100
Number of samples x highest rating scale

2) Bioefficacy : Species wise weed count recorded at 20 and 40 DAA (Days After Application) by using 0.25 m2 quadrant, treatment wise in minimum 3 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 two herbicide.

3) Zinc deficiency: Observations on zinc deficiency should be recorded when crop is at stem elongation stage or before booting stage.
Scale Descriptions
1 Growth and tillering nearly normal; healthy
2 Growth and tillering nearly normal; basal leaves slightly discolored
3 Stunting slight, tillering decreased, some basal leaves brown or yellow
5 Growth and tillering severely retarded, about half of all leaves brown or yellow
7 Growth and tillering ceases, most leaves brown or yellow
9 Almost all plants dead or dying

4) Tiller count: Count the number of tillers at 40 days after application and also count the number of effective tillers, tiller bearing panicle at the growth stage of grain filling from 1 sq.mt spot. Record such counts from 5 spot per plot. The tiller count observations are for assessing the phytotoxicity and zinc deficiency in the plot.
5) Yield: Record the grain weight in gram from 5 sq. m spot per plot and convert it to quintal per acre at the time of harvest.
Table 1: Treatment details
Treatments Product (per hectare) Active Ingredient (g per hectare) Application Time & Method

T1-Recipe 1-Pendimethalin 15%+Pyrazosulfuron Ethyl 0.15% GR. 15 kg 1500+15 1 DATP, Broadcast in standing water
T2-Recipe 2-Pendimethalin 15%+Pyrazosulfuron Ethyl 0.15% GR. 15 kg 1500+15 1 DATP, Broadcast in standing water
T3-Prior Art 1-Pendimethalin 30% EC+ Pyrazosulfuron Ethyl 10% WP (tank mix) + Zinc sulphate heptahydrate (21% Zn) 5 lit+ 150 g+10 kg 1500+15 (Zn-2100 g) 1 DATP, Sand mix and broadcast in standing water
T4-Pendimethalin 15% Granule 15 kg 1500 1 DATP, Broadcast in standing water
T5 Pyrazosulfuron Ethyl 0.15% Granule 15 kg 15 1 DATP, Broadcast in standing water
T6-Untreated Check (UTC) - - -
DATP Days After Transplanting, Kg Kilogram, GR Granule / Soil Applied Granule, EC Emulsifiable Concentrate, WP Wettable Powder

Table 2: Phytotoxicity in Rice (Oryza sativa)

Treatments Stunting Yellowing No. of Tillers/m2 at 40 DAA
5 DAA 10 DAA 15 DAA 20 DAA 25 DAA 5 DAA 10 DAA 15 DAA 20 DAA 25 DAA
T1 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 34.3
T2 0.0 0.0 0.0 0.0 0.0 0.0 1.4 1.4 1.0 1.0 29.2
T3 0.0 1.4 1.8 1.8 1.4 0.0 1.4 1.4 1.0 1.0 28.4
T4 0.0 1.4 1.8 1.8 1.4 0.0 1.4 1.4 1.0 1.0 22.7
T5 0.0 0.0 0.0 0.0 0.0 0.0 1.4 1.4 1.0 1.0 21.4
T6 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 18.7
DAA Days after Application

The results of field trial shows that treatment T1 (Recipe 1) is safe to the rice crop compared to T2 (Recipe 2) and other prior art treatments. Treatment T1 produces highest number of tillers at 40 days after application which also indicates its safety to the rice crop. The tillers count is directly correlated to better weed control, correction in zinc deficiency and herbicide safety.

Table 3: Synergistic weed control in Rice (Oryza sativa)
Treatments % Weed Control Observed % Weed Control Expected Colby Ratio o/e
15 DAA 30 DAA 45 DAA 15 DAA 30 DAA 45 DAA 15 DAA 30 DAA 45 DAA
T1 99.28 98.64 95.64 90.06 76.80 59.82 1.10 1.28 1.60
T2 98.76 95.42 92.23 90.06 76.80 59.82 1.10 1.24 1.54
T3 93.62 88.37 80.64 90.06 76.80 59.82 1.04 1.15 1.35
T4 74.28 54.84 40.16
T5 61.37 48.63 32.85
T6 0.00 0.00 0.00
DAA Days after Application
Weed flora present in trial plots are Grasses- Echinochloa colonum, Leptochloa chinensis, BROAD LEAF WEEDS – Sphenoclea zeylanica, Eclipta alba, Ludwigia parviflora, Alternanthera sessile, SEDGES- Cyperus difformis, Cyperus iria, Scirpus royelei.

The observation on weed control efficacy shows that T1, T2 and T3 show synergistic weed control of mixed flora comprises of grasses, broad leaf weeds and sedges.

Table 4: Zinc deficiency, Effective Tillers and yield at harvest
Treatments Zinc deficiency scale at booting stage Effective Tillers count at grain filling stage Yield (quintal/acre)
Observed Scale Calculated Value Colby Ratio o/e Observed Scale Calculated Value Colby Ratio o/e
T1 1.00 44.62 39.65 1.13 23.42 19.94 1.17
T2 9.00 20.84 39.65 0.53 10.46 19.94 0.52
T3 3.33 34.56 39.65 0.87 16.74 19.94 0.84
T4 2.00 23.92 11.26
T5 2.00 20.68 9.78
T6 9.00 17.66 8.12

The field observation shows that T1-Recipe1-Pendimehtalin 15%+ Pyrazosulfuron Ethyl 0.15% Granule does not express zinc deficiency symptoms. The observations on number of effective tillers and grain yield at harvest time shows that zinc deficiency causes adverse impact on rice tillering and grain yield. The synergistic effect of weed control along with zinc supplement of T1-Recipe 1-Pendimethalin 15%+Pyrazosulfuron Ethyl 0.15% Granule, produce highest number of effective tillers and grain yield at the time of harvest.

Trial 2: Bioefficacy in Direct Sown Rice-DSR (Oryza sativa L.) crop
The field experiment was conducted on direct sown Rice (DSR) and experimental details as below:
Crop & Variety: Rice, Arize 6129
Experimental design: Randomized block design (R.B.D)
Replications: Four
No. of Treatments: Six (including untreated check)
Plot size: 25 sq. mt.
Application Time: 2 DAS (Days after sowing)
Application Method: Irrigation was given on 2nd days of sowing and herbicide application was done manually by broadcasting after 48 hrs of irrigation.
Experimental Method:
Rice crop was sown directly in the field by using seed rate 10 kg per acre. The field was well prepared and fine seed bed was prepared. After sowing, a light irrigation was followed on 2nd day and treatments were applied after 48 hrs of irrigation. The plots were prepared by manual bunding with separate irrigation channel before irrigaiton. The bunds were covered with plastic. Each plot of 5 m X 5 m and such 24 plots were prepared considering 7 treatments with 4 replications. All standard agronomic practices were followed to raise the crop in the main field including fertilizer application and protecting the crop from insect pests and fungal diseases up to the harvest. The treatments were applied as per the details given in the Table 1.
Observations Method:
1) Bioefficacy: Weed counting and % weed control calculated as given in Trial 1.
2) Zinc deficiency: Observations on zinc deficiency were recorded as given in Trial 1.
3) Tiller count: As given in Trial 1.
4) Yield: Record the grain weight in gram as per method given in Trial 1.
Table 5 : Treatment Details

Treatments Product (per hectare) Active Ingredient (g per hectare) Application Time & Method

T1-Recipe 1-Pendimethalin 15%+Pyrazosulfuron Ethyl 0.15% GR. 15 kg 1500+15 2 days after irrigation by broadcasting
T2-Recipe 2-Pendimethalin 15%+Pyrazosulfuron Ethyl 0.15% GR. 15 kg 1500+15 2 days after irrigation by broadcasting
T3-Prior Art 1-Pendimethalin 30% EC+ Pyrazosulfuron Ethyl 10% WP (tank mix) + Zinc sulphate heptahydrate (21% Zn) 5 lit+ 150 g+10 kg 1500+15 (Zn-2100 g) 2 days after irrigation by broadcasting
T4-Pendimethalin 15% Granule 15 kg 1500 2 days after irrigation by broadcasting
T5 Pyrazosulfuron Ethyl 0.15% Granule 15 kg 15 2 days after irrigation by broadcasting
T6-Untreated Check (UTC) - - -
Kg Kilogram, GR Granule / Soil Applied Granule, EC Emulsifiable Concentrate, WP Wettable Powder

Table 6: Synergistic weed control in Direct sown Rice (Oryza sativa)
Treatments % Weed Control Observed % Weed Control Expected Colby Ratio o/e
15 DAA 30 DAA 45 DAA 15 DAA 30 DAA 45 DAA 15 DAA 30 DAA 45 DAA
T1 99.72 95.16 90.48 94.41 82.85 61.46 1.06 1.15 1.47
T2 98.64 93.76 89.26 94.41 82.85 61.46 1.04 1.13 1.45
T3 94.66 89.12 80.84 94.41 82.85 61.46 1.00 1.08 1.32
T4 80.54 64.72 44.42
T5 71.26 51.38 30.66
T6 0.00 0.00 0.00
DAA Days after Application
Weed flora present in trial plots are Grasses- Leptochloa chinensis, Eleusine indica, Echinochloa colonum, Eleocharis spp., Broad leaf weeds- Trainthema monogyna, Commelina SEDGES- Cyperus difformis, Cyperus iria, Scirpus royelei.

The field experiment result shows that T1-Recipe-1-Pendimethalin 15%+Pyrazosulfuron Ethyl 0.15% Gr provides synergistic weed control of all kind of weeds i.e. grasses, broad leaf and sedges in direct sown rice compared. The residual control was also observed longer in T1 compared to other treatments.

Table 7: Zinc deficiency, Effective Tillers and yield at harvest
Treatments Zinc deficiency scale at booting stage Effective Tillers count at grain filling stage Yield (quintal/acre)
Observed Scale Calculated Value Colby Ratio o/e Observed Scale Calculated Value Colby Ratio o/e
T1 1.00 39.62 35.49 1.12 21.82 19.49 1.12
T2 9.00 19.86 35.49 0.56 13.58 19.49 0.70
T3 4.00 26.74 35.49 0.75 17.46 19.49 0.90
T4 4.00 21.84 12.64
T5 3.67 17.46 7.84
T6 9.00 12.34 5.78

The zinc deficiency was not observed in T1-Recipe1-Pendimehtalin 15%+ Pyrazosulfuron Ethyl 0.15% Granule treatment. The observations on number of effective tillers and grain yield at harvest time shows treatment of T1-Recipe 1-Pendimethalin 15%+Pyrazosulfuron Ethyl 0.15% Granule, produce highest number of effective tillers and grain yield at the time of harvest compared to other treatments.
,CLAIMS:[CLAIM 1]. A novel herbicide composition comprises synergistic bioactive amounts of Pendimethalin in combination with Pyrazosulfuron-ethyl and Zinc and at least one more inactive excipients.

[CLAIM 2]. A novel herbicide composition as claimed in claim 1 wherein Pendimethalin in range of 1-40%, Pyrazosulfuron-ethyl in range of 0.01-20% and Zinc in range of 1-40%.

[CLAIM 3]. A novel herbicide composition as claimed in claim 1 or 2 wherein Zinc is any one of the form Zinc Sulfate Monohydrate (ZnSO4,H2O), Zinc Sulfate Heptahydrate (ZnSO4,7H2O), Zinc Oxysulphate (ZnSO4xZnO), Zinc Oxide (ZnO), Zinc carbonate (ZnCO3), Zinc Chloride (ZnCl2), Zinc EDTA/Zinc chelate, Zinc Gluconate, Zinc Lactate Gluconate, Zinc Polyflavonoid, Zinc lignosulphate.

[CLAIM 4]. A novel herbicide composition as claimed in claim 1-3, wherein various forms of zinc is optionally in nanoparticles comprises particle size of the nanoparticles of is in the range from 1 to 1000 nm, preferably 1 to 100, more preferably 1 to 50 nm.

[CLAIM 5]. A novel herbicide 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 and buffering agent.

[CLAIM 6]. A novel herbicide composition as claimed in claim 1 or 2, wherein the composition are selected from formulations comprising of Soil Applied Granules (SAG), Water Dispersible Granules (WDG), ZC formulation (ZC), dustable powder (DP), a gel, a wettable powder (WP), a granule (GR) (such as an emulsifiable granule (EG) or more particularly a water-dispersible granule (WG)), a water-dispersible tablet (WT), an emulsifiable concentrate (EC), a micro- emulsifiable concentrate, an oil-in-water emulsion (EW), an oil flowable (e.g. a spreading oil (SO)), an aqueous dispersion (e.g. aqueous suspension concentrate (SC)), an oily dispersion (OD), a suspo-emulsion (SE), a capsule suspension (CS), a soluble liquid, a water-soluble concentrate (with water or a water-miscible organic solvent as carrier), an impregnated polymer film, or jumbo formulation.

[CLAIM 7]. A novel herbicide composition as claimed in claim 6, wherein the preferable formulations are Soil Applied Granules (SAG), Water Dispersible Granules (WDG), ZC formulation (ZC).

[CLAIM 8]. A novel herbicide composition as claimed in claim 6, wherein Soil Applied Granules (SAG) formulation comprises:
a) Pendimethalin in range of 1-40%;
b) Pyrazosulfuron-ethyl in range of 0.01-20%;
c) Zinc in range of 1-40% optionally in nanoparticle form and
d) Filler, Absorbent, Emulsifier, Wetting agents, Dispersants & Stabilizers, Anti-caking and Free-flow agent.

[CLAIM 9]. A novel herbicide composition as claimed in claim 6, wherein in Soil Applied Granules (SAG) formulation, Pendimethalin may optionally be in capsule suspension (CS) formulation.

[CLAIM 10]. A novel herbicide composition as claimed in claim in any of the preceding claims, wherein the said composition is used for effective control or management of weeds in Crops like Paddy (Oryza sativa L.) including Indica, Japonica and Javanica race. GMO Paddy, Sugarcane (Saccharumofficinarum), Cotton (Gossypium spp.), Jute (Corchorusoliotorus), Wheat (Triticumaestavum), Barley (Hordeumvulgare), Maize (Zea mays), Sorghum (Sorghum bicolor), Ragi (Eleusinecoracana), Pearl millet (Pennisetumglaucum), Brinjal (Solanummelongena), Onion (Allium cepa L.), Tomato (Solanumlycopersicun) , Potato (Solanumtuberosum) , Sweet potato (Ipomoea batatas), Chilly (Capsicum annum), Garlic (Allium sativum).

[CLAIM 11]. A novel herbicide composition as claimed in in any preceding claims, wherein the composition controls the weed Aeschynomeneaspera, Aeschynomeneindica, Ageratum conyzoides, Alternantherasessilis, Alternantheraphiloxeroides, Amaranthusspinosus, Amaranthusviridis, Ammaniabaccifera, Cynodondactylon, Dactylocteniumaegyptium, Digitariaciliaris, Digitariasetigera, Ischaemumrugosum, Echinochloacolona, Echinochloa crus-galli, Echinochloaglabrescens, Echinochloa crus-pavonis, Echinochloaesculenta, Echinochloafrumentacea, Echinochloamuricata, Echinochloaoryzoides, Echinochloapaludigena, Eleochariskuruguwai, Laptochloachinensis, Eleusineindica, Eclipta alba, Eclipta prostate, Imperata cylindrical, Leersiahexandra, Leptochloachinensis, Oryza sativa, Panicumrepens, Paspalumdistichum, Paspalumscrobiculatum, Rottboelliacochinchinensis, Setariaglauca, Bolboschoenusmaritimus, Bergiacapensis, Commelinabenghalensis, Commelinadiffusa, Cyanotisaxillaris, Eclipta alba, Eclipta prostrate, Eichhorniacrassipes, Ipomoea aquatic, Ludwigiaadscendens, Ludwigiahyssopifolia, Ludwigiaoctovalvis, Ludwigiaparviflora, Marsileaminuta, Marsileaquadrifoliata, Mimosa diplotricha, Monochoriavaginalis, Pistiastratiotes, Polygonumhydropiper, Portulacaoleracea, Sagittariamilliacea, Sagittariasagittifolia, Sphenocleazeylanica, Trianthemaportulacastrum, Typha spp., Isachneglobosa, Paspalumdistichum, Cyperusdifformis, Cyperushaspen, Cyperusiria, Cyperusrotundus, Fimbristylisdichotoma, Fimbristylismiliacea, Scirpusjuncoides, Scirpusnipponicus, Scirpusplaniculmis, Scirpurroyelei, Scirpusjuncoides.