WO2018051372A1 - Stable formulation of water sensitive active - Google Patents

Stable formulation of water sensitive active Download PDF

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Publication number
WO2018051372A1
WO2018051372A1 PCT/IN2017/050408 IN2017050408W WO2018051372A1 WO 2018051372 A1 WO2018051372 A1 WO 2018051372A1 IN 2017050408 W IN2017050408 W IN 2017050408W WO 2018051372 A1 WO2018051372 A1 WO 2018051372A1
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WO
WIPO (PCT)
Prior art keywords
granular composition
agrochemical
composition
active ingredient
stable
Prior art date
Application number
PCT/IN2017/050408
Other languages
French (fr)
Inventor
Arun SAWANT
Original Assignee
Sawant Arun
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sawant Arun filed Critical Sawant Arun
Priority to CN201780057151.2A priority Critical patent/CN110519986A/en
Publication of WO2018051372A1 publication Critical patent/WO2018051372A1/en
Priority to AU2018266949A priority patent/AU2018266949B2/en
Priority to US15/976,304 priority patent/US10492489B2/en
Priority to MYPI2019006531A priority patent/MY192628A/en
Priority to MX2019013379A priority patent/MX2019013379A/en
Priority to CN201880046082.XA priority patent/CN110868861B/en
Priority to BR112019023615-5A priority patent/BR112019023615B1/en
Priority to JP2019561264A priority patent/JP6949996B2/en
Priority to EP18798485.1A priority patent/EP3644740A4/en
Priority to KR1020197036529A priority patent/KR102296841B1/en
Priority to PE2019002383A priority patent/PE20200234A1/en
Priority to NZ759443A priority patent/NZ759443A/en
Priority to TNP/2019/000307A priority patent/TN2019000307A1/en
Priority to UAA201911711A priority patent/UA124787C2/en
Priority to CA3062598A priority patent/CA3062598C/en
Priority to PCT/IB2018/053251 priority patent/WO2018207124A1/en
Priority to EA201992672A priority patent/EA201992672A1/en
Priority to IL270514A priority patent/IL270514B/en
Priority to PH12019502502A priority patent/PH12019502502A1/en
Priority to SA519410520A priority patent/SA519410520B1/en
Priority to CONC2019/0013834A priority patent/CO2019013834A2/en
Priority to ECSENADI201987631A priority patent/ECSP19087631A/en
Priority to ZA2020/00207A priority patent/ZA202000207B/en

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Classifications

    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring

Definitions

  • the present invention relates to a stable granular composition including at least one agrochemical active ingredient, wherein the agrochemical active includes one or more of water soluble active ingredient or a water sensitive active ingredient for agrochemical purposes. More particularly, the invention relates to a stable agrochemical granular composition including at least one agrochemical active ingredient, wherein the agrochemical active includes one or more of a water soluble active ingredient or a water sensitive active ingredient, at least one thermostable plasticizer wherein the plasticizer has a melting point greater than 20°C and less than 150°C; and at least one agrochemically acceptable excipient.
  • the granular composition has a wettability of less than 20 minutes.
  • the invention further relates to a process of preparing a stable agrochemical granular composition including one or more of water soluble active ingredient or a water sensitive active ingredient.
  • the invention furthermore relates to a method of treating the plants or the soil with the stable agrochemical granular composition including the water soluble active ingredient or the water sensitive active ingredient.
  • Granular agrochemical compositions have become very popular in recent years because they are safe and more convenient to handle than conventional agrochemical formulations such as wettable powders and emulsfiable concentrates.
  • Various agrochemical actives are known to be developed in the form of water dispersible granular formulation due to the advantages offered by such formulation.
  • active agents have the disadvantage of being highly sensitive and unstable in aqueous media and of being readily degraded or modified under the influence of water due to poor chemical stability.
  • hydrolysis is the most common water-mediated degradation mechanism; however, such actives are also likely to undergo oxidation, dehalogenation, bond cleavage, Beckmann rearrangement and other forms of degradation on coming in contact with water.
  • the actives tend to lose their activity or convert into another form on coming into contact with water.
  • Such actives typically lose their activity over time, and this instability goes against the desired field efficacy making them unavailable to the soil or plants or the desired target.
  • some of the agrochemical actives due to their water soluble nature cannot be formulated into a stable water dispersible granular formulation.
  • active agents have been formulated in an anhydrous liquid medium.
  • such a formulation does not permit the incorporation of hydrophilic active agents.
  • these actives have been known to be formulated as Emulsifiable concentrates, dusts, wettable powders, etc.
  • compositions are also required to be applied at very high dosages of application.
  • Prior art compositions comprising water sensitive or soluble active ingredients provide compositions which do not possess good properties of wettability and disintegration time. These prior art compositions also tend to float for long durations and also do not reach the plant root zone, or desired target area, and therefore tend to leach away, contributing to inadequate pest control, loss to the farmer and damage to the environment.
  • a stable agrochemical granular composition of one or more water soluble or a water sensitive active ingredient provides excellent efficacy, ease of application, retains all the properties of the active, avoids decomposition of the active and is friendly to the farmers as well as the environment, as compared to conventional formulations.
  • the stable water free granular composition of water soluble or a water sensitive active with at least one thermostable plasticizer works effectively at a reduced dosage, offers broader crop protection spectrum and control against various insects, weeds, mites and fungi, improves growth and quality of crops/plants and thus, highly cost effective in nature, which not only exhibits enhanced wettability but also shows improved hardness and good disintegration in water thus ensuring a uniform application and availability for an extended period of time.
  • the present invention relates to a stable agrochemical granular composition of at least one or more agrochemical active ingredient, wherein the agrochemical active includes one or more water soluble active ingredient or a water sensitive active ingredient; at least one thermostable plasticizer with a melting point greater than 20°C and less than 150°C; and at least one agrochemically acceptable excipient; wherein the granular composition exhibits a wettability of less than 20 minutes.
  • the invention further relates to a process of preparing a stable granular composition, involving mixing and blending at least one agrochemical active ingredient selected from one or more of a water soluble active ingredient or a water sensitive active ingredient; with at least one thermostable polymer to obtain a mixture; heating and cooling the mixture to arrive at the stable agrochemical granular composition; wherein the granular composition exhibits a wettability of less than 20 minutes.
  • the invention further relates to method of protection of crop or improving its health or yield, by treating at least one of a plant, crop, a plant propagation material, a seed, seedling or surrounding soil with a stable granular composition of at least one agrochemical active ingredients selected from one or more of a water soluble active ingredient or a water sensitive active ingredient; at least one thermostable plasticizer; and, at least one agrochemically acceptable excipient; wherein the granular composition exhibits a wettability of less than 20 minutes.
  • composition not only exhibits wettability of less than 20 minutes but also has a hardness of less than 5 N, demonstrates reduced decomposition of the active, good physical properties of disintegration, dispersion and suspension, good release properties for the entire crop life cycle. Moreover, the composition exhibits a surprisingly higher field efficacy at significantly reduced dosages of application of the composition.
  • the invention relates to a stable agrochemical granular composition which includes: at least one agrochemical active ingredient.
  • the agrochemical active ingredient includes one or more of water soluble active ingredient or a water sensitive active ingredient.
  • the composition further includes at least one thermostable plasticizer which has a melting point greater than 20°C and less than 150°C;
  • the granular composition exhibits a wettability of less than 20 minutes.
  • water sensitive active ingredient means a chemically and/or physically unstable active agent.
  • chemical instability especially means degradation of the active principle.
  • Water-sensitive agrochemically active ingredients are those which are subject to a water-mediated degradation such as hydrolysis, oxidation, dehalogenation, bond cleavage, Beckmann rearrangement and other forms of degradation on exposure to water.
  • degradation denotes loss of activity of the water sensitive active ingredient, upon coming in contact with water. Degradation can be determined simply by measuring the amount of the active ingredient present before and after contact with water.
  • physical instability especially means crystallization or precipitation of the active agent, or modification of its colour within the composition.
  • water soluble active ingredient is an agrochemical active ingredient which is soluble in water to little extent or even a large extent.
  • the agrochemical active ingredient has a solubility of more than 0.1 mg/liter in water at 20°C.
  • the agrochemical active ingredient has a solubility of more than 0.5 mg/liter in water at 20°C.
  • the agrochemical active ingredient has a solubility of more than 1 mg/liter in water at 20°C.
  • the agrochemical active ingredient has a solubility of more than lg/liter in water at 20°C.
  • the agrochemical active is at least one selected from an antifoulant, an attractant, an insecticide, a fungicide, a herbicide, a nematicide, a pheromone, a defoliant, an acaricide, a plant growth regulator, an algicide, an antifeedant, an avicide, a bactericide, a bird repellent, a biopesticide, a biocide, a chemosterilant, a safener, an insect attractant, an insect repellent, a insect growth regulator, a mammal repellent, a mating disrupter, a desiccant, a disinfectant, a molluscicide, an antimicrobial, a miticide, an ovicide, a fumigant, a plant activator, a rodenticide, a synergist, a virucide, a repellent, a microbial pesticide, a plant incorporated protectant, other miscellaneous pest
  • the first or second agrochemical active is at least one selected from but are not limited to one or more of "abamectin, abamectin-aminomethyl, abscisic acid, ACC, acephate, acequinocyl, acetamiprid, acethion, acetochlor, acetofenate, acetophos, acetoprole, acibenzolar, acifluorfen, aclonifen, acetonitrile, acrep, acrinathrin, acrolein, acrylonitrile, acynonapyr, acypetacs, afidopyropen, afoxolaner, alachlor, alanap, alanycarb, albendazole, aldicarb, aldicarb sulfone, aldimorph, aldoxycarb, aldrin, allethrin, d-trans-allethrin, allicin
  • the first agrochemical active ingredient is a water sensitive active ingredient.
  • the water sensitive active include one or more of but not limited to, clodinafop-propargyl, acetamiprid, pinoxaden, azimsulfuron, berssu!furon, chlorimuron, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron, ethoxysulfuron, flazasulfuron, flupyrsulfuron, halosulfuron, imazosulfuron, iodosulfuron, mesosulfuron, metsulfuron, nicosulfuron, primisulfuron, prosulfuron, pyrazosulfuron, rimsulfuron, sulfometuron, sulfosulfuron, thifensulfuron, triasulfuron, tribenuron, triflus
  • the first agrochemical active ingredient is a water soluble active.
  • the water soluble active includes one or more of but not limited to acephate, acetamiprid, acethion, acetic acid, acetochlor, acetoprole, acibenzolar-S-methyl, acifluorfen, acifluorfen-sodium, aclonifen, acrolein, acrylonitrile, afidopyropen, alachlor, alanycarb, aldicarb, aldimorph, aldoxycarb, allidochlor, alloxydim, allyl alcohol, allyxycarb, alorac, alpha-chlorohydrin, alpha-endosulfan, alpha-hexachlorocyclohexane, alpha- naphthylthiourea, aluminium ammonium sulphate, aluminium phosphide, aluminium silicate, ametoctra
  • the agrochemical active is a pesticidal active including but are not limited to one or more of class of actives selected from, neonicotinoid insecticides, oxyphenoxy acid esters, cyclohexanedione oxime herbicides the sulfonyl ureas and the cloquintocet herbicide safeners, the HPPD-inhibiting herbicides, phenylpyrazoles, nereistoxin analogue insecticides,and organophosphate insecticides.
  • class of actives selected from, neonicotinoid insecticides, oxyphenoxy acid esters, cyclohexanedione oxime herbicides the sulfonyl ureas and the cloquintocet herbicide safeners, the HPPD-inhibiting herbicides, phenylpyrazoles, nereistoxin analogue insecticides,and organophosphate insecticides.
  • the first agrochemical active ingredient is preferably selected from one or more of Acequinocyl, acrolein, alachlor, alloxydim, alpha-endosulfan, aminocarb, amitraz, anilazine, azamethiphos, azinphos-ethyl, barban, benfuracarb, benomyl, bensultap, bifenazate, bromomethane, bromoxynil heptanoate, bromoxynil octanoate, butoxycarboxim, captan, carbaryl Carbetamide, carbosulfan, carfentrazone-ethyl, cartap, cartap hydrochloride, chinomethionat, cinidon-ethyl, clodinafop-propargyl, Clofentezine, cyflumetofen, cymoxanil, dazomet, desmedipham, dichlofluanid
  • the first agrochemical active ingredient is preferably selected from one or more of Acequinocyl, acrolein, alachlor, amitraz, barban, benfuracarb, benomyl, bensultap, bifenazate, captan, carbosulfan, cartap, cartap hydrochloride, chinomethionat, cinidon-ethyl, clodinafop-propargyl, clofentezine, cyflumetofen, cymoxanil, dazomet, desmedipham, dichlorvos, dicofol, dithianon, ethephon, famoxadone, fentin acetate, ferbam, fluazinam, flumiclorac-pentyl, flumioxazin, folpet, formetanate, Formothion, haloxyfop-etotyl, heptachlor, i
  • the first agrochemical active ingredient is preferably selected from one or more of Alachlor, amitraz, barban, benomyl, bensultap, bifenazate, captan, carbosulfan, cartap, cartap hydrochloride, cyflumetofen, Dazomet, desmedipham, dithianon, fentin acetate, flumiclorac-pentyl, flumioxazin, folpet, formothion, heptachlor, isoxaflutole, maneb, metiram, naled, ofurace, phenmedipham, Phosmet, pinoxaden, sulfuryl fluoride, tetraethyl pyrophosphate and ziram.
  • the agrochemical active can be any one of cartap, cartap hydrochloride, pinoxaden.
  • the second agrochemical active is fipronil.
  • the first or second agrochemical active is present in a concentration range of at least 0.01% by by weight of the total composition.
  • the agrochemical active is present in a concentration range of at least 1% by by weight of the total composition.
  • the agrochemical active is present in a concentration range of at least 5 % by weight of the total composition.
  • the agrochemical active is present in a concentration range of at least 10 % by weight of the total composition.
  • the agrochemical active is present in a concentration range of at least 20 % by weight of the total composition.
  • the agrochemical active is present in a concentration range of at least 30% by weight of the total composition.
  • the agrochemical active is present in a concentration range of at least 40% by weight of the total composition. According to an embodiment, the agrochemical active is present in a concentration range of at least 50 % by weight of the total composition. According to an embodiment, the agrochemical active is present in a concentration range of at least 60% by weight of the total composition. According to an embodiment, the agrochemical active is present in a concentration range of at least 70% by weight of the total composition. According to an embodiment, the agrochemical active is present in a concentration range of at least 80% by weight of the total composition. According to an embodiment, the agrochemical active is present in a concentration range of at least 90% by weight of the total composition.
  • the agrochemical granules are selected from water dispersible granules, fine granules; microgranules; soluble granules, Emulsifiable granules, dispersible granules, broadcast granules, disintegrable granules or extruded granules.
  • the agrochemical granules are preferably broadcast granules, disintegrable granules or extruded granules.
  • the granular composition includes granules which arepolygonal, spherical, oval, or any polyhedral granules, without affecting the superior properties observed.
  • the agricultural granules are substantially spherical.
  • the granular composition is in a size range of 0.1 mm to 6 mm.
  • the granular composition is in the size range of 0.1 mm to 3 mm.
  • the granular composition is in the size range of 0.1 mm to 2 mm.
  • the granular composition is in the size range of 0.1 mm to 1 mm.
  • the granules formed have a particle size in the range of 0.1 micron to 100 microns. According to an embodiment, the granules formed have a particle size in the range of 0.1 micron to 60 microns. According to an embodiment, the granules formed have a particle size in the range of 0.1 micron to 30 microns. According to an embodiment, the granules formed have a particle size in the range of 0.1 micron to 20 microns.
  • the granular composition of the invention exhibits a reduced bulk density compared to known compositions, which facilitates faster disintegration of the granules and also prevents settling of the composition in water.
  • the granular composition also exhibited an improved hardness and attrition resistance as compared to known pellets or granules.
  • the granular composition surprisingly possesses good hardness.
  • the hardness exhibited by the the granular composition is at least 1 Newton.
  • the granular composition has a hardness of at least 3 Newtons. According to an embodiment, the granular composition has a hardness of at least 5 Newtons. According to another embodiment, the granular composition has a hardness of at least 10 Newtons. According to another embodiment, the granular composition has a hardness of at least 20 Newtons. According to another embodiment, the granular composition has a hardness of at least 30 Newtons.
  • the granular composition has a hardness of at least 40 Newtons. According to another embodiment, the granular composition has a hardness of at least 60 Newtons.
  • the hardness exhibited by the granules is estimated by hardness testers such as the ones provided by Shimadzu, Brinell Hardness (AKB-3000 Model), Mecmesin, Agilent, Vinsyst, Ametek and Rockwell.
  • the granular composition has a disintegration time of less than 30 minutes. According to an embodiment, the granular composition has a disintegration time of less than 20 minutes. According to an embodiment, the granular composition has a disintegration time of less tha 10 minutes. According to an embodiment, the granular composition has a disintegration time of less than 5 minutes. According to an embodiment, the granular composition has a disintegration time of less than 3 minutes. According to an embodiment, the granular composition has a disintegration time of less than 2 minutes. According to an embodiment, the granular composition has a disintegration time of less than 1 minute. According to an embodiment, the granular composition has a disintegration time of less than 30 seconds. The disintegration time is estimated by disintegration testing equipments such as the ones provided by Electrolab Edutec, Arentek and Shimadzu.
  • At least 99% of the granular composition disintegrates in less than 30 minutes. According to yet another embodiment, at least 50% of the granular composition disintegrates in less than 20 minutes. According to yet another embodiment, at least 30% of the granular composition disintegrates in less than 10 minutes. According to yet another embodiment, at least 20% of the granular composition disintegrates in less than 5 minutes. According to yet another embodiment, at least 10% of the granular composition disintegrates in less than 3 minutes. According to yet another embodiment, at least 5% of the granular composition disintegrates in less than 1 minute. According to a still further embodiment, at least 2% of the granular composition disintegrates in less than 30 seconds.
  • the bulk density of the granular composition is less than 1.5 gms/ml. According to an embodiment, the bulk density of the granular composition is preferably less than 1.2 gms/ml. According to another embodiment, the bulk density of the granular composition is preferably less than 1.0 g/ml. According to another embodiment, the bulk density of granular composition is preferably less than 0.9 g/ml.
  • the granular composition of the invention exhibits a improved floatability compared to known granules, which facilitates superior availability of the composition to the crops or plants, reduced leaching of the actives.
  • the composition exhibits reduced settling of the composition in water.
  • the granules composition also exhibited an improved disintegration, dispersion and suspension as compared to known granules.
  • Floatability can be defined as the ability of the granular composition to remain on the surface of the fluid without sinking.
  • the floatability of the granular composition is less than 99%.
  • the floatability of the granular composition is less than 90%.
  • the floatability of the granular composition is less than 80%.
  • the floatability of the granular composition is less than 70%. According to an embodiment, the floatability of the granular composition is less than 60%. According to an embodiment, the floatability of the granular composition is less than 50%. According to an embodiment, the floatability of the granular composition is less than 40%. According to an embodiment, the floatability of the granular composition is less than 30%. According to an embodiment, the agrochemical granular composition has floatability less than 25%. According to an embodiment, the agrochemical granular composition has floatability less than 15%. According to an embodiment, the agrochemical granular composition has floatability less than 10%. According to an embodiment, the agrochemical granular composition has floatability less than 5%.
  • the agrochemical granular composition has floatability less than 3%. According to an embodiment, the agrochemical granular composition has floatability less than 1%. According to an embodiment, the agrochemical granular composition has floatability less than 0.5%.
  • Attrition resistance determines the resistance of a granular material to wear.
  • the process of determining attrition resistance involves agitating the granules, by tumbling within a drum to simulate a fluidized bed. After a certain time has elapsed, the material is sieved and weighed to determine the amount of material which has been reduced to below a certain size (referred to as 'fines').
  • the attrition resistance of the granules is at least 30%.
  • the attrition resistance of the granules or pellets is at least 40%.
  • the attrition resistance exhibited by the granules isat least 50%.
  • the attrition resistance of the granules is at least 60%. According to an embodiment, the attrition resistance of the granules is at least 70%. According to another embodiment, the granules exhibit an attrition resistance of at least 80%. According to an embodiment, the granules exhibit an attrition resistance at least 90%.
  • the specifics of the test are defined by various standards as applicable to the purpose in question, such as those defined by ASTM, well known to a person skilled in the art.
  • Dispersibility is defined as the ability of the granules to disperse upon addition to a liquid such as water or a solvent.
  • a liquid such as water or a solvent.
  • MT 174 a known amount of the granular composition was added to a defined volume of water and mixed by stirring to form a suspension. After standing for a short period, the top nine-tenths are drawn off and the remaining tenth dried and determined gravimetrically. The method is virtually a shortened test of suspensibility and is appropriate for establishing the ease with which the granular composition dispersed uniformly in water.
  • the granular composition have a dispersibility of at least 40%.
  • the granular composition have a dispersibility of at least 50%.
  • the granular composition have a dispersibility of at least 60%.
  • the granular composition have a dispersibility of at least 70%. According to an embodiment, the granular composition have a dispersibility of at least 80%.
  • the granular composition have a dispersibility of at least 90%.
  • Suspensibility is defined as the amount of active ingredient suspended after a given time in a column of liquid, of stated height, expressed as a percentage of the amount of active ingredient in the original suspension.
  • a suspension of known concentration of the granular composition in CIPAC Standard Water was prepared and placed in a prescribed measuring cylinder at a constant temperature, and allowed to remain undisturbed for a specified time. The top 9/10ths were drawn off and the remaining 1/lOth was then assayed either chemically, gravimetrically, or by solvent extraction, and the suspensibility was calculated.
  • the granular composition have a suspensibility of at least 10%.
  • the granular composition have a suspensibility of at least 20%. According to an embodiment, the granular composition have a suspensibility of at least 30%. According to an embodiment, the granular composition have a suspensibility of at least 40%. According to an embodiment, the granular composition have a suspensibility of at least 50%.
  • the granular composition has a suspensibility of at least 60%.
  • the granular composition has a suspensibility of at least 70%.
  • Wettability is the condition or the state of being wettable and can be defined as the degree to which a solid is wetted by a liquid, measured by the force of adhesion between the solid and liquid phases
  • the wettability of the granular composition was measured using the Standard Cipac Test MT-53 which describes a procedure for the determination of the time of complete wetting of wettable formulations. A weighed amount of the granular composition was dropped on water in a beaker from a specified height and the time for complete wetting was determined. According to an embodiment, the granular composition has a wettability of less than 30 minutes. According to another embodiment, the granular composition has a wettability of less than 20 minutes.
  • the granular compostion has a wettability of less than 15 minutes. According to another embodiment, the granular composition has a wettability of less than 10 minutes. According to another embodiment, the granular composition has a wettability of less than 5 minutes. According to another embodiment, the granular composition has a wettability of less than 2 minutes. According to another embodiment, the granular composition has a wettability of less than 1 minute. According to another embodiment, the granular composition has a wettability of less than 30 seconds.
  • an agrochemical active is a solid active. According to further embodiment, the agrochemical active has a melting point greater than 35°C. According to further embodiment, the agrochemical active has a melting point greater than 40°C. According to further embodiment, the agrochemical active has a melting point greater than 45°C. According to further embodiment, the agrochemical active has a melting point greater than 50°C. According to an embodiment, the composition further comprises one or more of fertilizers, a second pesticidal active, macronutrients and micronutrients or salts thereof.
  • the fertilizer includes one or more of but not limited to single nutrient fertilizers, multi nutrient fertilizers, micro-nutrients, binary fertilizers, compound fertilizers, organic fertilizers, derivatives or mixtures thereof.
  • the fertilizers include, but not limited to at least one of nitrogen fertilizer, sulphur fertilizer, phosphate fertilizer, potash fertilizer or salts, derivatives and mixtures thereof.
  • the nitrogen fertilizer can include urea, ammonium sulphate, ammonium nitrate, anhydrous ammonia, ammonium nitrate sulphate, Diammonium phosphate, Nitrogen solutions, Monoammonium phosphate, Ammonium polyphosphate, Triple superphosphate, their derivatives, oxides, salts and mixtures thereof.
  • the sulphur based fertilizer can include elemental sulphur, Ammonium thiosulfate, Calcium sulphate, Gypsum or derivatives, oxides, salts and mixtures thereof.
  • the macronutrients include one or more of, but not limited to carbohydrates, fats, and proteins or salts, derivatives and mixtures therefore.
  • the micronutrients include one or more of but not limited to Vitamins such as Vitamin A, Vitamin B, Vitamin C, Vitamin D, Vitamin E, Vitamin K, Carotenoids, Minerals such as Boron, Calcium, Chloride, Chromium, Cobalt, Copper, Fluoride, Iodine, Iron, Magnesium, Manganese, Molybdenum, Phosphorous, Potassium, Selenium, Sodium, Zinc and Organic Acids such as Acetic acid, Citric acid, Lactic acid, Malic acid, Choline and Taurine or salts, derivatives and mixtures therefore.
  • the one or more of fertilizers, a second pesticidal active, macronutrients and micronutrients or salts thereof are in a concentration range of 0.01% to 95% by weight ot the total composition.
  • thermostable plasticizer includes one or more of surfactants, polyethers, thermoplastic materials, resins, lubricants, protective colloids, water soluble salts, nitrogen fertilizers, water soluble polymers, water soluble co-polymers, complexing agents, carbohydrates or derivatives and combinations thereof.
  • the thermostable plasticizer is selected from one or more of Polyoxyethylene oxide, Vitamin E polyethylene glycol succinate, Macrogolglycerol Hydroxystearate, Polyethylene glycol, Polaxomer (block copolymer of polyoxyethylene- polyoxypropylene), Polyoxyethylene-polyoxypropylene block copolymer, l-phenyl-l,2-ethanediol, Poly(ethylene )adipate, Ethylene Oxide/Propylene Oxide Block Copolymer, ethylene-vinyl acetate copolymers, Copovidone of vinyl-pyrrolidone and vinyl acetate, polyvinyl caprolactam-polyvinyl acetate-polyethylene glycol graft co-polymer, Polyvinyl alcohol (PVA)-polyethylene glycol (PEG) graft co-polymer and Hydroxypropylcellulose.
  • PVA polyvinyl alcohol
  • PEG polyvinyl alcohol
  • thermostable plasticizer has a melting point less than 250°C. According to further embodiment, the thermostable plasticizer has a melting point less than 200°C. According to further embodiment, the thermostable plasticizer has a melting point less than 150°C. According to further embodiment, the thermostable plasticizer has a melting point less than 100°C.
  • thermostable plasticizer has a melting point less than 80°C. According to another embodiment, the thermostable plasticizer has a melting point lower than the melting point of agrochemical active ingredient. According to an embodiment, the thermostable plasticizer has a molecular weight of less than 100 gms/mol. According to an embodiment, the thermostable plasticizer has a molecular weight of less than 500 gms/mol. According to an embodiment, the thermostable plasticizer has a molecular weight of less than 1000 gms/mol. According to an embodiment, the thermostable plasticizer has a molecular weight of less than 2000 gms/mol.
  • the thermostable plasticizer has a molecular weight of less than 5000 gms/mol. According to another embodiment, the thermostable plasticizer has a molecular weight of less than 10,000 gms/mol. According to another embodiment, the thermostable plasticizer has a molecular weight of less than 15,000 gms/mol. According to another embodiment, the thermostable plasticizer has a molecular weight of less than 20,000 gms/mol. According to another embodiment, the thermostable plasticizer has a molecular weight of less than 30,000 gms/mol. According to another embodiment, the thermostable plasticizer has a molecular weight of less than 50,000 gms/mol.
  • the thermostable plasticizer has a molecular weight of less than 60, 000 gms/mol. According to another embodiment, the thermostable plasticizer has a molecular weight of less than 70,000 gms/mol. According to another embodiment, the thermostable plasticizer has a molecular weight of less than 80,000 gms/mol. According to another embodiment, the thermostable plasticizer has a molecular weight of less than 90,000 gms/mol. According to another embodiment, the thermostable plasticizer has a molecular weight of less than 1,00,000 gms/mol. According to another embodiment, the thermostable plasticizer has a molecular weight of less than 1,00,000 gms/mol. According to another embodiment, the thermostable plasticizer has a molecular weight of less than 1,00,000 gms/mol.
  • thermostable plasticizer has a molecular weight of less than 1,20,000 gms/mol. According to another embodiment, the thermostable plasticizer has a molecular weight of less than 1,50,000 gms/mol. According to another embodiment, the thermostable plasticizer has a molecular weight of less than 2,00,000 gms/mol.
  • the thermostable plasticizer is water soluble.
  • water soluble active plasticizer includes any plasticizer which is soluble in water.
  • the thermostable plasticizer has a solubility of more than 0.1 mg/liter in water at 20°C.
  • the thermostable plasticizer has a solubility of more than 0.5 mg/liter in water at 20°C.
  • the thermostable plasticizer has a solubility of more than 1 mg/liter in water at 20°C.
  • the thermostable plasticizer has a solubility of more than 1 g/liter in water at 20°C.
  • thermostable plasticizer has a solubility of more than 10 g/liter in water at 20°C. According to an embodiment, the thermostable plasticizer has a solubility of more than 25 g/liter in water at 20°C.
  • thermostable plasticizer is present in a concentration range of at least 0.01% by weight of the total composition. According to another embodiment, the thermostable plasticizer is present in a concentration range of at least 0.1% by weight of the total composition. According to another embodiment, the thermostable plasticizer is present in a concentration range of at least 1% by weight of the total composition. According to another embodiment, the thermostable plasticizer is present in a concentration range of at least 5% by weight of the total composition. According to another embodiment, the thermostable plasticizer is present in a concentration range of at least 10% by weight of the total composition. According to another embodiment, the thermostable plasticizer is present in a concentration range of at least 20% by weight of the total composition.
  • thermostable plasticizer is present in a concentration range of at least 30% by weight of the total composition. According to another embodiment, the thermostable plasticizer is present in a concentration range of at least 40% by weight of the total composition. According to another embodiment, the thermostable plasticizer is present in a concentration range of at least 50% by weight of the total composition. According to another embodiment, the thermostable plasticizer is present in a concentration range of at least 60% by weight of the total composition.
  • the agrochemically acceptable excipients, auxiliaries or additives comprise wetting agents, dispersing agents, emulsifiers, binding agents, biocides, sticking agents, disintegrating agents, fillers, diluents, plasticizers, spreading agents, surfactants, solvents, coating agents, pigments, dyes, anti caking agents, thixotropic agents, anti-drift agents, colorants, buffers, pH adjusters, adhesives, fragrances, evaporation inhibitors, fertilizers, micronutrients, macro- nutrients, protective colloids, antifoam agents, antimicrobial agents, complexing agents, neutralizing agents, odorants, viscosity modifiers, thickeners, penetration aids, processing additives, sequestering agents, humectants, preservatives, polyethers, lubricants, protective colloids, solvents, coating agents, antioxidants and stabilizers or derivatives, an anti-mold agent, a bubble agent, agglomeration suppressants, wax,
  • Surfactants can include one or more of non-ionic surfactants, anionic surfactants or derivatives and mixtures thereof.
  • the agrochemically acceptable excipients are commercially manufactured and available through various companies. According to an embodiment, the agrochemically acceptable excipients are present in a concentration range of 0.01% to 99% by weight of the total composition. According to an embodiment, the agrochemically acceptable excipients are present in a concentration range of 0.01% to 80% by weight of the total composition. According to an embodiment, the agrochemically acceptable excipients are present in a concentration range of 0.01% to 60% by weight of the total composition.
  • the disintegrants used in the granular composition include, but not limited to one or more of sodium, potassium bicarbonates/ carbonates or their mixtures or salts with acids such as citric and fumaric acid, Polyplasdone ® XL-10 crosslinked polyvinylpyrrolidone, microcrystalline cellulose, cross-linked sodium carboxymethyl cellulose and salts of polyacrylates of methacrylates.
  • the dispersants are present in a concentration range of 0.01% to 80% by weight of the total composition.
  • the dispersants used in the granular composition include, but not limited to one or more of polyvinyl pyrrolidone, polyvinyl alcohol, lignin sulphonates, phenol naphthalene sulphonates, ethoxylated alkyl phenols, ethoxylated fatty acids, alkoxylated linear alcohols, polyaromatic sulfonates, sodium alkyl aryl sulfonates, glyceryl esters, maleic anhydride copolymers, phosphate esters, condensation products of aryl sulphonic acids and formaldehyde, condensation products of aryl sulphonic acids and urea formaldehyde with formaldehyde condensate of naphthalene sulfonic acid, addition products of ethylene oxide and fatty acid esters, salts of addition products of ethylene oxide and fatty acid esters, sulfonates of condensed naphthalene,
  • the dispersants that are commercially available under the trademark but are not limited to Norlig ® lid calcium lignosulfate, sodium naphthalene formaldehyde condensate available under brands Morwet ® D425 Lomar ® PW (emery 5353), Polyfon ® AF sodium modified kraft lignin, Morwet ® EFW Mixture of sodium alkyl naphthalene sulfonates and alkyl carboxylate. According to an embodiment, the dispersants are present in a concentration range of 0.01% to 80% by weight of the total composition.
  • the wetting agents used in the granular composition include, but not limited to one or more of phenol naphthalene sulphonates, alkyl naphthalene sulfonate, sodium alkyl naphthalene sulfonate, sodium salt of sulfonated alkylcarboxylate, polyoxyalkylated ethyl phenols, polyoxyethoxylated fatty alcohols, alkyl sulfosuccinates, polyoxyethoxylated fatty amines, lignin derivatives, lignosulfonates, alkane sulfonates, taurates, alkylbenzene sulfonates, salts of polycarboxylic acids, salts of esters of sulfosuccinic acid, alkylnaphthalenesulphonates, phosphate esters condensation products of formaldehyde, phenol sulfonic acid condensates, acety
  • the wetting agents are commercially manufactured and available through various companies. Some of them that are available under brand names, but not limited to Petro * Ag-Special sodium alkylnaphthalene sulfonate, Masil * 280LP silicone surfactant, Alkanol ® XC Sodium alkyl naphthalene sulfonate, Siponate ® DS-10 Sodium dodecyl benzene sulfonate, Siponate ® 301- 10F Sodium alkyl alpha-olefin sulfonate, Tamol ® SN Sodium naphthalene sulfonate formaldehyde condensate, C 14 -C 19 olefin sulfonate sodium salt (eg (R) Hostapur OS.) And Alkyldiglykolathersulfat sodium salt (for example (R) Genapol LRO.). According to an embodiment, the wetting agents are present in a concentration range of 0.01% to
  • the carbohydrate binders can include one or more of glucose, mannose, fructose, galactose, sucrose, lactose, maltose, xylose, arabinose, trehalose and mixtures thereof.
  • the binding agents can also include corn syrup; celluloses such as carboxymethylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxy-methylethylcellulose, hydroxyethylpropylcellulose, methylhydroxyethylcellulose, methylcellulose; starches such as amylose, seagel, starch acetates, starch hydroxyethyl ethers, ionic starches, long-chain alkyl starches, dextrins, maltodextrin, corn starch, amine starches, phosphates starches, and dialdehyde starches; plant starches such as corn starch and potato starch; other carbohydrates such as pectin, amylopectin, xylan, xanthan gum, glycogen, agar, alginic acid, phycocolloids, chitin, gum arabic, guar gum, gum karaya, gum tragacanth and locust bean gum.
  • corn syrup celluloses such as carb
  • the binding agents can also include complex organic substances such as phenyl naphthalene sulphonate, lignin and nitrolignin; derivatives of lignin such as lignosulfonate salts illustratively including calcium lignosulfonate and sodium lignosulfonate and complex carbohydrate-based compositions containing organic and inorganic ingredients such as molasses.
  • Suitable protein binders illustratively can include soy extract, zein, protamine, collagen, and casein.
  • the functional binding agents can also include synthetic organic polymers such as ethylene oxide polymers or copolymers, propylene oxide copolymer, polyethylene glycols, polyethylene oxides, polyacrylamides, polyacrylates, polyvinyl pyrrolidone, polyalkyl pyrrolidone, polyvinyl alcohol, polyvinylmethyl ether, polyvinyl acrylates, hydrated inorganics such as sodium silicate, sorbitol, or urea, polylactic acid, polyethoxylated fatty acids, polyethoxylated fatty alcohols and latex.
  • synthetic organic polymers such as ethylene oxide polymers or copolymers, propylene oxide copolymer, polyethylene glycols, polyethylene oxides, polyacrylamides, polyacrylates, polyvinyl pyrrolidone, polyalkyl pyrrolidone, polyvinyl alcohol, polyvinylmethyl ether, polyvinyl acrylates, hydrated inorganics such as sodium silicate, sorb
  • the binding agents are present in a concentration range of 0.01% to 80% by weight of the total composition.
  • the fillers or carriers include, but not limited to one or more of attapulgite, kaolinites, clays, montmorillonite, montromolite, bauxite, hydrated aluminas, perlite, calcined aluminas, diatomaceous earth, chalk, fuller's earth, dolomite, kiesulguhr, loess, prophyllites, talc, mirabilite, starch, lactose, white carbon, Sericite, slaked lime, sodium carbonate, sodium bicarbonate, volclay, vermiculites, limestone, natural and synthetic silicates, calcium and magnesium silicates, titanium dioxide, hydroxides, silicates, carbonates and sulfates of calcium, magnesium, aluminum and titanium, aluminum, titanium, magnesium, calcium and zinc oxide, calcium and magnesium carbonate, and charcoal, silicas, mica, china clay, swelling and non- swelling clays, synthetic and diatomaceous silicas, , ammonium, sodium, potassium,
  • Silicates are Aerosil brands, Sipemat brands as Sipernat ® 50S and CALFLO E, and aerogels Fa. Cabot, kaolin 1777, aluminosilicates, Wessalon * 50S.
  • Preferred carriers include, but not limited to one or more of attapulgite, kaolinites, clays, montmorillonite, montromolite, bauxite, hydrated aluminas, perlite and its derivatives calcined aluminas, diatomaceous earth, chalk, fuller's earth, dolomite, kiesulguhr, loess, prophyllites, talc, vermiculites, limestone, natural and synthetic silicates, silicas, mica.
  • the fillers that are commercially available under the trademark but are not limited to According to an embodiment, the fillers or carriers are present in a concentration range of 0.01% to 90% by weight of the total composition.
  • filler has an oil absorption capacity of at least 30%. According to further embodiment, the filler has an oil absorption capacity of more than 35%. According to further embodiment, the filler has oil absorption capacity of more than 50%. According to further embodiment, the filler has an oil absorption capacity of more than 75%. According to further embodiment, the filler has the oil absorption capacity of more than 100%. According to another embodiment, the filler has an oil absorption capacity of up to 175%. According to further embodiment, the filler has an oil absorption capacity of up to 160%. According to further embodiment, the filler has an oil absorption capacity of up to 115%. According to an embodiment, the filler has oil absorption capacity in the range of 30% to 175%.
  • the composition optionally include anti-caking agents such as Foammaster ® Soap L sodium stearate, Brij ® 700 polyoxyethylene (100) stearyl ether, Aerosol ® OT- B sodium dioctyl sulfosuccinate, Silwet ® L-77 silicone-polyether copolymer, sodium and ammonium phosphates, sodium acetate, sodium metasilicate, magnesium, zinc and calcium sulfates, magnesium hydroxide, anhydrous calcium chloride, molecular sieves, sodium alkylsulfosuccinates, calcium and barium oxides, sodium carbonate or bicarbonate.
  • anti-caking agents such as Foammaster ® Soap L sodium stearate, Brij ® 700 polyoxyethylene (100) stearyl ether, Aerosol ® OT- B sodium dioctyl sulfosuccinate, Silwet ® L-77 silicone-polyether copolymer, sodium and ammoni
  • the emulsifiers or surfactants include one or more of ionic, non- ionic and amphoteric surfactants.
  • the ionic surfactants include one or more of, but not limited to carboxylates, alkyl carboxylates, fatty acid salts, fluoro carboxylate, alkyl sulfates, alkyl ether sulfates, sulfonates, alkyl benzene sulfonates, alpha olefin sulphonates, aromatic hydrocarbon sulphonates, naphthalene sulfonate salts, fatty alcohol sulphates, mono-alkyl sulphosuccinates, alkyl sulphosuccinamates, naphthalene sulphonates, sulfonate docusates, phosphate esters, alkyl aryl ether phosphates, alkyl ether phosphates, quaternary ammonium salt
  • the non-ionic surfactants include one or more of, but not limited to polyol esters, polyol fatty acid esters, polyethoxylated esters, polyethoxylated alcohols, block copolymers of polyethylene glycol and polypropylene glycol, poloxamers, polysorbates, alkyl polysaccharides such as alkyl polyglycosides and blends thereof, amine ethoxylates, sorbitan fatty acid ester , glycol and glycerol esters , glucosidyl alkyl ethers, sorbitan alkyl esters, sodium tallowate, polyoxyethylene glycol sorbitan alkyl esters, sorbitan derivatives, fatty acid esters of sorbitan (Spans) and their ethoxylated derivatives (Tweens), and sucrose esters of fatty acids.
  • polyol esters polyol fatty acid esters, polyethoxylated esters, polye
  • nonionic emulsifier include one or more of, but not limited to polyethylene glycol, glyceryl laureate, lauryl glucoside, nonylphenolpolyethoxyethanols, nonyl phenol polyglycol ether , castor oil ethoxylate, polyglycol ethers, polyadducts of ethylene oxide and propylene oxide, block copolymer of polyalkylene glycol ether and hydroxystearic acid, ethylene oxide propylene oxide block copolymer, tributylphenoxypolyethoxy ethanol, octylphenoxypolyethoxy ethanol, etho- propoxylatedtristyrlphenols, ethoxylated alcohols, polyoxy ethylene sorbitan, a sorbitan fatty acid ester, a glycerin fatty acid ester, a fatty acid polyglyceride, a fatty acid alcohol polyglycol ether, acety
  • the anionic surfactants include one or more of, but not limited to a salt of fatty acid, a benzoate, a polycarboxylate, a salt of alkylsulfuric acid ester, an alkyl sulfate, an alkylaryl sulfate, an alkyl diglycol ether sulfate, a salt of alcohol sulfuric acid ester, an alkyl sulfonate, an alkylaryl sulfonate, an aryl sulfonate, a lignin sulfonate, an alkyldiphenylether disulfonate, a polystyrene sulfonate, a salt of alkylphosphoric acid ester, an alkylaryl phosphate, a styrylaryl phosphate, a salt of polyoxyethylene alkyl ether sulfuric acid ester, a polyoxyethylene alkylaryl ether sulfate, a salt of polyoxyethylene
  • Non-ionic emulsifiers or surfactant that are commercially available under the trademark but are not limited to Atlas G5000 and TERMUL 5429JERMU L 2510, ECOTERIC ® , EU LSOG EN ® 118,Genapol ® X , Genapol ® OX -080 , Genapol ® C 100, Emulsogen ® EL 200, Arlacel P135, Hypermer 8261, Hypermer B239, Hypermer B261, Hypermer B246sf, Solutol HS 15,PromulgenTM D,Soprophor 7961P, Soprophor TSP/461, Soprophor TSP/724, Croduret 40, Etocas 200, Etocas 29, Rokacet R26 ,CHEMONIC OE-20, TritonTM N-101,Tween 20,40,60,65,80, Span20, 40,60,80,83,85,120, Brij ® , TritonTM can also be used.
  • Amphoteric surfactants can include one or more of betaine, imidazolines, alkyl amphoacetates and proprionates, alkyl Ampho(di)acetates, and diproprionates, lecithin. According to an embodiment, the surfactants or emulsifiers are present in a concentration range of 0.01% to 90% by weight of the total composition.
  • the antioxidants can be selected from, but not limited to one or more of amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and derivatives thereof, imidazole and imidazole derivatives (e.g. urocanic acid), peptides, such as, D,L-carnosine, D- carnosine, L-carnosine and derivatives thereof (e.g. anserine), caro- tenoids, carotenes (e.g. ct- carotene, ⁇ -carotene, lycopene) and derivatives thereof, lipoic acid and derivatives thereof (e.g.
  • amino acids e.g. glycine, histidine, tyrosine, tryptophan
  • imidazole and imidazole derivatives e.g. urocanic acid
  • peptides such as, D,L-carnosine, D- carnosine, L-carnosine and derivatives thereof (e
  • thioglycerol thiosorbitol, thioglycolic acid, thioredoxin, glutathione, cysteine, cystine, cystamine and the glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl, lauryl, palmitoyl, oleyl, y-linoleyl, cholesteryl and glyceryl esters thereof
  • salts thereof dilauryl thiodipropionate, distearyl thiodipropion- ate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts), and sulfoximine compounds (e.g.
  • buthionine sulfoximi- nes homocysteine sulfoximine, buthionine sulfones, penta-, hexa-, heptathionine sul- foximine
  • metal chelating agents e.g. a-hydroxy fatty acids, EDTA, EGTA, phytic acid, lactoferrin
  • ⁇ -hydroxy acids e.g. citric acid, lactic acid, malic acid
  • humic acids bile acid, bile extracts, gallic esters
  • propyl, octyl and dodecyl gallate flavonoids, catechins, bilirubin, biliverdin and derivatives thereof, unsaturated fatty acids and derivatives thereof (e.g. y-linolenic acid, linoleic acid, arachidonic acid, oleic acid), folic acid and derivatives thereof, hy- droquinone and derivatives thereof (e.g. arbutin), ubiquinone and ubiquinol, and derivatives thereof, vitamin C and derivatives thereof (e.g.
  • vitamin A palmitate the coniferyl benzoate of benzoin resin, rutin, rutinic acid and derivatives thereof, disodium rutinyl disulfate, cinnamic acid and deriva- tives thereof (e.g. ferulic acid, ethyl ferulate, caffeeic acid), kojic acid, chitosan glyco- late and salicylate, butylhydroxytoluene, butylhydroxyanisol, nordihydroguaiacic acid, nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid and derivatives thereof, mannose and derivatives thereof, selenium and selenium derivatives (e.g.
  • stilbenes and stilbene derivatives e.g. stilbene oxide, trans-stilbene oxide
  • suitable derivatives salts, esters, sugars, nucleotides, nucleosides, peptides and lipids
  • mixtures of these specified active ingredients or plant extracts e.g. teatree oil, rosemary extract and rosemarinic acid
  • teatree oil, rosemary extract and rosemarinic acid e.g. teatree oil, rosemary extract and rosemarinic acid
  • the antioxidants are present in a concentration range of 0.01% to 60% by weight of the total composition.
  • the composition can also comprise a pH adjuster or buffer or neutralizing agent.
  • the pH buffer or neutralizing agent can include both acids and bases of organic or inorganic origin.
  • the pH buffer or neutralizing agent include but are not limited to organic acids, inorganice acids and alkali metal compounds or salts.
  • the organic acids can include, but not limited to one or more of citric, malic, adipic, cinnamic, fumaric, maleic, succinic and tartaric acid or salts or derivatives thereof, and the mono-, di- or tribasic salts of these acids or derivatives thereof.
  • Suitable salts of these acids can be the soluble or meltable salts and include those salts in which one or more acidic protons are replaced with a cation such as sodium, potassium, calcium , magnesiu, and ammonium and mixtures thereof.
  • Alkali metal compounds can include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, carbonates of alkali metals such as sodium carbonate, magnesium carbonates and potassium carbonate, hydrogen carbonates of alkali metals such as sodium hydrogencarbonate and alkali metal phosphates such as sodium phosphate and mixtures thereof.
  • the salts of inorganic acids include, but are not limited to one or more of alkali metal salts such as lithium chloride, sodium chloride, potassium chloride, lithium nitrate, sodium nitrate, potassium nitrate, lithium sulfate, sodium sulfate , potassium sulfate, sodium monohydrogen phosphate, potassium monohydrogen phosphate, sodium dihydrogen phohsphate potassium dihydrogen phosphate and the like; alkaline earth metal salts such as magnesium choliride, calcium chloride, ammonium sulphate, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate and the like.
  • alkali metal salts such as lithium chloride, sodium chloride, potassium chloride, lithium nitrate, sodium nitrate, potassium nitrate, lithium sulfate, sodium sulfate , potassium sulfate, sodium monohydrogen phosphate, potassium monohydrogen phosphate, sodium dihydrogen phohs
  • the invention further relates to the process of preparing a stable granular composition.
  • the process involves mixing and blending at least one agrochemical active ingredient wherein the agrochemical active comprises at least one of a water soluble active ingredient or a water sensitive active ingredient; with at least one thermostable polymer to obtain a mixture.
  • premilled fillers and surfactants are blended.
  • the entire mixture of the active, plasticizer, filler and surfactants, disintegrants, are then heated in an oil bath at a temperature appropriate for melting the thermostable polymer or plasticizer.
  • the melted mixture was then extruded through a medium pressure extruder to give the the stable agrochemical granular composition; such that the granular composition has a wettability of less than 20 minutes.
  • the process conditions need to be carefully managed so as to give a final granular product, which has the desired properties of disintegration time, wettability, dispersibility and floatability.
  • a person skilled in the art can, using the right amount of pressure during extrusion, provide the desired composition.
  • Cartaphydrochloride 65 parts by weight of Cartaphydrochloride was further mixed thoroughly with 22 parts by wet of citric acid to obtain a mixture A.
  • filler including dolomite, kiesulguhr, perlite and WitconateTM (Sodium alkyl aryl sulfonate) was added and mixed thoroughly. Further 200 parts by weight of PEG 4000 was added. The mixture was then heated and extruded and cooled to obtain a granular composition of 6.5% Cartap hydrochloride.
  • Granular Composition containing 4% Cartap hydrochloride and 72.5% Sulphur
  • WitconateTM (Sodium
  • Example 1 Bioefficacy of Cartap hydrochloride granules as per the embodiment of the present invention: The field trials were carried out in the Hissar district of Haryana state in India on rice, to evaluate the effectiveness of Cartap hydrochloride granules prepared as per the embodiment of the present invention as well as Sulphur plus Cartap hydrochloride granules as per the embodiment of the present invention. The experiments were also conducted using Sulphur 90% WG standalone and Cartap hydrochloride 4% Granules standalone used as standards for comparison as well as an untreated control. The treatments also included compositions of Sulphur 70% + Cartap Hydrochloride 4% WP prepared as per the embodiment of 251/MU M/2011. The treatments also included compositions as per the embodiments of EP1882414, EP2460408 and US6703350B 5 which disclose granular compositions of Cartap.
  • the treatments were carried out following the randomized block design and keeping all the agronomic practices uniform for all the treatments.
  • the treatments were imposed as and when a significant number of stem borer (Scirpophaga incertulas Walker) population per leaf were observed. All the agronomic practices were adopted as per recommendations.
  • the treatments were carried out by broadcasting the compositions twice the on 30 th and the 60 th days after rice transplantation. To avoid intermixing of treatments about 20 to 30 cm thick false bund boundaries were prepared all around plots having the treatments of granular insecticides. Both the applications and their efficacy were evaluated.
  • treatment 1 with 4% Cartap hydrochloride granules
  • treatment 2 with 6% Cartap hydrochloride granules
  • treatment 3 with Sulphur 75%+Cartap Hydrochloride 4% granules
  • treatment 4 with Sulphur 75%+Cartap Hydrochloride 6% granules
  • Treatment 1 with 4% Cartap hydrochloride granules
  • treatment 2 with 6% Cartap hydrochloride granules
  • treatment 3 with Sulphur 75%+Cartap Hydrochloride 4% granules
  • treatment 4 with Sulphur 75%+Cartap Hydrochloride 6% granules
  • the crops also exhibited enhanced chlorophyll content due to the application of sulphur in combination with cartap hydrochloride in varying concentrations.
  • composition in practice serves the purpose of simultaneously managing the damage caused by stem borer and leaf folder and the need of sulphur fertilizer required in the initial stages of plant growth, thereby rendering the composition more economical and beneficial to the end-users when compared to the individual application of Cartap hydrochloride or Sulphur.

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Abstract

The invention relates to a stable agrochemical granular composition comprising: at least one first agrochemical active ingredient, wherein the first agrochemical active comprises at least one of a water soluble active ingredient or a water sensitive active ingredient; at least one thermostable plasticizer wherein the plasticizer has a melting point greater than 20°C and less than 150°C; at least one agrochemically acceptable excipient; wherein the granular composition has a wettability of less than 20 minutes. The invention further relates to a process of preparation of the stable agrochemical granular composition. It also further relates to a method of application of the stable agrochemical granular composition.

Description

STABLE FORMULATION OF WATER SENSITIVE ACTIVE
1. FIELD OF INVENTION:
The present invention relates to a stable granular composition including at least one agrochemical active ingredient, wherein the agrochemical active includes one or more of water soluble active ingredient or a water sensitive active ingredient for agrochemical purposes. More particularly, the invention relates to a stable agrochemical granular composition including at least one agrochemical active ingredient, wherein the agrochemical active includes one or more of a water soluble active ingredient or a water sensitive active ingredient, at least one thermostable plasticizer wherein the plasticizer has a melting point greater than 20°C and less than 150°C; and at least one agrochemically acceptable excipient. The granular composition has a wettability of less than 20 minutes.
The invention further relates to a process of preparing a stable agrochemical granular composition including one or more of water soluble active ingredient or a water sensitive active ingredient. The invention furthermore relates to a method of treating the plants or the soil with the stable agrochemical granular composition including the water soluble active ingredient or the water sensitive active ingredient.
2. DESCRIPTION OF THE RELATED ART:
In describing the embodiment of the invention, specific terminology is chosen for the sake of clarity. However, it is not intended that the invention be limited to the specific terms so selected and it is to be understood that each specific term includes all technical equivalents that operate in a similar manner to accomplish a similar purpose.
Granular agrochemical compositions have become very popular in recent years because they are safe and more convenient to handle than conventional agrochemical formulations such as wettable powders and emulsfiable concentrates. Various agrochemical actives are known to be developed in the form of water dispersible granular formulation due to the advantages offered by such formulation. Most granulation methods in current use, generally referred to herein as wet granulation, require introduction of water for granulation and then a drying step to remove the water.
Unfortunately, certain active agents have the disadvantage of being highly sensitive and unstable in aqueous media and of being readily degraded or modified under the influence of water due to poor chemical stability. Typically, hydrolysis is the most common water-mediated degradation mechanism; however, such actives are also likely to undergo oxidation, dehalogenation, bond cleavage, Beckmann rearrangement and other forms of degradation on coming in contact with water. The actives tend to lose their activity or convert into another form on coming into contact with water. Such actives typically lose their activity over time, and this instability goes against the desired field efficacy making them unavailable to the soil or plants or the desired target. Further, some of the agrochemical actives due to their water soluble nature cannot be formulated into a stable water dispersible granular formulation.
To overcome these drawbacks such active agents have been formulated in an anhydrous liquid medium. However, such a formulation does not permit the incorporation of hydrophilic active agents. Furthermore, in order to avoid the exposure with water, generally these actives have been known to be formulated as Emulsifiable concentrates, dusts, wettable powders, etc.
However, these formulations include a large amount of organic solvents such as toluene, xylene and the like, leading to thousands of tons per year of organic solvent emissions in the nature, posing severe risk and threat to the environment and the soil in terms of toxicity and pollution.
Furthermore, these compositions are also required to be applied at very high dosages of application.
Especially, in a rice paddy field such agrochemical formulations are premised on being scattered unevenly. In recent years, saving labor for scattering (applying) agricultural chemicals and cutting down of agricultural chemicals has become important and improvement of the formulation form of the agricultural chemicals is required.
Also, commercially available formulations tend to either settle or sediment at the bottom at one location or float, spread on the water surface without providing good dispersion or disintegration of the active which in turn fail to obtain a desirable spreadability and uniform distribution of the components to the crops for uptake. Moreover, such granular formulations have a very poor hardness leading to a premature breakdown of these compositions during production, storage, handling and application of these granules or powders resulting in substantial loss of release control, phytotoxic problems, and excessive nutrient leaching in turn reducing their efficacy on field application. Such compositions are therefore being applied at significantly higher dosages thereby also increasing the cost of application to the farmer. Prior art compositions comprising water sensitive or soluble active ingredients provide compositions which do not possess good properties of wettability and disintegration time. These prior art compositions also tend to float for long durations and also do not reach the plant root zone, or desired target area, and therefore tend to leach away, contributing to inadequate pest control, loss to the farmer and damage to the environment.
Consequently, making a stable water free agrochemical granular formulation of a water soluble active ingredient or a water sensitive active ingredient, is a great challenge. There is thus a need for a composition of a water soluble or a water sensitive active ingredient that can provide good stability of the formulation under cold and warm conditions, show good resistance of the active agent to oxidation or hydrolysis, exhibits good hardness during storage or handling while providing improved crop protection from pests attack, at reduced application rates over an extended period of time.
It has now been, surprisingly, found that a stable agrochemical granular composition of one or more water soluble or a water sensitive active ingredient provides excellent efficacy, ease of application, retains all the properties of the active, avoids decomposition of the active and is friendly to the farmers as well as the environment, as compared to conventional formulations. Interestingly, it has been found that the stable water free granular composition of water soluble or a water sensitive active with at least one thermostable plasticizer works effectively at a reduced dosage, offers broader crop protection spectrum and control against various insects, weeds, mites and fungi, improves growth and quality of crops/plants and thus, highly cost effective in nature, which not only exhibits enhanced wettability but also shows improved hardness and good disintegration in water thus ensuring a uniform application and availability for an extended period of time.
SUMMARY OF THE INVENTION
The present invention relates to a stable agrochemical granular composition of at least one or more agrochemical active ingredient, wherein the agrochemical active includes one or more water soluble active ingredient or a water sensitive active ingredient; at least one thermostable plasticizer with a melting point greater than 20°C and less than 150°C; and at least one agrochemically acceptable excipient; wherein the granular composition exhibits a wettability of less than 20 minutes. The invention further relates to a process of preparing a stable granular composition, involving mixing and blending at least one agrochemical active ingredient selected from one or more of a water soluble active ingredient or a water sensitive active ingredient; with at least one thermostable polymer to obtain a mixture; heating and cooling the mixture to arrive at the stable agrochemical granular composition; wherein the granular composition exhibits a wettability of less than 20 minutes.
The invention further relates to method of protection of crop or improving its health or yield, by treating at least one of a plant, crop, a plant propagation material, a seed, seedling or surrounding soil with a stable granular composition of at least one agrochemical active ingredients selected from one or more of a water soluble active ingredient or a water sensitive active ingredient; at least one thermostable plasticizer; and, at least one agrochemically acceptable excipient; wherein the granular composition exhibits a wettability of less than 20 minutes.
It has been surprisingly observed that composition not only exhibits wettability of less than 20 minutes but also has a hardness of less than 5 N, demonstrates reduced decomposition of the active, good physical properties of disintegration, dispersion and suspension, good release properties for the entire crop life cycle. Moreover, the composition exhibits a surprisingly higher field efficacy at significantly reduced dosages of application of the composition. DESCRIPTION OF THE INVENTION:
In describing the embodiments of the invention, specific terminology is resorted for the sake of clarity. However, it is not intended that the invention be limited to the specific terms so selected and it is to be understood that each specific term includes all technical equivalents that operate in a similar manner to accomplish a similar purpose.
The invention relates to a stable agrochemical granular composition which includes: at least one agrochemical active ingredient. The agrochemical active ingredient includes one or more of water soluble active ingredient or a water sensitive active ingredient. The composition further includes at least one thermostable plasticizer which has a melting point greater than 20°C and less than 150°C;
and at least one agrochemically acceptable excipient. The granular composition exhibits a wettability of less than 20 minutes.
According to the invention, the term "water sensitive active ingredient" means a chemically and/or physically unstable active agent. The term "chemical instability" especially means degradation of the active principle. Water-sensitive agrochemically active ingredients are those which are subject to a water-mediated degradation such as hydrolysis, oxidation, dehalogenation, bond cleavage, Beckmann rearrangement and other forms of degradation on exposure to water.
As used herein, the term "degradation" denotes loss of activity of the water sensitive active ingredient, upon coming in contact with water. Degradation can be determined simply by measuring the amount of the active ingredient present before and after contact with water.
The term "physical instability" especially means crystallization or precipitation of the active agent, or modification of its colour within the composition.
The term "water soluble active ingredient" is an agrochemical active ingredient which is soluble in water to little extent or even a large extent. According to an embodiment, the agrochemical active ingredient has a solubility of more than 0.1 mg/liter in water at 20°C. According to an embodiment, the agrochemical active ingredient has a solubility of more than 0.5 mg/liter in water at 20°C. According to an embodiment, the agrochemical active ingredient has a solubility of more than 1 mg/liter in water at 20°C. According to an embodiment, the agrochemical active ingredient has a solubility of more than lg/liter in water at 20°C.
According to an embodiment, the agrochemical active is at least one selected from an antifoulant, an attractant, an insecticide, a fungicide, a herbicide, a nematicide, a pheromone, a defoliant, an acaricide, a plant growth regulator, an algicide, an antifeedant, an avicide, a bactericide, a bird repellent, a biopesticide, a biocide, a chemosterilant, a safener, an insect attractant, an insect repellent, a insect growth regulator, a mammal repellent, a mating disrupter, a desiccant, a disinfectant, a molluscicide, an antimicrobial, a miticide, an ovicide, a fumigant, a plant activator, a rodenticide, a synergist, a virucide, a repellent, a microbial pesticide, a plant incorporated protectant, other miscellaneous pesticidal active, or salts, derivatives and mixtures therefore. According to an embodiment, the first or second agrochemical active is at least one selected from but are not limited to one or more of "abamectin, abamectin-aminomethyl, abscisic acid, ACC, acephate, acequinocyl, acetamiprid, acethion, acetochlor, acetofenate, acetophos, acetoprole, acibenzolar, acifluorfen, aclonifen, acetonitrile, acrep, acrinathrin, acrolein, acrylonitrile, acynonapyr, acypetacs, afidopyropen, afoxolaner, alachlor, alanap, alanycarb, albendazole, aldicarb, aldicarb sulfone, aldimorph, aldoxycarb, aldrin, allethrin, d-trans-allethrin, allicin, allidochlor, allosamidin, alloxydim, allyl alcohol, allyxycarb, alorac, alpha-bromadiolone, alpha- cypermethrin, alpha-endosulfan, alphamethrin, altretamine, aluminium phosphide, aluminum phosphide, ametoctradin, ametridione, ametryn, ametryne, amibuzin, amicarbazone, amicarthiazol, amidithion, amidochlor, amidoflumet, amidosulfuron, aminocarb, aminocyclopyrachlor, aminopyralid, 4-aminopyridine, aminotriazole, amiprofos-methyl, amiprophos, amiprophos-methyl, amisulbrom, amiton, amitraz, amitrole, ammonium sulfamate, amobam, amorphous silica gel, amorphous silicon dioxide, ampropylfos, AMS, anabasine, ancymidol, anilazine, anilofos, anisuron, anthraquinone, antu, apholate, aramite, arprocarb, arsenous oxide, asomate, aspirin, asulam, athidathion, atraton, atrazine, aureofungin, avermectin Bl, AVG, aviglycine, azaconazole, azadirachtin, azafenidin, azamethiphos, azidithion, azimsulfuron, azinphos-ethyl, azinphosethyl, azinphos-methyl, azinphosmethyl, aziprotryn, aziprotryne, azithiram, azobenzene, azocyclotin, azothoate, azoxystrobin, bachmedesh, barban, barbanate, barium hexafluorosilicate, barium polysulfide, barium silicofluoride, barthrin, basic copper carbonate, basic copper chloride, basic copper sulfate, BCPC, beflubutamid, benalaxyl, benalaxyl-M, benazolin, bencarbazone, benclothiaz, bendaqingbingzhi, bendiocarb, bendioxide, benefin, benfluralin, benfuracarb, benfuresate, , benodanil, benomyl, benoxacor, benoxafos, benquinox, bensulfuron, bensulide, bensultap, bentaluron, bentazon, bentazone, benthiavalicarb, benthiazole, benthiocarb, bentranil, benzadox, benzalkonium chloride, benzamacril, benzamizole, benzamorf, benzene hexachloride, benzfendizone, benzimine, benzipram, benzobicyclon, benzoepin, benzofenap, benzofluor, benzohydroxamic acid, benzomate, benzophosphate, benzothiadiazole, benzovindiflupyr, benzoximate, benzoylprop, benzpyrimoxan, benzthiazuron, , benzyladenine, benzyl benzoate, berberine, beta-cyfluthrin, beta-cypermethrin, bethoxazin, BHC, gamma-BHC, bialaphos, bicyclopyrone, bifenazate, bifenox, bifenthrin, kappa-bifenthrin, bilanafos, binapacryl, bingqingxiao, bioallethrin, S-bioallethrin, bioethanomethrin, biopermethrin, bioresmethrin, biphenyl, bisazir, bismerthiazol, bismerthiazol-copper, bisphenylmercury methylenedi(x-naphthalene-y-sulphonate), bispyribac, bistrifluron, bisultap, bitertanol, bithionol, bixafen, blasticidin-S, borax, Bordeaux mixture, boric acid, boscalid, BPCMS, BPPS, brassinolide, brassinolide-ethyl, brevicomin, brodifacoum, brofenprox, brofenvalerate, broflanilide, brofluthrinate, bromacil, bromadiolone, alpha-bromadiolone, bromchlophos, bromethalin, bromethrin, bromfenvinfos, bromoacetamide, bromobonil, bromobutide, bromociclen, bromocyclen, bromo-DDT, bromofenoxim, bromofos, bromomethane, bromophos, bromophos- ethyl, bromopropylate, bromothalonil, bromoxynil, brompyrazon, bromuconazole, bronopol, BRP, BTH, bucarpolate, bufencarb, buminafos, bupirimate, buprofezin, Burgundy mixture, busulfan, busulphan, butacarb, butachlor, butafenacil, butam, butamifos, butane-fipronil, butathiofos, butenachlor, butene-fipronil, butethrin, buthidazole, buthiobate, buthiuron, butifos, butocarboxim, butonate, butopyronoxyl, butoxycarboxim, butralin, butrizol, butroxydim, buturon, butylamine, butylate, butylchlorophos, butylene-fipronil, cacodylic acid, cadusafos, cafenstrole, calciferol, calcium arsenate, calcium chlorate, calcium cyanamide, calcium cyanide, calcium polysulfide, calvinphos, cambendichlor, camphechlor, camphor, d-camphor, captafol, captan, carbarn, carbamorph, carbanolate, carbaril, carbaryl, carbasulam, carbathion, carbendazim, carbendazol, carbetamide, carbofenotion, carbofuran, carbon disulfide, carbon tetrachloride, carbonyl sulfide, carbophenothion, carbophos, carbosulfan, carboxazole, carboxide, carboxin, carfentrazone, carpropamid, cartap, cartap hydrochloride, carvacrol, carvone, CAVP, CDAA, CDEA, CDEC, cellocidin, CEPC, ceralure, cerenox, cevadilla, Cheshunt mixture, chinalphos, chinalphos- methyl, chinomethionate, chiralaxyl, chitosan, chlobenthiazone, chlomethoxyfen, , chloralose, chloramben, chloramine phosphorus, chloramphenicol, chloraniformethan, chloranil, chloranocryl, chlorantraniliprole, chlorazifop, chlorazine, chlorbenside, chlorbenzuron, chlorbicyclen, chlorbromuron, chlorbufam, chlordane, chlordecone, chlordimeform, chlorempenthrin, chloretazate, chlorethephon, chlorethoxyfos, chloreturon, chlorfenac, chlorfenapyr, chlorfenazole, chlorfenethol, chlorfenidim, chlorfenprop, chlorfenson, chlorfensulphide, chlorfenvinphos, chlorfenvinphos-methyl, chlorfluazuron, chlorflurazole, chlorflurecol, chlorfluren, chlorflurenol, chloridazon, chlorimuron, chlorinate, chlormephos, chlormequat, chlormesulone, chlormethoxynil, chlornidine, chlornitrofen, chloroacetic acid, chlorobenzilate, chlorodinitronaphthalenes, chlorofenizon, chloroform, ct-chlorohydrin, chloromebuform, chloromethiuron, chloroneb, chlorophacinone, chlorophos, chlorophthalim, chloropicrin, chloropon, chloroprallethrin, chloropropylate, chlorothalonil, chlorotoluron, chloroxifenidim, chloroxuron, chloroxynil, chlorphonium, chlorphoxim, chlorphthalim, chlorprazophos, chlorprocarb, chlorpropham, chlorpyrifos, chlorpyrifos-methyl, chlorquinox, chlorsulfuron, chlorthal, chlorthiamid, chlorthiophos, chlortoluron, chlozolinate, , cholecalciferol, choline chloride, chromafenozide, cicloheximide, cimectacarb, cimetacarb, cinerin I, cinerin II, cinerins, cinidon-ethyl, cinmethylin, cinosulfuron, cintofen, ciobutide, cisanilide, cismethrin, clacyfos, clefoxydim, clenpirin, clenpyrin, clethodim, climbazole, cliodinate, clodinafop, cloethocarb, clofencet, clofenotane, clofentezine, clofenvinfos, clofibric acid, clofop, clomazone, clomeprop, clonitralid, cloprop, cloproxydim, clopyralid, cloquintocet, cloransulam, closantel, clothianidin, clotrimazole, cloxyfonac, cloxylacon, clozylacon, CMA, CM MP, CM P, CMU, codlelure, colecalciferol, colophonate, copper acetate, copper acetoarsenite, copper arsenate, copper carbonate, basic, copper hydroxide, copper naphthenate, copper oleate, copper oxychloride, copper 8-quinolinolate, copper silicate, copper sulfate, copper sulfate, basic, copper zinc chromate, coumachlor, coumafene, coumafos, coumafuryl, coumaphos, coumatetralyl, coumethoxystrobin, coumithoate, coumoxystrobin, 4-CPA, 4-CPB, CPMC, CPM F, 4-CPP, CPPC, credazine, cresol, cresylic acid, crimidine, crotamiton, crotoxyfos, crotoxyphos, crufomate, cryolite, cue-lure, cufraneb, cumyleron, cumyluron, cuprobam, cuprous oxide, curcumenol, CVM P, cyanamide, cyanatryn, cyanazine, cyanofenphos, cyanogen, cyanophos, cyanthoate, cyan- traniliprole, cyanuric acid, cyazofamid, cybutryne, cyclafuramid, cyclanilide, cyclaniliprole, cyclethrin, cycloate, cycloheximide, cycloprate, cycloprothrin, cyclopyrimorate, cyclosulfamuron, cycloxydim, cycluron, cyenopyrafen, cyflufenamid, cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalodiamide, cyhalofop, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cyhexatin, cymiazole, cymoxanil, cyometrinil, cypendazole, cypermethrin, alpha-cypermethrin, beta- cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyperquat, cyphenothrin, cyprazine, cyprazole, cyproconazole, cyprodinil, cyprofuram, cypromid, cyprosulfamide, cyromazine, cythioate, cytrex, 1,3-D, 2,4-D, 3,4-DA, daimuron, dalapon, daminozide, , dazomet, 2,4-DB, 3,4-DB, DBCP, d-camphor, DCB, DCI P, DCPA (USA), DCPA (Japan), DCPTA, DCU, DDD, DDPP, DDT, ppH-DDT, DDVP, 2,4-DEB, debacarb, decafentin, decamethrin, decarbofuran, deet, dehydroacetic acid, deiquat, delachlor, delnav, deltamethrin, demephion, demephion-O, demephion-S, demeton, demeton-methyl, demeton-O, demeton-O-methyl, demeton-S, demeton-S-methyl, demeton-S- methylsulphon, demeton-S-methyl sulphone, DEP, 2,4-DEP, depallethrine, derris, 2,4-DES, desmedipham, desmetryn, desmetryne, d-fanshiluquebingjuzhi, diafenthiuron, dialifor, dialifos, di-allate, diallate, diamidafos, dianat, diatomaceous earth, diatomite, diazinon, dibrom, 1,2- dibromoethane, dibutyl phthalate, dibutyl succinate, dicamba, dicapthon, dichlobenil, dichlobentiazox, dichlofenthion, dichlofluanid, dichlone, dichloralurea, dichlorbenzuron, dichlorfenidim, dichlorflurecol, dichlorflurenol, dichlormate, dichlormid, o-dichlorobenzene, ortho-dichlorobenzene, p-dichlorobenzene, para-dichlorobenzene, 1,2-dichloroethane, dichloromethane, dichlorophen, 3,6-dichloropicolinic acid, 1,2-dichloropropane, 1,3- dichloropropene, dichlorprop, dichlorprop-P, dichlorvos, dichlozolin, dichlozoline, diclobutrazol, diclocymet, diclofop, diclomezine, dicloran, dicloromezotiaz, diclosulam, dicofol, dicophane, dicou-marol, dicresyl, dicrotophos, dicryl, dicumarol, dicyclanil, dicyclonon, dieldrin, dienochlor, dietham-quat, diethatyl, diethion, diethion, diethofencarb, dietholate, diethon, diethyl pyrocarbonate, di-ethyltoluamide, difenacoum, difenoconazole, difenopenten, difenoxuron, difenzoquat, difethialone, diflovidazin, diflubenzuron, diflufenican, diflufenicanil, diflufenzopyr, diflumetorim, dikegulac, dilor, dimatif, dimefluthrin, dimefox, dimefuron, dimehypo, dimepiperate, dimetachlone, dimetan, dimethacarb, dimethachlone, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimethipin, dimethirimol, dimethoate, dimethomorph, dimethrin, dimethyl carbate, dimethyl disulfide, dimethyl phthalate, dimethylvinphos, dimetilan, dimexano, dimidazon, dimoxystrobin, dimpylate, dimuron, dinex, diniconazole, diniconazole-M, R-diniconazole, dinitramine, dinitrophenols, dinobuton, dinocap, dinocap-4, dinocap-6, dinocton, dinofenate, dinopenton, dinoprop, dinosam, dinoseb, dinosulfon, dinotefuran, dinoterb, dinoterbon, diofenolan, dioxabenzofos, dioxacarb, dioxathion, dioxation, diphacin, diphacinone, diphenadione, diphenamid, diphenamide, diphenylamine, diphenyl sulfone, diphenylsulphide, diprogulic acid, dipropalin, dipropetryn, dipterex, dipymetitrone, dipyrithione, diquat, disosultap, disparlure, disugran, disul, disulfiram, disulfoton, ditalimfos, dithianon, dithicrofos, dithioether, dithiometon, dithiopyr, diuron, dixanthogen, d-limonene, DM DS, DM PA, DNOC, dodemorph, dodicin, dodine, dofenapyn, doguadine, dominicalure, doramectin, 2,4-DP, 3,4-DP, DPC, drazoxolon, DSMA, d-trans-allethrin, d-trans-resmethrin, dufulin, dymron, EBEP, EBP, ebufos, a-ecdysone, β-ecdysone, ecdysterone, echlomezol, EDB, EDC, EDDP, edifenphos, eglinazine, emamectin, EMPC, empenthrin, enadenine, endosulfan, alpha- endosulfan, endothal, endothall, endothion, endrin, enestroburin, enilconazole, enoxastrobin, ephirsulfonate, EPN, epocholeone, epofenonane, epoxiconazole, eprinomectin, epronaz, epsilon- metofluthrin, epsilon-momfluorothrin, EPTC, erbon, ergocalciferol, , esdepallethrine, esfenvalerate, ESP, esprocarb, etacelasil, etaconazole, etaphos, etem, ethaboxam, ethachlor, ethalfluralin, ethametsulfuron, ethaprochlor, ethephon, ethidimuron, ethiofencarb, ethiolate, ethion, ethiozin, ethiprole, ethirimol, ethoate-methyl, ethobenzanid, ethofumesate, ethohexadiol, ethoprop, ethoprophos, ethoxyfen, (3-ethoxypropyl)mercury bromide, ethoxyquin, ethoxysulfuron, ethychlozate, ethylan, ethyl-DDD, ethylene, ethylene dibromide, ethylene dichloride, ethylene oxide, ethyl formate, ethylicin, ethylmercury acetate, ethylmercury bromide, ethylmercury chloride, ethylmercury 2,3-dihydroxypropyl mercaptide, ethylmercury phosphate, N-(ethylmercury)-p-toluenesulfonanilide, N-(ethylmercury)-p-toluenesulphonanilide, ethyl pyrophosphate, etinofen, ETM, etnipromid, etobenzanid, etofenprox, etoxazole, etridiazole, etrimfos, etrimphos, eugenol, EXD, famoxadone, famphur, , fenac, fenamidone, fenaminosulf, fenaminstrobin, fenamiphos, fenapanil, fenarimol, fenasulam, fenazaflor, fenazaquin, fenbuconazole, fenbutatin oxide, fenchlorazole, fenchlorphos, fenclofos, fenclorim, fenethacarb, fenfluthrin, fenfuram, fenhexamid, fenidin, fenitropan, fenitrothion, fenizon, fenjuntong, fenobucarb, fenolovo, fenoprop, fenothiocarb, fenoxacrim, fenoxanil, fenoxaprop, fenoxaprop-P, fenoxasulfone, fenoxycarb, fenpiclonil, fenpicoxamid, fenpirithrin, fenpropathrin, fenpropidin, fenpropimorph, fenpyrazamine, fenpyroximate, fenquinotrione, fenridazon, fenson, fensulfothion, fenteracol, fenthiaprop, fenthion, fenthion-ethyl, fentiaprop, fentin, fentrazamide, fentrifanil, fenuron, fenuron-TCA, fenvalerate, ferbam, ferimzone, ferric phosphate, ferrous sulfate, fipronil, flamprop, flamprop-M, flazasulfuron, flocoumafen, flometoquin, flonicamid, florasulam, florpyrauxifen, fluacrypyrim, fluazaindolizine, fluazifop, fluazifop-P, fluazinam, fluazolate, fluazuron, flubendiamide, flubenzimine, flubrocythrinate, flucarbazone, flucetosulfuron, fluchloralin, flucofuron, flucycloxuron, flucythrinate, fludioxonil, fluenethyl, fluenetil, fluensulfone, flufenacet, flufenerim, flufenican, flufenoxuron, flufenoxystrobin, flufenprox, flufenpyr, flufenzine, flufiprole, fluhexafon, fluindapyr, flumethrin, flumetover, flumetralin, flumetsulam, flumezin, flumiclorac, flumioxazin, flumipropyn, flumorph, fluometuron, fluopicolide, fluopyram, fluorbenside, fluoridamid, fluoroacetamide, fluoroacetic acid, fluorochloridone, fluorodifen, fluoroglycofen, fluoroimide, fluoromide, fluoromidine, fluoronitrofen, fluoroxypyr, fluothiuron, fluotrimazole, fluoxastrobin, flupoxam, flupropacil, flupropadine, flupropanate, flupyradifurone, flupyrsulfuron, fluquinconazole, fluralaner, flurazole, flurecol, flurenol, fluridone, flurochloridone, fluromidine, fluroxypyr, flurprimidol, flursulamid, flurtamone, flusilazole, flusulfamide, flutenzine, fluthiacet, fluthiamide, flutianil, flutolanil, flutriafol, fluvalinate, tau-fluvalinate, fluxametamide, fluxapyroxad, fluxofenim, folpel, folpet, fomesafen, fonofos, foramsulfuron, forchlorfenuron, formaldehyde, formetanate, formothion, formparanate, fosamine, fosetyl, fosmethilan, fospirate, fosthiazate, fosthietan, frontalin, fthalide, fuberidazole, fucaojing, fucaomi, fujunmanzhi, fulumi, fumarin, funaihecaoling, fuphenthiourea, furalane, furalaxyl, furamethrin, furametpyr, furan tebufenozide, furathiocarb, furcarbanil, furconazole, furconazole-cis, furethrin, furfural, furilazole, furmecyclox, furophanate, furyloxyfen, gamma-BHC, gamma-cyhalothrin, gamma-HCH, genit, gibberellic acid, gibberellin A3, gibberellins, gliftor, glitor, glucochloralose, glufosinate, glufosinate-P, glyodin, glyoxime, glyphosate, glyphosine, gossyplure, grandlure, griseofulvin, guanoctine, guazatine, halacrinate, halauxifen, halfenprox, halofenozide, halosafen, halosulfuron, haloxydine, haloxyfop, haloxyfop-P, haloxyfop-R, HCA, HCB, HCH, gamma-HCH, hemel, hempa, HEOD, heptachlor, heptafluthrin, heptenophos, heptopargil, herbimycin, herbimycin A, heterophos, hexachlor, hexachloran, hexachloroacetone, hexachlorobenzene, hexachlorobutadiene, hexachlorophene, hexaconazole, hexaflumuron, hexafluoramin, hexaflurate, hexalure, hexamide, hexazinone, hexylthiofos, hexythiazox, HHDN, holosulf, homobrassinolide, huancaiwo, huanchongjing, huangcaoling, huanjunzuo, hydramethylnon, hydrargaphen, hydrated lime, hydrogen cyanamide, hydrogen cyanide, hydroprene, S-hydroprene, hydroxyisoxazole, 4-hydroxyphenethyl alcohol, 8- hydroxyquinoline sulfate, hymexazol, hyquincarb, IAA, I BA, IBP, icaridin, imazalil, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, imibenconazole, imicyafos, imidacloprid, imidaclothiz, iminoctadine, imiprothrin, inabenfide, indanofan, indaziflam, indoxacarb, inezin, infusorial earth, iodobonil, iodocarb, iodofenphos, iodomethane, iodosulfuron, iofensulfuron, ioxynil, ipazine, I PBC, I PC, ipconazole, ipfencarbazone, ipfentrifluconazole, iprobenfos, iprodione, iprovalicarb, iprymidam, ipsdienol, ipsenol, IPSP, IPX, isamidofos, isazofos, isobenzan, isocarbamid, isocarbamide, isocarbophos, isocil, isodrin, isofenphos, isofenphos-methyl, isofetamid, isoflucypram, isolan, isomethiozin, isonoruron, isopamphos, isopolinate, isoprocarb, isoprocil, isopropalin, isopropazol, isoprothiolane, isoproturon, isopyrazam, isopyrimol, isothioate, isotianil, isouron, isovaledione, isoxaben, isoxachlortole, isoxadifen, isoxaflutole, isoxapyrifop, isoxathion, isuron, ivermectin, ixoxaben, izopamfos, izopamphos, japonilure, japothrins, jasmolin I, jasmolin II, jasmonic acid, jiahuangchongzong, jiajizengxiaolin, jiaxiangjunzhi, jiecaowan, jiecaoxi, Jinganmycin A, jodfenphos, juvenile hormone I, juvenile hormone I I, juvenile hormone II I, kadethrin, kappa- bifenthrin, kappa-tefluthrin, karbutilate, karetazan, kasugamycin, kejunlin, kelevan, ketospiradox, kieselguhr, kinetin, kinoprene, S-kinoprene, kiralaxyl, kresoxim-methyl, kuicaoxi, lactofen, lambda- cyhalothrin, lancotrione, latilure, lead arsenate, lenacil, lepimectin, leptophos, lianbenjingzhi, lime sulfur, d-limonene, lindane, lineatin, linuron, lirimfos, litlure, looplure, lufenuron, lufuqingchongxianan, luxiancaolin, Ivdingjunzhi, Ivfumijvzhi, Ivxiancaolin, lythidathion, M-74, M- 81, MAA, magnesium phosphide, malathion, maldison, maleic hydrazide, malonoben, maltodextrin, MAMA, mancopper, mancozeb, mandestrobin, mandipropa-mid, maneb, matrine, mazidox, MCC, MCP, 1-MCP, MCPA, 2,4-MCPA, MCPA-thioethyl, MCPB, 2,4-MCPB, MCPP, mebenil, mecarbam, mecarbinzid, mecarphon, mecoprop, mecoprop-P, medimeform, medinoterb, medlure, mefenacet, mefenoxam, mefenpyr, mefentrifluconazole, mefluidide, megatomoic acid, melissyl alcohol, melitoxin, M EMC, menazon, MEP, mepanipyrim, meperfluthrin, mephenate, mephosfolan, mepiquat, mepronil, meptyldinocap, mercaptodimethur, mercaptophos, mercaptophos thiol, mercaptothion, mercuric chloride, mercuric oxide, mercurous chloride, merphos, merphos oxide, mesoprazine, mesosulfuron, mesotrione, mesulfen, mesulfenfos, mesulphen, metacresol, metaflumizone, metalaxyl, metalaxyl-M, R-metalaxyl, metaldehyde, metam, metamifop, metamitron, metaphos, metaxon, metazachlor, metazosulfuron, metazoxolon, metcamifen, metconazole, metepa, metflurazon, methabenzthiazuron, methacrifos, methalpropalin, metham, methamidophos, methasulfocarb, methazole, methfuroxam, methibenzuron, methidathion, methiobencarb, methiocarb, methiopyrisulfuron, methiotepa, methiozolin, methiuron, methocrotophos, metholcarb, methometon, methomyl, methoprene, S-methoprene, methoprotryn, methoprotryne, methoquin-butyl, methothrin, methoxychlor, 2-methoxyethylmercury chloride, methoxyfenozide, methoxyphenone, methyl apholate, methyl bromide, methyl eugenol, methyl iodide, methyl- isofenphos, methyl isothiocyanate, methyl parathion, methylacetophos, methylchloroform, 1- methylcyclopropene, methyldithiocarbamic acid, methyldymron, methylene chloride, methylmer- captophos, methylmercaptophos oxide, methylmercaptophos thiol, methylmercury benzoate, methylmercury dicyandiamide, methylmercury pentachlorophenoxide, methylneodecanamide, methylnitrophos, methyltriazothion, metiozolin, metiram, metiram-zinc, metobenzuron, metobromuron, metofluthrin, epsilon-metofluthrin, metolachlor, S-metolachlor, metolcarb, metometuron, metominostrobin, metosulam, metoxadiazone, metoxuron, metrafenone, metriam, metribuzin, metrifonate, metriphonate, metsulfovax, metsulfuron, mevinphos, mexacarbate, miechuwei, mieshuan, miewenjuzhi, milbemectin, milbemycin oxime, milneb, mimanan, mipafox, M IPC, mirex, MNAF, moguchun, molinate, molosultap, monalide, monalide, momfluorothrin, epsilon-momfluorothrin, monisuron, monoamitraz, monochloroacetic acid, monocrotophos, monolinuron, monomehypo, monosulfiram, monosulfuron, monosultap, monuron, monuron-TCA, morfamquat, moroxydine, morphothion, morzid, moxidectin, M PMC, MSMA, MTMC, ct-multistriatin, muscalure, myclobutanil, myclozolin, myricyl alcohol, NAA, NAAm, nabam, naftalofos, naled, naphthalene, naphthaleneacetamide, ct-naphthaleneacetic acids, naphthalic anhydride, naphthalophos, 1-naphthol, naphthoxyacetic acids, naphthylacetic acids, naphthylindane-l,3-diones, naphthyloxyacetic acids, naproanilide, napropamide, napropamide- M, naptalam, natamycin, NBPOS, neburea, neburon, nendrin, neonicotine, nichlorfos, niclofen, niclosamide, nicobifen, nicosulfuron, nicotine, nicotine sulfate, nifluridide, nikkomycins, NI P, nipyraclofen, nipyralofen, nitenpyram, nithiazine, nitralin, nitrapyrin, nitrilacarb, nitrofen, nitrofluorfen, nitrostyrene, nitrothal-isopropyl, nobormide, nonanol, norbormide, norea, nor- flurazon, nornicotine, noruron, novaluron, noviflumuron, NPA, nuarimol, nuranone, OCH, octa- chlorodipropyl ether, octhilinone, 2-(octylthio)ethanol, o-dichlorobenzene, ofurace, omethoate, o-phenylphenol, orbencarb, orfralure, orthobencarb, ortho-dichlorobenzene, orthosulfamuron, oryctalure, orysastrobin, oryzalin, osthol, osthole, ostramone, ovatron, ovex, oxabetrinil, oxadiargyl, oxadiazon, oxadixyl, oxamate, oxamyl, oxapyrazon, oxapyrazone, oxasulfuron, oxathiapiprolin, oxaziclomefone, oxine-copper, oxine-Cu, oxolinic acid, oxpoconazole, oxycarboxin, oxydemeton-methyl, oxydeprofos, oxydisulfoton, oxyenadenine, oxyfluorfen, oxymatrine, oxytetracycline, oxythioquinox, PAC, paclobutrazol, paichongding, pallethrine, PAP, para-dichlorobenzene, parafluron, paraquat, parathion, parathion-methyl, parinol, Paris green, PCNB, PCP, PCP-Na, p-dichlorobenzene, PDJ, pebulate, pedinex, pefurazoate, pelargonic acid, penconazole, pencycuron, pendimethalin, penfenate, penflufen, penfluron, penoxalin, penoxsulam, pentachlorophenol, pentachlorophenyl laurate, pentanochlor, penthiopyrad, pentmethrin, pentoxazone, perchlordecone, perfluidone, permethrin, pethoxamid, PHC, phenamacril, phenamacril-ethyl, phenaminosulf, phenazine oxide, phenetacarbe, phenisopham, phenkapton, phenmedipham, phenmedipham-ethyl, phenobenzuron, phenothiol, phenothrin, phenproxide, phenthoate, 8-phenylmercurioxyquinoline, phenylmercuriurea, phenylmercury acetate, phenylmercury chloride, phenylmercury derivative of pyrocatechol, phenylmercury nitrate, phenylmercury salicylate, 2-phenylphenol, phorate, phosacetim, phosalone, phosametine, phosazetim, phosazetin, phoscyclotin, phosdiphen, phosethyl, phosfolan, phosfolan-methyl, phos- glycin, phosmet, phosnichlor, phosphamide, phosphamidon, phosphine, phosphinothricin, phosphocarb, phosphorus, phostin, phoxim, phoxim-methyl, phthalide, phthalophos, phthalthrin, picarbutrazox, picaridin, picloram, picolinafen, picoxystrobin, pimaricin, pindone, pinoxaden, piperalin, piperazine, piperonyl butoxide, piperonyl cyclonene, piperophos, piproctanly, piproctanyl, piprotal, pirimetaphos, pirimicarb, piriminil, pirimioxyphos, pirimiphos-ethyl, pirimiphos-methyl, pival, pivaldione, plifenate, PMA, PM P, polybutenes, polycarbamate, polychlorcamphene, polyethoxyquinoline, polyoxin D, polyoxins, polyoxorim, polythialan, potassium arsenite, potassium azide, potassium cyanate, potassium ethylxanthate, potassium naphthenate, potassium polysulfide, potassium thiocyanate, ppH-DDT, prallethrin, precocene I, precocene I I, precocene II I, pretilachlor, primidophos, primisulfuron, probenazole, prochloraz, proclonol, procyazine, procymidone, prodiamine, profenofos, profluazol, profluralin, profluthrin, profoxydim, profurite-aminium, proglinazine, prohexadione, prohydrojasmon, promacyl, promecarb, prometon, prometryn, prometryne, promurit, pronamide, propachlor, propafos, propamidine, propamocarb, propanil, propaphos, propaquizafop, propargite, proparthrin, propazine, propetamphos, propham, propiconazole, propidine, propineb, propisochlor, propoxur, propoxycarbazone, propyl isome, propyrisulfuron, propyzamide, proquinazid, prosuler, prosulfalin, prosulfocarb, prosulfuron, prothidathion, prothiocarb, prothioconazole, prothiofos, prothoate, protrifenbute, proxan, prymidophos, prynachlor, psoralen, psoralene, pydanon, pydiflumetofen, pyflubumide, pymetrozine, pyracarbolid, pyraclofos, pyraclonil, pyraclostrobin, pyraflufen, pyrafluprole, pyramat, pyrametostrobin, pyraoxystrobin, pyrasulfotole, pyraziflumid, pyrazolate, pyrazolynate, pyrazon, pyrazophos, pyrazosulfuron, pyrazothion, pyrazoxyfen, pyresmethrin, pyrethrin I, pyrethrin II, pyrethrins, pyribambenz-isopropyl, pyribambenz-propyl, pyribencarb, pyribenzoxim, pyributicarb, pyriclor, pyridaben, pyridafol, pyridalyl, pyridaphenthion, pyridaphenthione, pyridate, pyridinitril, pyrifenox, pyrifluquinazon, pyriftalid, pyrimetaphos, pyrimethanil, pyrimicarbe, pyrimidifen, pyriminobac, pyriminostrobin, pyrimiphos- ethyl, pyrimiphos-methyl, pyrimisulfan, pyrimitate, pyrinuron, pyriofenone, pyriprole, pyripropanol, pyriproxyfen, pyrisoxazole, pyrithiobac, pyrolan, pyroquilon, pyroxasulfone, pyroxsulam, pyroxychlor, qincaosuan, qingkuling, quassia, quinacetol, quinalphos, quinalphos- methyl, quinazamid, quinclorac, quinconazole, quinmerac, quinoclamine, quinofumelin, quinomethionate, quinonamid, quinothion, quinoxyfen, quintiofos, quintozene, quizalofop, quizalofop-P, quwenzhi, quyingding, rabenzazole, rafoxanide, R-diniconazole, rebemide, reglone, renofluthrin, renriduron, rescalure, resmethrin, d-trans-resmethrin, rhodethanil, rhodojaponin-l ll, ribavirin, rimsulfuron, rizazole, R-metalaxyl, rodethanil, ronnel, rotenone, ryania, sabadilla, saflufenacil, saijunmao, saisentong, salicylanilide, salifluofen, sanguinarine, santonin, sarolaner, S- bioallethrin, schradan, scilliroside, sebuthylazine, secbumeton, sedaxane, selamectin, semiamitraz, sesamex, sesamolin, sesone, sethoxydim, sevin, S-hydroprene, shuangjiaancaolin, shuangjianancaolin, siduron, sifumijvzhi, siglure, silafluofen, silatrane, silica aerogel, silica gel, silthiofam, silthiopham, silthiophan, silvex, simazine, simeconazole, simeton, simetryn, simetryne, sintofen, S-kinoprene, slaked lime, SMA, S-methoprene, S-metolachlor, sodium arsenite, sodium azide, sodium chlorate, sodium cyanide, sodium fluoride, sodium fluoroacetate, sodium hexafluorosilicate, sodium naphthenate, sodium orthophenylphenoxide, sodium pentachlorophenate, sodium pentachloro-phenoxide, sodium o-phenylphenoxide, sodium polysulfide, sodium silicofluoride, disodium tetraborate, sodium tetrathiocarbonate, sodium thiocyanate, solan, sophamide, spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, spiroxamine, stirofos, streptomycin, strychnine, sulcatol, sulcofuron, sulcotrione, sulfallate, sulfentrazone, sulfiram, sulfluramid, sulfodiazole, sulfometuron, sulfosate, sulfosulfuron, sulfotep, sulfotepp, sulfoxaflor, sulfoxide, sulfoxime, sulfur, sulfuric acid, sulfuryl fluoride, sulglycapin, sulphosate, sulprofos, sultropen, swep, 2,4,5-T, tau-fluvalinate, tavron, tazimcarb, 2,4,5-TB, 2,3,6- TBA, TBTO, TBZ, TCA, TCBA, TCMTB, TCNB, TDE, tebuconazole, tebufenozide, tebufenpyrad, tebufloquin, tebupirimfos, tebutam, tebuthiuron, tecloftalam, tecnazene, tecoram, tedion, teflubenzuron, tefluthrin, kappa-tefluthrin, tefuryltrione, tembotrione, temefos, temephos, tepa, TEPP, tepraloxydim, teproloxydim, terallethrin, terbacil, terbucarb, terbuchlor, terbufos, terbumeton, terbuthylazine, terbutol, terbutryn, terbutryne, terraclor, terramicin, terramycin, tetcyclacis, tetrachloroethane, tetrachlorvinphos, tetraconazole, tetradifon, tetradisul, tetrafluron, tetramethrin, tetramethylfluthrin, tetramine, tetranactin, tetraniliprole, tetrapion, tetrasul, thallium sulfate, thallous sulfate, thenylchlor, theta-cypermethrin, thiabendazole, thiacloprid, thiadiazine, thiadifluor, thiamethoxam, thiameturon, thiapronil, thiazafluron, thiazfluron, thiazone, thiazopyr, thicrofos, thicyofen, thidiazimin, thidiazuron, thiencarbazone, thifensulfuron, thifluzamide, thimerosal, thimet, thiobencarb, thiocarboxime, thiochlorfenphim, thiochlorphenphime, thiocyanatodinitrobenzenes, thiocyclam, thiodan, thiodiazole-copper, thiodicarb, thiofanocarb, thiofanox, thiofluoximate, thiohempa, thiomersal, thiometon, thionazin, thiophanate, thiophanate-ethyl, thiophanate-methyl, thiophos, thioquinox, thiosemicarbazide, thiosultap, thiotepa, thioxamyl, thiram, thiuram, thuringiensin, tiabendazole, tiadinil, tiafenacil, tiaojiean, TIBA, tifatol, tiocarbazil, tioclorim, tioxazafen, tioxymid, TMTD, tirpate, tolclofos-methyl, tolfenpyrad, tolprocarb, tolpyralate, tolyfluanid, tolylfluanid, tolylmercury acetate, tomarin, topramezone, toxaphene, 2,4,5-TP, 2,3,3-TPA, TPN, tralkoxydim, tralocythrin, tralomethrin, tralopyril, d-trans-allethrin, d-trans-resmethrin, transfluthrin, transpermethrin, tretamine, tri- allate, triacontanol, triadimefon, triadimenol, triafamone, triallate, triamiphos, triapenthenol, triarathene, triarimol, triasulfuron, triazamate, triazbutil, triaziflam, triazophos, triazothion, triazoxide, tribasic copper chloride, tribasic copper sulfate, tribenuron, tribufos, tributyltin oxide, tricamba, trichlamide, trichlopyr, trichlorfon, trichlormetaphos-3, trichloronat, trichloronate, trichlorotrinitrobenzenes, trichlorphon, triclopyr, triclopyricarb, tricresol, tricyclazole, tricyclohexyltin hydroxide, tridemorph, tridiphane, trietazine, trifenmorph, trifenofos, trifloxystrobin, trifloxysulfuron, trifludimoxazin, triflumezopyrim, triflumizole, triflumuron, trifluralin, triflusulfuron, trifop, trifopsime, triforine, trihydroxytriazine, 2,3,5-tri-iodobenzoic acid, 2,3,5-triiodobenzoic acid, trimedlure, trimethacarb, trimeturon, trinexapac, triphenyltin, triprene, tripropindan, triptolide, tritac, trithialan, triticonazole, tritosulfuron, trunc-call, tuoyelin, uniconazole, uniconazole-P, urbacide, uredepa, valerate, validamycin, validamycin A, valifenalate, valone, vamidothion, vangard, vaniliprole, vernolate, vinclozolin, vitamin D3, warfarin, xiaochongliulin, xinjunan, xiwojunan, xiwojunzhi, XMC, xylachlor, xylenols, xylylcarb, xymiazole, yishijing, zarilamid, zeatin, zengxiaoan, zengxiaolin, zeta-cypermethrin, zinc naphthenate, zinc phosphide, zinc thiazole, zinc thiozole, zinc trichlorophenate, zinc trichlorophenoxide, zineb, ziram, zolaprofos, zoocoumarin, zoxamide, zuoanjunzhi, zuocaoan, zuojunzhi, zuomihuanglong, 1- MCP, 1-methylcyclopropene, 1-naphthol, 1,2-dichloropropane, 1,3-D, 1,3-dichloropropene, 2iP, 2- methoxyethylmercury chloride, 2-(octylthio)ethanol, 2-phenylphenol, 2,3,3-TPA, 2,3,5- triiodobenzoic acid, 2,3,6-TBA, 2,4- D, 2,4-DB, 2,4-DEB, 2,4-DEP, 2,4-DES, 2,4-DP, 2,4-MCPA, 2,4- MCPB, 2,4,5-T, 2,4,5-TB, 2,4,5-TP, (3-ethoxypropyl)mercury bromide, 3,4-DA, 3,4-DB, 3,4-DP, 3,6- dichloropicolinic acid, 4-aminopyridine, 4-CPA, 4-CPB, 4-CPP, 4-hydroxyphenethyl alcohol, 8- hydroxyquinoline sulfate, 8-phenylmercurioxyquinoline, or salts, derivatives and mixtures therefore. According to an embodiment, the first agrochemical active ingredient is a water sensitive active ingredient. According to an embodiment, the water sensitive active include one or more of but not limited to, clodinafop-propargyl, acetamiprid, pinoxaden, azimsulfuron, berssu!furon, chlorimuron, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron, ethoxysulfuron, flazasulfuron, flupyrsulfuron, halosulfuron, imazosulfuron, iodosulfuron, mesosulfuron, metsulfuron, nicosulfuron, primisulfuron, prosulfuron, pyrazosulfuron, rimsulfuron, sulfometuron, sulfosulfuron, thifensulfuron, triasulfuron, tribenuron, triflusulfuron, trifloxysulfuron, tritosulfuron; ,cloquintocet-mexyl, thiamethoxam, mesotrione, cartap, cartap hydrochloride, acephate, acifluorfen, acifluorfen-sodium, aldicarb, aminocarb, aminopyralid , asulam sodium, azamethiphos, bromoxynil, chloropicrin, dazomet, dicamba, diflufenzopyr, dimethachlor, dimethenamid, bispyribac-sodium, dimethenamid-P, dimethoate, dinotefuran, DNOC, dodine, endothion, ethephon, ethiprole, ethylene bisisothiocyanate sulphide, fenoxanil, fosetyl- aluminium, fosthiazate, glufosinate-ammonium, guazatine, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, ioxynil, isocarbamide, MCPA, MCPB, mecoprop, metalaxyl , metamitron, metam-sodium, methamidophos, metribuzin, monocrotophos, oxamyl, oxasulfuron, oxycarboxin, picloram-dimethylammonium, picloram-trolamine, pirimicarb, propoxycarbazone-sodium, pyrazoxyfen, pyrithiobac-sodium, pyroquilone, pyroxsulam, quinclorac-dimethylammonium, quinmerac, quinoclamine, saflufenacil, sethoxydim, sulfometuron-methyl, tembotrione , terbuthylazine, thifensulfuron-methyl, thifluzamide, thiocyclam hydrogen oxalate, thiocyclam, thiofanox, topramezone, tribenuron-methyl, trichlorfon, triclopyr, uniconazole, fipronil and salts or derivatives thereof.
According to an embodiment, the first agrochemical active ingredient is a water soluble active. According to an embodiment, the water soluble active includes one or more of but not limited to acephate, acetamiprid, acethion, acetic acid, acetochlor, acetoprole, acibenzolar-S-methyl, acifluorfen, acifluorfen-sodium, aclonifen, acrolein, acrylonitrile, afidopyropen, alachlor, alanycarb, aldicarb, aldimorph, aldoxycarb, allidochlor, alloxydim, allyl alcohol, allyxycarb, alorac, alpha-chlorohydrin, alpha-endosulfan, alpha-hexachlorocyclohexane, alpha- naphthylthiourea, aluminium ammonium sulphate, aluminium phosphide, aluminium silicate, ametoctradin, ametridione, ametryn, amibuzin, amicarbazone, amidithion, amidochlor, amidosulfuron, amidothioate, aminocarb, aminocyclopyrachlor, aminopyralid, amiprofos-methyl, amisulbrom, amiton, amitraz, amitrole, ammonium acetate, ammonium carbonate, ammonium hydroxide, ammonium sulphamate, ammonium sulphate, ammonium thiocyanate, ampropylfos, ancymidol, anilazine, anilofos, anisuron, ANTU, aramite, arsenous oxide, asomate, asulam sodium, asulam, athidathion, atraton, atrazine, azaconazole, azafenidin, azamethiphos, azimsulfuron, azinphos-ethyl, azinphos-methyl, aziprotryne, azithiram, azobenzene, azothoate, azoxybenzene, azoxystrobin, barban, barium carbonate, barium polysulphide, beflubutamid, benalaxyl, benalaxyl-M, benazolin ethyl, benazolin, bencarbazone, benclothiaz, bendiocarb, benfuracarb, benfuresate, benodanil, benomyl, benquinox, bensulfuron, bensulfuron-methyl, bensulide, bensultap, bentaluron, bentazone, benthiavalicarb isopropyl, benthiavalicarb, benzadox ammonium, benzadox, benzalkonium chloride, benzamacril isobutyl, benzamacril, benzamorf, benzfendizone, benzipram, benzofenap, benzofluor, benzoic acid, benzovindiflupyr, benzoximate, benzoylprop, benzoylprop-ethyl, benzthiazuron, benzyl benzoate, beta- cypermethrin, bethoxazin, bicyclopyrone, bifenazate, bifenox, binapacryl, bioallethrin, biopermethrin, bioresmethrin, biphenyl, bis(2-chloroethyl)ether, bis(methylmercury) sulphate, bispyribac-sodium, bisthiosemi, bis-trichloromethyl sulfone, bitertanol, bithionol, bixafen, bone oil, Bordeaux mixture, boric acid, boscalid, brassinolide, brofluthrinate, bromacil, bromadiolone, bromfenvinfos, bromobonil, bromobutide, bromocyclen, bromofenoxim, bromomethane, bromophos, bromophos-ethyl, bromopropylate, bromoxynil, brompyrazon, bromuconazole, bromuron, bronopol, bufencarb, buminafos, bupirimate, buprofezin, butachlor, butafenacil, butamifos, butanethiol, butathiofos, butenachlor, buthidazole, buthiobate, buthiuron, butocarboxim, butonate, butopyronoxyl, butoxycarboxim, butralin, butroxydim, buturon, butylate, cacodylic acid, cadusafos, cafenstrole, calciferol, calcium acid methanearsonate, calcium arsenate, calcium carbide, calcium carbonate, calcium chloride, calcium cyanamide, calcium hydroxide, calcium phosphate, calcium phosphide, cambendichlor, camphechlor, captafol, captan, carbamorph, carbanolate, carbaryl, carbasulam, carbendazim, carbetamide, carbofuran, carbon dioxide, carbon disulphide, carbon tetrachloride, carbophenothion, carbosulfan, carboxazole, carboxin sulfoxide, carboxin, carfentrazone-ethyl, carpropamid, cartap, cartap hydrochloride, chinomethionat, chlobenthiazone, chlomethoxyfen, chloralose, chloramben, chloraniformethan, chloranil, chloranocryl, chlorantraniliprole, chlorazifop propargyl, chlorazifop, chlorazine, chlorbenside, chlorbicyclen, chlorbromuron, chlorbufam, chlordane, chlordecone, chlordimeform, chloretazate, chlorethoxyfos, chloreturon, chlorfenac, chlorfenapyr, chlorfenazole, chlorfenethol, chlorfenprop-methyl, chlorfenson, chlorfensulphide, chlorfenvinphos, chlorfluazole, chlorfluren methyl, chlorfluren, chlorflurenol methyl, chlorflurenol, chloridazon, chlorimuron-ethyl, chlormephos, chlormequat chloride, chlornitrofen, chlorobenzilate, chloromebuform, chloromethiuron, chloroneb, chlorophacinone, chloropicrin, chloropon, chloropropylate, chlorothalonil, chlorotoluron, chloroxuron, chloroxylenol, chloroxynil, chlorphonium chloride, chlorphoxim, chlorprazophos, chlorprocarb, chlorpropham, chlorpyrifos, chlorpyrifos-methyl, chlorquinox, chlorsulfuron, chlortetracycline, chlorthal-dimethyl, chlorthiamid, chlorthion, chlorthiophos, chlozolinate, choline chloride, chromafenozide, cinmethylin, cinosulfuron, ciobutide, cisanilide, cispermethrin, clethodim, climbazole, cliodinate, clodinafop, clodinafop-propargyl, cloethocarb, clofencet, clofop, clofop- isobutyl, clomazone, cloprop, cloproxydim, clopyralid monoethanolamine salt, clopyralid, cloransulam-methyl, closantel, clothianidin, cloxyfonac, copper (1) oxide, copper acetoarsenite, copper bis(3-phenylsalicyate), copper I I acetate, copper II chloride, copper I I hydroxide, copper oxychloride, copper sulphate, COS-OGA, coumachlor, coumafuryl, coumatetralyl, coumethoxystrobin, coumithoate, coumoxystrobin, credazine, crimidine, crotamiton, crotoxyphos, cufraneb, cumyluron, cuprobam, cyanamide, cyanatryn, cyanazine, cyanophos, cyanthoate, cyantraniliprole, cyazofamid, cybutryne, cyclanilide, cyclaniliprole, cyclethrin, cycloate, cycloheximide, cyclopyrimorate, cyclosulfamuron, cycloxydim, cycluron, cyenopyrafen, cyflufenamid, cyhalofop, cyhalofop-butyl, cyhexatin, cymiazol, cymoxanil, cypendazole, cyperquat chloride, cyperquat, cyprazine, cyproconazole, cyprodinil, cyprofuram, cypromid, cyprosulfamide, cyromazine, dazomet, daminozide, dalapon-sodium, dalapon, DAEP, debacarb, decafentin, defenuron, dehydroacetic acid, delachlor, demephion, demephion-O, demephion-S, demeton, demeton-O-methyl sulfone, demeton-O-methyl, demeton-S-methyl sulfone, demeton-S-methyl, denatonium benzoate, desmedipham, desmetryn, dialifos, di-allate, diamidaphos, diammonium ethylenebis(dithiocarbamate), diammonium phosphate, diazinon, dibromochloropropane, dicamba, dichlobenil, dichlofenthion, dichlofluanid, dichlone, dichlorophen, dichlorprop, dichlorprop-P, dichlorvos, diclobutrazol, diclocymet, diclofop, diclofop-methyl, diclomezine, dicloran, diclosulam, dicofol, dicrotophos, dicyclopentadiene, didecyldimethylammonium chloride, dieldrin, diethatyl ethyl, diethofencarb, diethyltoluamide, difenacoum, difenoconazole, difenopenten ethyl, difenopenten, difenoxuron, difenzoquat metilsulfate, difenzoquat, difethialone, diflovidazin, diflufenzopyr, diflumetorim, difunon, dikegulac, dikegulac-sodium, dimefox, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimethipin, dimethirimol, dimethoate, dimethomorph, dimethyl disulfide, dimethyl(4-piperidinocarbonyloxy-2, 5-xylyl)sulfonium toluene-4-sulfonate, dimethylvinphos, dimexano, dimidazon, dimoxystrobin, dinex, dinex-diclexine, diniconazole, diniconazole-M, dinitramine, dinobuton, dinocap, dinocton, dinofenate, dinopenton, dinosam, dinoseb acetate, dinoseb, dinosulfon, dinotefuran, dinoterb, diofenolan, dioxabenzophos, dioxacarb, dioxathion, diphacinone, diphenamid, diphenylamine, dipropalin, dipropetryn, dipyrithione, diquat dibromide, diquat, disodium methanearsonate, disodium octaborate tetrahydrate, disodium phosphonate, disul, disulfoton, disul-sodium, ditalimfos, dithianon, dithiopyr, diuron, dixanthogen, DNOC, dodemorph acetate, dodemorph, dodine, dormant oil, drazoxolon, dufulin, edifenphos, eglinazine-ethyl, empenthrin, endosulfan, endothal, endothion, endrin, enoxastrobin, epichlorohydrin, EPN, epocholeone, epofenonane, epoxiconazole, EPTC, erbon, esprocarb, etacelasil, etaconazole, etaphos, etem, ethaboxam, ethametsulfuron acid, ethametsulfuron-methyl, ethanamine, ethanedial, ethanethiol, ethephon, ethidimuron, ethiofencarb, ethion, ethiozin, ethiprole, ethirimol, ethofumesate, ethoate-methyl, ethoprophos, ethoxyfen ethyl, ethoxyfen, ethoxyquin, ethoxysulfuron, ethylene bisisothiocyanate sulphide, ethylene dichloride, ethylmercury bromide, etinofen, etridiazole, etrimfos, fenamidone, fenaminosulf, fenaminstrobin, fenamiphos, fenapanil, fenarimol, fenasulam, fenazaflor, fenazaquin, fenbuconazole, fenchlorazole-ethyl, fenchlorphos, fenfluthrin, fenfuram, fenhexamid, fenitropan, fenitrothion, fenobucarb, fenoprop, fenoprop- butotyl, fenothiocarb, fenoxanil, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenoxasulfone, fenoxycarb, fenpiclonil, fenpirithrin, fenpropathrin, fenpropidin, fenpropimorph, fenpyrazamine, fenquinotrione, fenridazon, fenson, fensulfothion, fenthiaprop ethyl, fenthiaprop, fenthion, fentin acetate, fentin chloride, fentin hydroxide, fentrazamide, fenuron, ferbam, ferric phosphate, fipronil, flamprop, flamprop-M-isopropyl, flazasulfuron, flocoumafen, flonicamid, florasulam, fluacrypyrim, fluazifop-butyl, fluazifop-P-butyl, fluazinam, flubenzimine, flucarbazone-sodium, flucetosulfuron, fluchloralin, flucythrinate, fludioxonil, fluenetil, fluensulfone, flufenacet, flufenerim, flufenoxystrobin, flufenpyr-ethyl, flufiprole, flumetsulam, flumiclorac-pentyl, flumioxazin, flumipropyn, flumorph, fluometuron, fluopicolide, fluopyram, fluorbenside, fluoroacetamide, fluorodifen, fluoroglycofen, fluoromidine, fluothiuron, fluotrimazole, fluoxastrobin, flupoxam, flupropacil, flupropadine hydrochloride, flupropadine, flupropanate-sodium, flupyradifurone, flupyrsulfuron, flupyrsulfuron-methyl-sodium, fluquinconazole, flurenol, fluridone, flurochloridone, fluroxypyr, fluroxypyr-meptyl, flurprimidol, flurtamone, flusilazole, flusulfamide, fluthiacet methyl, flutianil, flutolanil, flutriafol, fluxapyroxad, fluxofenim, folpet, fomesafen, fonofos, foramsulfuron, forchlorfenuron, formaldehyde, formetanate, formothion, formparanate, fosamine, fosetyl, fosetyl-aluminium, fosmethilan, fospirate, fosthiazate, fosthietan, fuberidazole, fufenozide, fuphenthiourea, furalaxyl, furalaxyl-M, furametpyr, furathiocarb, furconazole, furconazole-cis, furfural, furilazole, furmecyclox, furyloxyfen, gliftor, gliotoxin, glufosinate, glufosinate-ammonium, glufosinate-P, glutaraldehyde, glyodin, glyphosate trimesium, glyphosate, isopropylamine salt, glyphosate, potassium salt, glyphosate, glyphosine, griseofulvin, guazatine, halacrinate, halauxifen methyl, halauxifen, halofenozide, halosafen, halosulfuron-methyl, haloxydine, haloxyfop, haloxyfop-etotyl, haloxyfop-P, haloxyfop-P-methyl, heptafluthrin, heptamaloxyloglucan, heptenophos, heptopargil, heterophos, hexachlorophene, hexaconazole, hexaflurate, hexazinone, hexylthiofos, hexythiazox, huanjunzuo, hydrogen peroxide, hydroprene, hymexazol, hyquincarb, icaridin, imazalil, imazamethabenz, imazamethabenz- methyl, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, imibenconazole, imicyafos, imidacloprid, iminoctadine triacetate, iminoctadine tris(albesilate), iminoctadine, imiprothrin, inabenfide, indanofan, indaziflam, indoxacarb, inezin, iodobonil, iodofenphos, iodomethane, iodosulfuron, iodosulfuron-methyl-sodium, iofensulfuron sodium, iofensulfuron, ioxynil lithium, ioxynil sodium, ioxynil sodium, ioxynil, ipconazole, ipfencarbazone, iprobenfos, iprodione, iprovalicarb, I PSP, iron sulphate, isamidofos, isazofos, isocarbamide, isocarbophos, isocil, isofenphos, isofenphos-methyl, isofetamid, isolan, isomethiozin, isonoruron, isopamphos, isopolinate, isoprocarb, isopropalin, isoprothiolane, isoproturon, isopyrazam, isopyrimol, isothioate, isotianil, isouron, isoval, isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop, izopamfos, kaolin, karbutilate, kelevan, kinoprene, kresoxim-methyl, lactofen, lenacil, leptophos, lime sulphur, limestone, lindane, linuron, lithium perfluorooctane sulfonate, lythidathion, magnesium phosphide, malathion, maleic hydrazide, malonoben, mancopper, mancozeb, mandestrobin, mandipropamid, maneb, mazidox, MCPA, MCPA-thioethyl, MCPB, m-cumenyl methyl carbamate, mebenil, mecarbam, mecarbinzid, mecarphon, mecoprop, mecoprop-P, medetomidine, medinoterb acetate, medinoterb, mefenacet, mefluidide, menadione, menazon, mepanipyrim, mephosfolan, mepiquat chloride, mepiquat, mepronil, meptyldinocap, mercuric oxide, mercurous chloride, merphos, mesosulfuron, mesosulfuron-methyl, mesotrione, mesulfenfos, metalaxyl, metalaxyl-M, metaldehyde, metamifop, metamitron, metam-potassium, metam-sodium, metazachlor, metazosulfuron, metazoxolon, metconazole, metepa, methabenzthiazuron, methacrifos, methamidophos, methasulfocarb, methazole, methfuroxam, methidathion, methiocarb, methiopyrsulfuron, methiotepa, methiozolin, methiuron, methocrotophos, methomyl, methoprene, methoprotryne, methoxychlor, methoxyfenozide, methoxyphenone, methyl isothiocyanate, methyl(((l-(5-(2-chloro-4-(trifluoromethyl)phenoxy)-2-nitrophenyl)-2- methoxyethylidene)amino)oxy)acetate (fucaomi), methylarsenic sulphide, methylarsonic acid, methyldymron, methylene bisthiocyanate, metiram, metobenzuron, metobromuron, metofluthrin, metolachlor, metolcarb, metominostrobin, metosulam, metoxuron, metrafenone, metribuzin, metsulfovax, metsulfuron, metsulfuron-methyl, mevinphos, mexacarbate, mipafox, molinate, momfluorothrin, monalide, monocrotophos, monolinuron, monosodium methylarsonate, monosulfuron, monosulfuron-methyl, monuron, morfamquat dichloride, morfamquat, morphothion, mucochloric anhydride, myclobutanil, myclozolin, N-(3-chloro-2, 6- dimethylphenyl)-2-methoxy-N-(tetrahydr-2-oxo-3-furanyl)acetamide, nabam, naled, Nanosilver pesticide, naphthalene, naphthalic anhydride, naproanilide, napropamide, napropamide-M, naptalam, neburon, nickel bis(dimethyldithiocarbamate), niclosamide, nicosulfuron, nitenpyram, nithiazine, nitralin, nitrapyrin, nitrilacarb, nitrofen, nitrothal isopropyl, N- methylneodecanamide, N-nitrosodimethylamine, norbormide, norflurazon, nornicotine, noruron, noviflumuron, nuarimol, O, O-dimethyl alpha-(2, 4- dichlorophenoxyacetoxy)ethylphosphonate, octhilinone, ofurace, omethoate, orbencarb, orthosulfamuron, orysastrobin, oryzalin, oxabetrinil, oxadiargyl, oxadiazon, oxadixyl, oxamyl, oxapyrazon, oxapyrazon-dimolamine, oxapyrazon-sodium, oxasulfuron, oxathiapiprolin, oxaziclomefone, oxolinic acid, oxpoconazole fumarate, oxycarboxin, oxydemeton-methyl, oxydeprofos, oxydisulfoton, oxyfluorfen, paclobutrazol, paraffin oil (C11-C30) [4c], paraffin oil (C15-C30) [4b], paraffin oil [3 Not NEU], paraquat dichloride, paraquat, parathion, parathion- methyl, pebulate, penconazole, pencycuron, pendimethalin, penflufen, penoxsulam, pentachlorophenol, pentanochlor, penthiopyrad, pentoxazone, perfluidone, permethrin, peroxyacetic acid, pethoxamid, phenisopham, phenmedipham, phenthoate, phenyl mercuric acetate, phenylmercury nitrate, phorate, phosacetim, phosalone, phosametine, phosdiphen, phosfolan, phosfolan, phosmet, phosnichlor, phosphamidon, phosphine, phoxim, phthalide, picarbutrazox, picloram, picloram-dimethylammonium, picloram-trolamine, picoxystrobin, pindone, pinoxaden, piperalin, piperophos, piproctanyl bromide, piproctanyl, pirimicarb, pirimiphos-ethyl, pirimiphos-methyl, plifenate, polybutene, potassium bicarbonate, potassium iodide, potassium phosphonates, potassium thiocyanate, prallethrin, pretilachlor, primisulfuron methyl, primisulfuron, prochloraz, procymidone, profenofos, profluazol, profluralin, profluthrin, profoxydim, proglinazine ethyl, proglinazine, prohexadione, prohexadione- calcium, promacyl, promecarb, prometon, prometryn, propachlor, propamocarb hydrochloride, propamocarb, propanil, propaphos, propaquizafop, propargite, propazine, propham, propiconazole, propineb, propionic acid, propisochlor, propoxur, propoxycarbazone, propoxycarbazone-sodium, propyrisulfuron, propyzamide, proquinazid, prosulfocarb, prosulfuron, prothidathion, prothiocarb, prothioconazole, prothoate, protrifenbute, proximpham, prynachlor, pymetrozine, pyracarbolid, pyraclofos, pyraclonil, pyraclostrobin, pyraflufen, pyramat, pyrametostrobin, pyraoxystrobin, pyrazophos, pyrazosulfuron-ethyl, pyrazoxyfen, pyribambenz-isopropyl, pyribambenz-propyl, pyribenzoxim, pyridafenthion, pyridafol, pyridafol-O-methyl, pyridate, pyrifenox, pyrifluquinazon, pyriftalid, pyrimethanil, pyriminobac-methyl, pyriminostrobin, pyrimisulfan, pyriofenone, pyriproxyfen, pyrisoxazole, pyrithiobac-sodium, pyroquilone, pyroxasulfone, pyroxsulam, QRD-460, quartz sand, quinalphos, quinclorac, quinclorac-dimethylammonium, quinmerac, quinoclamine, quinonamid, quinothion, quintiofos, quintozene, quizalofop-ethyl, quizalofop-P-ethyl, quizalofop- P-tefuryl, rimsulfuron, saflufenacil, schradan, sebuthylazine, secbumeton, sedaxane, sethoxydim, siduron, silica, silthiofam, silver sodium thiosulphate, silver thiosulphate, simazine, simeconazole, simetryn, sintofen, S-methoprene, S-metolachlor, sodium 5-nitroguaiacolate, sodium aluminium silicate, sodium arsenite, sodium carbonate, sodium chlorate, sodium chloride, hydrogen carbonate, sodium hypochlorite, sodium o-nitrophenolate, sodium p-nitrophenolate, sodium tetraborate pentahydrate, spinetoram, spiromesifen, spirotetramat, spiroxamine, strobane, sulcotrione, sulfallate, sulfentrazone, sulfluramid, sulfometuron-methyl, sulfosulfuron, sulfotep, sulfoxaflor, sulfuryl fluoride, sulphur, sulphuric acid, sulprofos, TCA-sodium, tebuconazole, tebufenozide, tebufenpyrad, tebufloquin, tebupirimfos, tebutam, tebuthiuron, tecloftalam, tecnazene, tefluthrin, tefuryltrione, tembotrione, tepraloxydim, terallethrin, terbacil, terbuchlor, terbufos, terbumeton, terbuthylazine, terbutryn, tetcyclacis, tetrachlorvinphos, tetraconazole, tetraethyl pyrophosphate, tetramethrin, tetramethylfluthrin, thenylchlor, thiabendazole, thiacloprid, thiamethoxam, thiapronil, thiazafluron, thiazopyr, thicyofen, thidiazimin, thidiazuron, thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl, thifluzamide, thiobencarb, thiocarboxime, thiocyclam hydrogen oxalate, thiocyclam, thiodicarb, thiofanox, thiometon, thionazin, thiophanate-methyl, thiosultap, thiosultap-disodium, thiosultap-monosodium, thiourea, thiram, tiadinil, tiafenacil, tiocarbazil, tioxazafen, tolclofos- methyl, tolfenpyrad, tolylfluanid, topramezone, tralkoxydim, tralocythrin, transpermethrin, triadimefon, triadimenol, tri-allate, triamiphos, triapenthenol, triarathene, triasulfuron, triazamate, triazophos, triazoxide, tribenuron, tribenuron-methyl, tribufos, tributyltin oxide, trichlamide, trichlorfon, trichloronate, triclopyr butotyl, triclopyr triethylammonium, triclopyr, triclopyricarb, tricyclazole, tridemorph, tridiphane, trietazine, trifenofos, trifloxystrobin, trifloxysulfuron, trifloxysulfuron-sodium, triflumezopyrim, triflumizole, triflumuron, triflumezopyrim, triflumizole, trifluralin, triflusulfuron, triflusulfuron-methyl, trifopsime, triforine, trimethacarb, trinexapac-ethyl, trioxymethylene, triprene, triticonazole, tritosulfuron, uniconazole, urea sulphate, urea, valifenalate, valinomycin, vamidothion, verbutin, vernolate, vinclozolin, warfarin, XMC, xylachlor, xylylcarb, zarilamid, zinc borate, zinc oxide, zineb, ziram, zoxamide or salts or mixtures thereof.
According to another embodiment, the agrochemical active is a pesticidal active including but are not limited to one or more of class of actives selected from, neonicotinoid insecticides, oxyphenoxy acid esters, cyclohexanedione oxime herbicides the sulfonyl ureas and the cloquintocet herbicide safeners, the HPPD-inhibiting herbicides, phenylpyrazoles, nereistoxin analogue insecticides,and organophosphate insecticides.
According to an embodiment, the first agrochemical active ingredient is preferably selected from one or more of Acequinocyl, acrolein, alachlor, alloxydim, alpha-endosulfan, aminocarb, amitraz, anilazine, azamethiphos, azinphos-ethyl, barban, benfuracarb, benomyl, bensultap, bifenazate, bromomethane, bromoxynil heptanoate, bromoxynil octanoate, butoxycarboxim, captan, carbaryl Carbetamide, carbosulfan, carfentrazone-ethyl, cartap, cartap hydrochloride, chinomethionat, cinidon-ethyl, clodinafop-propargyl, Clofentezine, cyflumetofen, cymoxanil, dazomet, desmedipham, dichlofluanid, dichlorvos, dicofol, Dithianon, edifenphos, endosulfan, ethephon, ethiofencarb, famoxadone, fenchlorazole-ethyl, enobucarb, fentin acetate, ferbam, flazasulfuron, fluazinam, flumiclorac-pentyl , flumioxazin, Fluoroglycofen, flupyrsulfuron-methyl-sodium, folpet, formetanate, formothion, halosulfuron-methyl, haloxyfop-etotyl, heptachlor, heptenophos, hydramethylnon, ioxynil octanoate, iprodione, Isoxaflutole, malathion, mancozeb, maneb, metam-sodium, methamidophos, metiram, mevinphos, Mexacarbate, naled, naptalam, nitrapyrin, ofurace, omethoate, oxamyl, oxasulfuron, oxycarboxin, Phenmedipham, phorate, phosdiphen, phosmet, phoxim, pinoxaden, piperalin, propineb, pyraflufen-ethyl, pyridate, quizalofop-ethyl, quizalofop-P-tefuryl, rimsulfuron, spirotetramat, sulfotep, sulfuryl fluoride, temephos, terbufos, tetraethyl pyrophosphate, thiocyclam hydrogen oxalate, thiocyclam, thiram, tolylfluanid, transfluthrin, triazamate, tribenuron-methyl, trichlorfon, triclopyr, trifloxysulfuron-sodium, triforine, valifenalate, vinclozolin, zineb, ziram and zoxamide.
According to another embodiment, the first agrochemical active ingredient is preferably selected from one or more of Acequinocyl, acrolein, alachlor, amitraz, barban, benfuracarb, benomyl, bensultap, bifenazate, captan, carbosulfan, cartap, cartap hydrochloride, chinomethionat, cinidon-ethyl, clodinafop-propargyl, clofentezine, cyflumetofen, cymoxanil, dazomet, desmedipham, dichlorvos, dicofol, dithianon, ethephon, famoxadone, fentin acetate, ferbam, fluazinam, flumiclorac-pentyl, flumioxazin, folpet, formetanate, Formothion, haloxyfop-etotyl, heptachlor, iprodione, isoxaflutole, mancozeb, maneb, metam-sodium, methamidophos, metiram, mexacarbate, naled, naptalam, ofurace, phenmedipham, Phorate, pinoxaden, phosmet, propineb, pyridate, quizalofop-ethyl, sulfuryl fluoride, tetraethyl pyrophosphate, Thiocyclam, thiram, tolylfluanid, transfluthrin, triazamate, trichlorfon, triforine, vinclozolin and ziram. According to another embodiment, the first agrochemical active ingredient is preferably selected from one or more of Alachlor, amitraz, barban, benomyl, bensultap, bifenazate, captan, carbosulfan, cartap, cartap hydrochloride, cyflumetofen, Dazomet, desmedipham, dithianon, fentin acetate, flumiclorac-pentyl, flumioxazin, folpet, formothion, heptachlor, isoxaflutole, maneb, metiram, naled, ofurace, phenmedipham, Phosmet, pinoxaden, sulfuryl fluoride, tetraethyl pyrophosphate and ziram.
According to yet another embodiment, the agrochemical active can be any one of cartap, cartap hydrochloride, pinoxaden.
According to another embodiment, the second agrochemical active is fipronil.
According to an embodiment, the first or second agrochemical active is present in a concentration range of at least 0.01% by by weight of the total composition. According to an embodiment, the agrochemical active is present in a concentration range of at least 1% by by weight of the total composition. According to an embodiment, the agrochemical active is present in a concentration range of at least 5 % by weight of the total composition. According to an embodiment, the agrochemical active is present in a concentration range of at least 10 % by weight of the total composition. According to an embodiment, the agrochemical active is present in a concentration range of at least 20 % by weight of the total composition. According to an embodiment, the agrochemical active is present in a concentration range of at least 30% by weight of the total composition. According to an embodiment, the agrochemical active is present in a concentration range of at least 40% by weight of the total composition. According to an embodiment, the agrochemical active is present in a concentration range of at least 50 % by weight of the total composition. According to an embodiment, the agrochemical active is present in a concentration range of at least 60% by weight of the total composition. According to an embodiment, the agrochemical active is present in a concentration range of at least 70% by weight of the total composition. According to an embodiment, the agrochemical active is present in a concentration range of at least 80% by weight of the total composition. According to an embodiment, the agrochemical active is present in a concentration range of at least 90% by weight of the total composition. According to another embodiment, the agrochemical granules are selected from water dispersible granules, fine granules; microgranules; soluble granules, Emulsifiable granules, dispersible granules, broadcast granules, disintegrable granules or extruded granules. According to yet another embodiment, the agrochemical granules are preferably broadcast granules, disintegrable granules or extruded granules.
According to an embodiment the granular composition includes granules which arepolygonal, spherical, oval, or any polyhedral granules, without affecting the superior properties observed. According to an embodiment, the agricultural granules are substantially spherical. According to an embodiment, the granular composition is in a size range of 0.1 mm to 6 mm. According to another embodiment, the granular composition is in the size range of 0.1 mm to 3 mm. According to yet another embodiment, the granular composition is in the size range of 0.1 mm to 2 mm. According to a still further embodiment, the granular composition is in the size range of 0.1 mm to 1 mm.
According to an embodiment, the granules formed have a particle size in the range of 0.1 micron to 100 microns. According to an embodiment, the granules formed have a particle size in the range of 0.1 micron to 60 microns. According to an embodiment, the granules formed have a particle size in the range of 0.1 micron to 30 microns. According to an embodiment, the granules formed have a particle size in the range of 0.1 micron to 20 microns.
According to another embodiment, the granular composition of the invention exhibits a reduced bulk density compared to known compositions, which facilitates faster disintegration of the granules and also prevents settling of the composition in water. The granular composition also exhibited an improved hardness and attrition resistance as compared to known pellets or granules.
The granular composition surprisingly possesses good hardness. According to an embodiment, the hardness exhibited by the the granular composition is at least 1 Newton.
According to an embodiment, the granular composition has a hardness of at least 3 Newtons. According to an embodiment, the granular composition has a hardness of at least 5 Newtons. According to another embodiment, the granular composition has a hardness of at least 10 Newtons. According to another embodiment, the granular composition has a hardness of at least 20 Newtons. According to another embodiment, the granular composition has a hardness of at least 30 Newtons.
According to another embodiment, the granular composition has a hardness of at least 40 Newtons. According to another embodiment, the granular composition has a hardness of at least 60 Newtons. The hardness exhibited by the granules is estimated by hardness testers such as the ones provided by Shimadzu, Brinell Hardness (AKB-3000 Model), Mecmesin, Agilent, Vinsyst, Ametek and Rockwell.
According to an embodiment, the granular composition has a disintegration time of less than 30 minutes. According to an embodiment, the granular composition has a disintegration time of less than 20 minutes. According to an embodiment, the granular composition has a disintegration time of less tha 10 minutes. According to an embodiment, the granular composition has a disintegration time of less than 5 minutes. According to an embodiment, the granular composition has a disintegration time of less than 3 minutes. According to an embodiment, the granular composition has a disintegration time of less than 2 minutes. According to an embodiment, the granular composition has a disintegration time of less than 1 minute. According to an embodiment, the granular composition has a disintegration time of less than 30 seconds. The disintegration time is estimated by disintegration testing equipments such as the ones provided by Electrolab Edutec, Arentek and Shimadzu.
According to yet another embodiment, at least 99% of the granular composition disintegrates in less than 30 minutes. According to yet another embodiment, at least 50% of the granular composition disintegrates in less than 20 minutes. According to yet another embodiment, at least 30% of the granular composition disintegrates in less than 10 minutes. According to yet another embodiment, at least 20% of the granular composition disintegrates in less than 5 minutes. According to yet another embodiment, at least 10% of the granular composition disintegrates in less than 3 minutes. According to yet another embodiment, at least 5% of the granular composition disintegrates in less than 1 minute. According to a still further embodiment, at least 2% of the granular composition disintegrates in less than 30 seconds.
According to an embodiment, the bulk density of the granular composition is less than 1.5 gms/ml. According to an embodiment, the bulk density of the granular composition is preferably less than 1.2 gms/ml. According to another embodiment, the bulk density of the granular composition is preferably less than 1.0 g/ml. According to another embodiment, the bulk density of granular composition is preferably less than 0.9 g/ml.
According to another embodiment, the granular composition of the invention exhibits a improved floatability compared to known granules, which facilitates superior availability of the composition to the crops or plants, reduced leaching of the actives. The composition exhibits reduced settling of the composition in water. The granules composition also exhibited an improved disintegration, dispersion and suspension as compared to known granules. Floatability can be defined as the ability of the granular composition to remain on the surface of the fluid without sinking. According to an embodiment, the floatability of the granular composition is less than 99%. According to another embodiment, the floatability of the granular composition is less than 90%. According to an embodiment, the floatability of the granular composition is less than 80%. According to an embodiment, the floatability of the granular composition is less than 70%. According to an embodiment, the floatability of the granular composition is less than 60%. According to an embodiment, the floatability of the granular composition is less than 50%. According to an embodiment, the floatability of the granular composition is less than 40%. According to an embodiment, the floatability of the granular composition is less than 30%. According to an embodiment, the agrochemical granular composition has floatability less than 25%. According to an embodiment, the agrochemical granular composition has floatability less than 15%. According to an embodiment, the agrochemical granular composition has floatability less than 10%. According to an embodiment, the agrochemical granular composition has floatability less than 5%. According to an embodiment, the agrochemical granular composition has floatability less than 3%. According to an embodiment, the agrochemical granular composition has floatability less than 1%. According to an embodiment, the agrochemical granular composition has floatability less than 0.5%.
Attrition resistance determines the resistance of a granular material to wear. The process of determining attrition resistance involves agitating the granules, by tumbling within a drum to simulate a fluidized bed. After a certain time has elapsed, the material is sieved and weighed to determine the amount of material which has been reduced to below a certain size (referred to as 'fines'). According to an embodiment, the attrition resistance of the granules is at least 30%. According to an embodiment, the attrition resistance of the granules or pellets is at least 40%. According to an embodiment, the attrition resistance exhibited by the granules isat least 50%. According to an embodiment, the attrition resistance of the granules is at least 60%. According to an embodiment, the attrition resistance of the granules is at least 70%. According to another embodiment, the granules exhibit an attrition resistance of at least 80%. According to an embodiment, the granules exhibit an attrition resistance at least 90%. The specifics of the test are defined by various standards as applicable to the purpose in question, such as those defined by ASTM, well known to a person skilled in the art.
Dispersibility is defined as the ability of the granules to disperse upon addition to a liquid such as water or a solvent. To determine dispersibility of the granular composition as per the standard CIPAC test, MT 174, a known amount of the granular composition was added to a defined volume of water and mixed by stirring to form a suspension. After standing for a short period, the top nine-tenths are drawn off and the remaining tenth dried and determined gravimetrically. The method is virtually a shortened test of suspensibility and is appropriate for establishing the ease with which the granular composition dispersed uniformly in water.
According to an embodiment, the granular composition have a dispersibility of at least 40%.
According to an embodiment, the granular composition have a dispersibility of at least 50%.
According to an embodiment, the granular composition have a dispersibility of at least 60%.
According to an embodiment, the granular composition have a dispersibility of at least 70%. According to an embodiment, the granular composition have a dispersibility of at least 80%.
According to an embodiment, the granular composition have a dispersibility of at least 90%.
Suspensibility is defined as the amount of active ingredient suspended after a given time in a column of liquid, of stated height, expressed as a percentage of the amount of active ingredient in the original suspension. To determine suspensibility of the granular composition (as per CIPAC MT-184), a suspension of known concentration of the granular composition in CIPAC Standard Water was prepared and placed in a prescribed measuring cylinder at a constant temperature, and allowed to remain undisturbed for a specified time. The top 9/10ths were drawn off and the remaining 1/lOth was then assayed either chemically, gravimetrically, or by solvent extraction, and the suspensibility was calculated. According to an embodiment, the granular composition have a suspensibility of at least 10%. According to an embodiment, the granular composition have a suspensibility of at least 20%. According to an embodiment, the granular composition have a suspensibility of at least 30%. According to an embodiment, the granular composition have a suspensibility of at least 40%. According to an embodiment, the granular composition have a suspensibility of at least 50%.
According to an embodiment, the granular composition has a suspensibility of at least 60%.
According to an embodiment, the granular composition has a suspensibility of at least 70%.
Wettability is the condition or the state of being wettable and can be defined as the degree to which a solid is wetted by a liquid, measured by the force of adhesion between the solid and liquid phases The wettability of the granular composition was measured using the Standard Cipac Test MT-53 which describes a procedure for the determination of the time of complete wetting of wettable formulations. A weighed amount of the granular composition was dropped on water in a beaker from a specified height and the time for complete wetting was determined. According to an embodiment, the granular composition has a wettability of less than 30 minutes. According to another embodiment, the granular composition has a wettability of less than 20 minutes. According to another embodiment, the granular compostion has a wettability of less than 15 minutes. According to another embodiment, the granular composition has a wettability of less than 10 minutes. According to another embodiment, the granular composition has a wettability of less than 5 minutes. According to another embodiment, the granular composition has a wettability of less than 2 minutes. According to another embodiment, the granular composition has a wettability of less than 1 minute. According to another embodiment, the granular composition has a wettability of less than 30 seconds.
According to another embodiment, an agrochemical active is a solid active. According to further embodiment, the agrochemical active has a melting point greater than 35°C. According to further embodiment, the agrochemical active has a melting point greater than 40°C. According to further embodiment, the agrochemical active has a melting point greater than 45°C. According to further embodiment, the agrochemical active has a melting point greater than 50°C. According to an embodiment, the composition further comprises one or more of fertilizers, a second pesticidal active, macronutrients and micronutrients or salts thereof.
According to another embodiment, the fertilizer includes one or more of but not limited to single nutrient fertilizers, multi nutrient fertilizers, micro-nutrients, binary fertilizers, compound fertilizers, organic fertilizers, derivatives or mixtures thereof. Preferably the fertilizers include, but not limited to at least one of nitrogen fertilizer, sulphur fertilizer, phosphate fertilizer, potash fertilizer or salts, derivatives and mixtures thereof. According to still further embodiment, the nitrogen fertilizer can include urea, ammonium sulphate, ammonium nitrate, anhydrous ammonia, ammonium nitrate sulphate, Diammonium phosphate, Nitrogen solutions, Monoammonium phosphate, Ammonium polyphosphate, Triple superphosphate, their derivatives, oxides, salts and mixtures thereof.
According to still further embodiment, the sulphur based fertilizer can include elemental sulphur, Ammonium thiosulfate, Calcium sulphate, Gypsum or derivatives, oxides, salts and mixtures thereof.
According to another embodiment, the macronutrients include one or more of, but not limited to carbohydrates, fats, and proteins or salts, derivatives and mixtures therefore.
According to another embodiment, the micronutrients include one or more of but not limited to Vitamins such as Vitamin A, Vitamin B, Vitamin C, Vitamin D, Vitamin E, Vitamin K, Carotenoids, Minerals such as Boron, Calcium, Chloride, Chromium, Cobalt, Copper, Fluoride, Iodine, Iron, Magnesium, Manganese, Molybdenum, Phosphorous, Potassium, Selenium, Sodium, Zinc and Organic Acids such as Acetic acid, Citric acid, Lactic acid, Malic acid, Choline and Taurine or salts, derivatives and mixtures therefore. According to an embodiment, the one or more of fertilizers, a second pesticidal active, macronutrients and micronutrients or salts thereof are in a concentration range of 0.01% to 95% by weight ot the total composition.
According to an embodiment, the thermostable plasticizer, includes one or more of surfactants, polyethers, thermoplastic materials, resins, lubricants, protective colloids, water soluble salts, nitrogen fertilizers, water soluble polymers, water soluble co-polymers, complexing agents, carbohydrates or derivatives and combinations thereof.
According to an embodiment, the thermostable plasticizer is selected from one or more of Polyoxyethylene oxide, Vitamin E polyethylene glycol succinate, Macrogolglycerol Hydroxystearate, Polyethylene glycol, Polaxomer (block copolymer of polyoxyethylene- polyoxypropylene), Polyoxyethylene-polyoxypropylene block copolymer, l-phenyl-l,2-ethanediol, Poly(ethylene )adipate, Ethylene Oxide/Propylene Oxide Block Copolymer, ethylene-vinyl acetate copolymers, Copovidone of vinyl-pyrrolidone and vinyl acetate, polyvinyl caprolactam-polyvinyl acetate-polyethylene glycol graft co-polymer, Polyvinyl alcohol (PVA)-polyethylene glycol (PEG) graft co-polymer and Hydroxypropylcellulose.
According to another embodiment, the thermostable plasticizer has a melting point less than 250°C. According to further embodiment, the thermostable plasticizer has a melting point less than 200°C. According to further embodiment, the thermostable plasticizer has a melting point less than 150°C. According to further embodiment, the thermostable plasticizer has a melting point less than 100°C.
According to further embodiment, the thermostable plasticizer has a melting point less than 80°C. According to another embodiment, the thermostable plasticizer has a melting point lower than the melting point of agrochemical active ingredient. According to an embodiment, the thermostable plasticizer has a molecular weight of less than 100 gms/mol. According to an embodiment, the thermostable plasticizer has a molecular weight of less than 500 gms/mol. According to an embodiment, the thermostable plasticizer has a molecular weight of less than 1000 gms/mol. According to an embodiment, the thermostable plasticizer has a molecular weight of less than 2000 gms/mol. According to another embodiment, the thermostable plasticizer has a molecular weight of less than 5000 gms/mol. According to another embodiment, the thermostable plasticizer has a molecular weight of less than 10,000 gms/mol. According to another embodiment, the thermostable plasticizer has a molecular weight of less than 15,000 gms/mol. According to another embodiment, the thermostable plasticizer has a molecular weight of less than 20,000 gms/mol. According to another embodiment, the thermostable plasticizer has a molecular weight of less than 30,000 gms/mol. According to another embodiment, the thermostable plasticizer has a molecular weight of less than 50,000 gms/mol. According to another embodiment, the thermostable plasticizer has a molecular weight of less than 60, 000 gms/mol. According to another embodiment, the thermostable plasticizer has a molecular weight of less than 70,000 gms/mol. According to another embodiment, the thermostable plasticizer has a molecular weight of less than 80,000 gms/mol. According to another embodiment, the thermostable plasticizer has a molecular weight of less than 90,000 gms/mol. According to another embodiment, the thermostable plasticizer has a molecular weight of less than 1,00,000 gms/mol. According to another embodiment, the thermostable plasticizer has a molecular weight of less than 1,00,000 gms/mol. According to another embodiment, the thermostable plasticizer has a molecular weight of less than 1,20,000 gms/mol. According to another embodiment, the thermostable plasticizer has a molecular weight of less than 1,50,000 gms/mol. According to another embodiment, the thermostable plasticizer has a molecular weight of less than 2,00,000 gms/mol.
According to an embodiment, the thermostable plasticizer is water soluble. The term "water soluble active plasticizer" includes any plasticizer which is soluble in water. According to an embodiment, the thermostable plasticizer has a solubility of more than 0.1 mg/liter in water at 20°C. According to an embodiment, the thermostable plasticizer has a solubility of more than 0.5 mg/liter in water at 20°C. According to an embodiment, the thermostable plasticizer has a solubility of more than 1 mg/liter in water at 20°C. According to an embodiment, the thermostable plasticizer has a solubility of more than 1 g/liter in water at 20°C. According to an embodiment, the thermostable plasticizer has a solubility of more than 10 g/liter in water at 20°C. According to an embodiment, the thermostable plasticizer has a solubility of more than 25 g/liter in water at 20°C.
According to another embodiment, the thermostable plasticizer is present in a concentration range of at least 0.01% by weight of the total composition. According to another embodiment, the thermostable plasticizer is present in a concentration range of at least 0.1% by weight of the total composition. According to another embodiment, the thermostable plasticizer is present in a concentration range of at least 1% by weight of the total composition. According to another embodiment, the thermostable plasticizer is present in a concentration range of at least 5% by weight of the total composition. According to another embodiment, the thermostable plasticizer is present in a concentration range of at least 10% by weight of the total composition. According to another embodiment, the thermostable plasticizer is present in a concentration range of at least 20% by weight of the total composition. According to another embodiment, the thermostable plasticizer is present in a concentration range of at least 30% by weight of the total composition. According to another embodiment, the thermostable plasticizer is present in a concentration range of at least 40% by weight of the total composition. According to another embodiment, the thermostable plasticizer is present in a concentration range of at least 50% by weight of the total composition. According to another embodiment, the thermostable plasticizer is present in a concentration range of at least 60% by weight of the total composition.
According to an embodiment, the agrochemically acceptable excipients, auxiliaries or additives comprise wetting agents, dispersing agents, emulsifiers, binding agents, biocides, sticking agents, disintegrating agents, fillers, diluents, plasticizers, spreading agents, surfactants, solvents, coating agents, pigments, dyes, anti caking agents, thixotropic agents, anti-drift agents, colorants, buffers, pH adjusters, adhesives, fragrances, evaporation inhibitors, fertilizers, micronutrients, macro- nutrients, protective colloids, antifoam agents, antimicrobial agents, complexing agents, neutralizing agents, odorants, viscosity modifiers, thickeners, penetration aids, processing additives, sequestering agents, humectants, preservatives, polyethers, lubricants, protective colloids, solvents, coating agents, antioxidants and stabilizers or derivatives, an anti-mold agent, a bubble agent, agglomeration suppressants, wax, fats and oils, such as, for example, carnauba wax, stearic acid, stearyl alcohol or castor oil, anti-caking agents and mixtures thereof. Surfactants can include one or more of non-ionic surfactants, anionic surfactants or derivatives and mixtures thereof. The agrochemically acceptable excipients are commercially manufactured and available through various companies. According to an embodiment, the agrochemically acceptable excipients are present in a concentration range of 0.01% to 99% by weight of the total composition. According to an embodiment, the agrochemically acceptable excipients are present in a concentration range of 0.01% to 80% by weight of the total composition. According to an embodiment, the agrochemically acceptable excipients are present in a concentration range of 0.01% to 60% by weight of the total composition.
According to an embodiment the disintegrants used in the granular composition include, but not limited to one or more of sodium, potassium bicarbonates/ carbonates or their mixtures or salts with acids such as citric and fumaric acid, Polyplasdone® XL-10 crosslinked polyvinylpyrrolidone, microcrystalline cellulose, cross-linked sodium carboxymethyl cellulose and salts of polyacrylates of methacrylates. According to an embodiment, the dispersants are present in a concentration range of 0.01% to 80% by weight of the total composition. According to an embodiment the dispersants used in the granular composition include, but not limited to one or more of polyvinyl pyrrolidone, polyvinyl alcohol, lignin sulphonates, phenol naphthalene sulphonates, ethoxylated alkyl phenols, ethoxylated fatty acids, alkoxylated linear alcohols, polyaromatic sulfonates, sodium alkyl aryl sulfonates, glyceryl esters, maleic anhydride copolymers, phosphate esters, condensation products of aryl sulphonic acids and formaldehyde, condensation products of aryl sulphonic acids and urea formaldehyde with formaldehyde condensate of naphthalene sulfonic acid, addition products of ethylene oxide and fatty acid esters, salts of addition products of ethylene oxide and fatty acid esters, sulfonates of condensed naphthalene, lignin derivatives, ligno sulphonates, naphthalene formaldehyde condensates, sodium salt of isodecyl sulfosuccinic acid half ester, polycarboxylates, sodium alkyl benzene sulfonates, sodium salts of sulfonated naphthalene, ammonium salts of sulfonated naphthalene, salts of polyacrylic acids, salts of phenol sulfonic acids and salts of naphthalene sulfonic acids, sodium and ammonium salts of maleic anhydride copolymers and sodium salts of condensed phenolsulfonic acid as well as the napthalene sulfonate-formaldehyde condensates or their salts, derivatives. The dispersants are commercially manufactured and available through various companies.
The dispersants that are commercially available under the trademark but are not limited to Norlig® lid calcium lignosulfate, sodium naphthalene formaldehyde condensate available under brands Morwet® D425 Lomar ® PW (emery 5353), Polyfon® AF sodium modified kraft lignin, Morwet® EFW Mixture of sodium alkyl naphthalene sulfonates and alkyl carboxylate. According to an embodiment, the dispersants are present in a concentration range of 0.01% to 80% by weight of the total composition.
According to an embodiment the wetting agents used in the granular composition include, but not limited to one or more of phenol naphthalene sulphonates, alkyl naphthalene sulfonate, sodium alkyl naphthalene sulfonate, sodium salt of sulfonated alkylcarboxylate, polyoxyalkylated ethyl phenols, polyoxyethoxylated fatty alcohols, alkyl sulfosuccinates, polyoxyethoxylated fatty amines, lignin derivatives, lignosulfonates, alkane sulfonates, taurates, alkylbenzene sulfonates, salts of polycarboxylic acids, salts of esters of sulfosuccinic acid, alkylnaphthalenesulphonates, phosphate esters condensation products of formaldehyde, phenol sulfonic acid condensates, acetylenic diols and alkyl phenol ethoxylates, methyl oleyltaurates alkylbenzenesulfonates, alkylpolyglycol ether sulfonates, ethoxylated silicones, alkyl ether phosphates, alkyl ether sulphates and alkyl sulfosuccinic monoesters or salts or derivatives thereof. The wetting agents are commercially manufactured and available through various companies. Some of them that are available under brand names, but not limited to Petro* Ag-Special sodium alkylnaphthalene sulfonate, Masil* 280LP silicone surfactant, Alkanol® XC Sodium alkyl naphthalene sulfonate, Siponate® DS-10 Sodium dodecyl benzene sulfonate, Siponate® 301- 10F Sodium alkyl alpha-olefin sulfonate, Tamol® SN Sodium naphthalene sulfonate formaldehyde condensate, C 14 -C 19 olefin sulfonate sodium salt (eg (R) Hostapur OS.) And Alkyldiglykolathersulfat sodium salt (for example (R) Genapol LRO.). According to an embodiment, the wetting agents are present in a concentration range of 0.01% to 80% by weight of the total composition.
According to an embodiment, illustrative examples of binding agents which are used in the granular composition can be selected from, but not limited to at least one of carbohydrates such as monosaccharides, disaccharides, oligosaccharides and polysaccharides; proteins; lipids; glycolipid; glycoprotein; lipoprotein; and combinations and derivatives of these. The carbohydrate binders can include one or more of glucose, mannose, fructose, galactose, sucrose, lactose, maltose, xylose, arabinose, trehalose and mixtures thereof. The binding agents can also include corn syrup; celluloses such as carboxymethylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxy-methylethylcellulose, hydroxyethylpropylcellulose, methylhydroxyethylcellulose, methylcellulose; starches such as amylose, seagel, starch acetates, starch hydroxyethyl ethers, ionic starches, long-chain alkyl starches, dextrins, maltodextrin, corn starch, amine starches, phosphates starches, and dialdehyde starches; plant starches such as corn starch and potato starch; other carbohydrates such as pectin, amylopectin, xylan, xanthan gum, glycogen, agar, alginic acid, phycocolloids, chitin, gum arabic, guar gum, gum karaya, gum tragacanth and locust bean gum. The binding agents can also include complex organic substances such as phenyl naphthalene sulphonate, lignin and nitrolignin; derivatives of lignin such as lignosulfonate salts illustratively including calcium lignosulfonate and sodium lignosulfonate and complex carbohydrate-based compositions containing organic and inorganic ingredients such as molasses. Suitable protein binders illustratively can include soy extract, zein, protamine, collagen, and casein. The functional binding agents can also include synthetic organic polymers such as ethylene oxide polymers or copolymers, propylene oxide copolymer, polyethylene glycols, polyethylene oxides, polyacrylamides, polyacrylates, polyvinyl pyrrolidone, polyalkyl pyrrolidone, polyvinyl alcohol, polyvinylmethyl ether, polyvinyl acrylates, hydrated inorganics such as sodium silicate, sorbitol, or urea, polylactic acid, polyethoxylated fatty acids, polyethoxylated fatty alcohols and latex. However, those skilled in the art will appreciate that it is possible to utilize different binding agents without departing from the scope of the present invention. The binding agents are commercially manufactured and available through various companies.
According to an embodiment, the binding agents are present in a concentration range of 0.01% to 80% by weight of the total composition.
According to an embodiment, the fillers or carriers include, but not limited to one or more of attapulgite, kaolinites, clays, montmorillonite, montromolite, bauxite, hydrated aluminas, perlite, calcined aluminas, diatomaceous earth, chalk, fuller's earth, dolomite, kiesulguhr, loess, prophyllites, talc, mirabilite, starch, lactose, white carbon, Sericite, slaked lime, sodium carbonate, sodium bicarbonate, volclay, vermiculites, limestone, natural and synthetic silicates, calcium and magnesium silicates, titanium dioxide, hydroxides, silicates, carbonates and sulfates of calcium, magnesium, aluminum and titanium, aluminum, titanium, magnesium, calcium and zinc oxide, calcium and magnesium carbonate, and charcoal, silicas, mica, china clay, swelling and non- swelling clays, synthetic and diatomaceous silicas, , ammonium, sodium, potassium, calcium and barium sulphate, sand, , gypsum and inorganic water-soluble salts. The fillers are commercially manufactured and available through various companies.
Commercially available Silicates are Aerosil brands, Sipemat brands as Sipernat ® 50S and CALFLO E, and aerogels Fa. Cabot, kaolin 1777, aluminosilicates, Wessalon* 50S. Preferred carriers include, but not limited to one or more of attapulgite, kaolinites, clays, montmorillonite, montromolite, bauxite, hydrated aluminas, perlite and its derivatives calcined aluminas, diatomaceous earth, chalk, fuller's earth, dolomite, kiesulguhr, loess, prophyllites, talc, vermiculites, limestone, natural and synthetic silicates, silicas, mica.
The fillers that are commercially available under the trademark but are not limited to According to an embodiment, the fillers or carriers are present in a concentration range of 0.01% to 90% by weight of the total composition.
According to an embodiment, filler has an oil absorption capacity of at least 30%. According to further embodiment, the filler has an oil absorption capacity of more than 35%. According to further embodiment, the filler has oil absorption capacity of more than 50%. According to further embodiment, the filler has an oil absorption capacity of more than 75%. According to further embodiment, the filler has the oil absorption capacity of more than 100%. According to another embodiment, the filler has an oil absorption capacity of up to 175%. According to further embodiment, the filler has an oil absorption capacity of up to 160%. According to further embodiment, the filler has an oil absorption capacity of up to 115%. According to an embodiment, the filler has oil absorption capacity in the range of 30% to 175%.
According to an embodiment, the composition optionally include anti-caking agents such as Foammaster® Soap L sodium stearate, Brij® 700 polyoxyethylene (100) stearyl ether, Aerosol® OT- B sodium dioctyl sulfosuccinate, Silwet® L-77 silicone-polyether copolymer, sodium and ammonium phosphates, sodium acetate, sodium metasilicate, magnesium, zinc and calcium sulfates, magnesium hydroxide, anhydrous calcium chloride, molecular sieves, sodium alkylsulfosuccinates, calcium and barium oxides, sodium carbonate or bicarbonate.
According to an embodiment, the emulsifiers or surfactants include one or more of ionic, non- ionic and amphoteric surfactants. The ionic surfactants include one or more of, but not limited to carboxylates, alkyl carboxylates, fatty acid salts, fluoro carboxylate, alkyl sulfates, alkyl ether sulfates, sulfonates, alkyl benzene sulfonates, alpha olefin sulphonates, aromatic hydrocarbon sulphonates, naphthalene sulfonate salts, fatty alcohol sulphates, mono-alkyl sulphosuccinates, alkyl sulphosuccinamates, naphthalene sulphonates, sulfonate docusates, phosphate esters, alkyl aryl ether phosphates, alkyl ether phosphates, quaternary ammonium salts, quaternised amine ethoxylates. The non-ionic surfactants include one or more of, but not limited to polyol esters, polyol fatty acid esters, polyethoxylated esters, polyethoxylated alcohols, block copolymers of polyethylene glycol and polypropylene glycol, poloxamers, polysorbates, alkyl polysaccharides such as alkyl polyglycosides and blends thereof, amine ethoxylates, sorbitan fatty acid ester , glycol and glycerol esters , glucosidyl alkyl ethers, sorbitan alkyl esters, sodium tallowate, polyoxyethylene glycol sorbitan alkyl esters, sorbitan derivatives, fatty acid esters of sorbitan (Spans) and their ethoxylated derivatives (Tweens), and sucrose esters of fatty acids. More particularly the nonionic emulsifier include one or more of, but not limited to polyethylene glycol, glyceryl laureate, lauryl glucoside, nonylphenolpolyethoxyethanols, nonyl phenol polyglycol ether , castor oil ethoxylate, polyglycol ethers, polyadducts of ethylene oxide and propylene oxide, block copolymer of polyalkylene glycol ether and hydroxystearic acid, ethylene oxide propylene oxide block copolymer, tributylphenoxypolyethoxy ethanol, octylphenoxypolyethoxy ethanol, etho- propoxylatedtristyrlphenols, ethoxylated alcohols, polyoxy ethylene sorbitan, a sorbitan fatty acid ester, a glycerin fatty acid ester, a fatty acid polyglyceride, a fatty acid alcohol polyglycol ether, acetylene glycol, acetylene alcohol, an oxyalkylene block polymer, a polyoxyethylene alkyl ether, a polyoxyethylene alkylaryl ether, a polyoxyethylene styrylaryl ether, a polyoxyethylene glycol alkyl ether, polyethylene glycol, a polyoxyethylene fatty acid ester, a polyoxyethylene sorbitan fatty acid ester, a polyoxyethylene glycerin fatty acid ester, a polyoxyethylene hydrogenated castor oil or a polyoxypropylene fatty acid ester; and mixtures thereof.
The anionic surfactants include one or more of, but not limited to a salt of fatty acid, a benzoate, a polycarboxylate, a salt of alkylsulfuric acid ester, an alkyl sulfate, an alkylaryl sulfate, an alkyl diglycol ether sulfate, a salt of alcohol sulfuric acid ester, an alkyl sulfonate, an alkylaryl sulfonate, an aryl sulfonate, a lignin sulfonate, an alkyldiphenylether disulfonate, a polystyrene sulfonate, a salt of alkylphosphoric acid ester, an alkylaryl phosphate, a styrylaryl phosphate, a salt of polyoxyethylene alkyl ether sulfuric acid ester, a polyoxyethylene alkylaryl ether sulfate, a salt of polyoxyethylene alkylaryl ether sulfuric acid ester, a polyoxyethylene alkyl ether phosphate, a salt of polyoxyethylene alkylaryl phosphoric acid ester, a salt of polyoxyethylene aryl ether phosphoric acid ester, a naphthalene sulfonic acid condensed with formaldehyde or a salt of alkylnaphthalene sulfonic acid condensed with formaldehyde and mixtures thereof.
Non-ionic emulsifiers or surfactant that are commercially available under the trademark but are not limited to Atlas G5000 and TERMUL 5429JERMU L 2510, ECOTERIC® , EU LSOG EN® 118,Genapol®X , Genapol®OX -080 , Genapol® C 100, Emulsogen ® EL 200, Arlacel P135, Hypermer 8261, Hypermer B239, Hypermer B261, Hypermer B246sf, Solutol HS 15,Promulgen™ D,Soprophor 7961P, Soprophor TSP/461, Soprophor TSP/724, Croduret 40, Etocas 200, Etocas 29, Rokacet R26 ,CHEMONIC OE-20, Triton™ N-101,Tween 20,40,60,65,80, Span20, 40,60,80,83,85,120, Brij®, Triton™ can also be used. Amphoteric surfactants can include one or more of betaine, imidazolines, alkyl amphoacetates and proprionates, alkyl Ampho(di)acetates, and diproprionates, lecithin. According to an embodiment, the surfactants or emulsifiers are present in a concentration range of 0.01% to 90% by weight of the total composition.
According to an embodiment, the antioxidants can be selected from, but not limited to one or more of amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and derivatives thereof, imidazole and imidazole derivatives (e.g. urocanic acid), peptides, such as, D,L-carnosine, D- carnosine, L-carnosine and derivatives thereof (e.g. anserine), caro- tenoids, carotenes (e.g. ct- carotene, β-carotene, lycopene) and derivatives thereof, lipoic acid and derivatives thereof (e.g. dihydrolipoic acid), aurothioglucose, propylthiouracil and further thio compounds (e.g. thioglycerol, thiosorbitol, thioglycolic acid, thioredoxin, glutathione, cysteine, cystine, cystamine and the glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl, lauryl, palmitoyl, oleyl, y-linoleyl, cholesteryl and glyceryl esters thereof), and salts thereof, dilauryl thiodipropionate, distearyl thiodipropion- ate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts), and sulfoximine compounds (e.g. buthionine sulfoximi- nes, homocysteine sulfoximine, buthionine sulfones, penta-, hexa-, heptathionine sul- foximine) in very low tolerated doses (e.g. pmol/kg to pmol/kg), also metal chelating agents (e.g. a-hydroxy fatty acids, EDTA, EGTA, phytic acid, lactoferrin), α-hydroxy acids (e.g. citric acid, lactic acid, malic acid), humic acids, bile acid, bile extracts, gallic esters (e.g. propyl, octyl and dodecyl gallate), flavonoids, catechins, bilirubin, biliverdin and derivatives thereof, unsaturated fatty acids and derivatives thereof (e.g. y-linolenic acid, linoleic acid, arachidonic acid, oleic acid), folic acid and derivatives thereof, hy- droquinone and derivatives thereof (e.g. arbutin), ubiquinone and ubiquinol, and derivatives thereof, vitamin C and derivatives thereof (e.g. ascorbyl palmitate, stearate, di- palmitate, acetate, Mg ascorbyl phosphates, sodium and magnesium ascorbate, diso- dium ascorbyl phosphate and sulfate, potassium ascorbyl tocopheryl phosphate, chito- san ascorbate), isoascorbic acid and derivatives thereof, tocopherols and derivatives thereof (e.g. tocopheryl acetate, linoleate, oleate and succinate, tocophereth-5, toco- phereth-10, tocophereth-12, tocophereth-18, tocophereth-50, tocophersolan), vitamin A and derivatives (e.g. vitamin A palmitate), the coniferyl benzoate of benzoin resin, rutin, rutinic acid and derivatives thereof, disodium rutinyl disulfate, cinnamic acid and deriva- tives thereof (e.g. ferulic acid, ethyl ferulate, caffeeic acid), kojic acid, chitosan glyco- late and salicylate, butylhydroxytoluene, butylhydroxyanisol, nordihydroguaiacic acid, nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid and derivatives thereof, mannose and derivatives thereof, selenium and selenium derivatives (e.g. selenomethionine), stilbenes and stilbene derivatives (e.g. stilbene oxide, trans-stilbene oxide). According to the invention, suitable derivatives (salts, esters, sugars, nucleotides, nucleosides, peptides and lipids) and mixtures of these specified active ingredients or plant extracts (e.g. teatree oil, rosemary extract and rosemarinic acid) which comprise these antioxidants can be used. The antioxidants are commercially manufactured and available through various companies.
According to an embodiment, the antioxidants are present in a concentration range of 0.01% to 60% by weight of the total composition. According to an embodiment, the composition can also comprise a pH adjuster or buffer or neutralizing agent. The pH buffer or neutralizing agent can include both acids and bases of organic or inorganic origin. According to an embodiment, the pH buffer or neutralizing agent include but are not limited to organic acids, inorganice acids and alkali metal compounds or salts. The organic acids can include, but not limited to one or more of citric, malic, adipic, cinnamic, fumaric, maleic, succinic and tartaric acid or salts or derivatives thereof, and the mono-, di- or tribasic salts of these acids or derivatives thereof. Suitable salts of these acids can be the soluble or meltable salts and include those salts in which one or more acidic protons are replaced with a cation such as sodium, potassium, calcium , magnesiu, and ammonium and mixtures thereof. Alkali metal compounds can include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, carbonates of alkali metals such as sodium carbonate, magnesium carbonates and potassium carbonate, hydrogen carbonates of alkali metals such as sodium hydrogencarbonate and alkali metal phosphates such as sodium phosphate and mixtures thereof. According to an embodiment, the salts of inorganic acids include, but are not limited to one or more of alkali metal salts such as lithium chloride, sodium chloride, potassium chloride, lithium nitrate, sodium nitrate, potassium nitrate, lithium sulfate, sodium sulfate , potassium sulfate, sodium monohydrogen phosphate, potassium monohydrogen phosphate, sodium dihydrogen phohsphate potassium dihydrogen phosphate and the like; alkaline earth metal salts such as magnesium choliride, calcium chloride, ammonium sulphate, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate and the like.
According to another embodiment, the invention further relates to the process of preparing a stable granular composition. The process involves mixing and blending at least one agrochemical active ingredient wherein the agrochemical active comprises at least one of a water soluble active ingredient or a water sensitive active ingredient; with at least one thermostable polymer to obtain a mixture. To the mixture, premilled fillers and surfactants are blended. The entire mixture of the active, plasticizer, filler and surfactants, disintegrants, are then heated in an oil bath at a temperature appropriate for melting the thermostable polymer or plasticizer. The melted mixture was then extruded through a medium pressure extruder to give the the stable agrochemical granular composition; such that the granular composition has a wettability of less than 20 minutes.
The process conditions need to be carefully managed so as to give a final granular product, which has the desired properties of disintegration time, wettability, dispersibility and floatability. A person skilled in the art, can, using the right amount of pressure during extrusion, provide the desired composition.
EXAMPLES:
PREPARATION EXAMPLES:
The following examples illustrate the basic methodology and versatility of the composition of the invention.
1. Granular Composition containing 6% Cartap hydrochloride
Table 1:
Figure imgf000042_0001
65 parts by weight of Cartaphydrochloride was further mixed thoroughly with 22 parts by wet of citric acid to obtain a mixture A. To this mixture 713 parts by weight of filler including dolomite, kiesulguhr, perlite and Witconate™ (Sodium alkyl aryl sulfonate) was added and mixed thoroughly. Further 200 parts by weight of PEG 4000 was added. The mixture was then heated and extruded and cooled to obtain a granular composition of 6.5% Cartap hydrochloride.
2. Granular Composition containing 4% Cartap hydrochloride and 72.5% Sulphur
Table 2:
Constituent Amount (gms) Percentage Cartap hydrochloride 45 4.5 %
Sulphur 765 76.5 %
Citric Acid 20 2%
PEG 4000 100 10%
Rhodamine B 3 0.3%
Filler including Clay, 67 6.7%
M ica, Perlite and
Witconate™ (Sodium
alkyl aryl sulfonate)
765 parts by weight of Sulphur Active ingredient and 67 parts by weight of Delta filler including dolomite, kiesulguhr, perlite and Witconate™ (Sodium alkyl aryl sulfonate) were mixed thoroughly to obtain a mixture A. 45 parts by weight of Cartap hydrochloride was further mixed with 20 parts by wet of citric acid to obtain a mixture B. Mixture A and Mixture B were then combined together and to this combination 100 parts by weight of PEG 4000 was added. The mixture was then heated and extruded and cooled to obtain a granular composition of 76.5% of sulphur and 4.5% Cartap hydrochloride. COMPARISON OF PHYSICAL PROPERTIES:
Figure imgf000043_0001
embodiment of
the present
invention
Sulphur 50% + 42 sees N.A. 35% 7 N.A. N.A. 5% 0.65 Cartap
Hydrochloride
7.5%WP as per
the
embodiment of
251/MU M/201
1
4% Cartap 75 sees 120-180 45% 28 1.5 N 4 mm to 8 8% 0.78 Granules as per sec mm
the
embodiment of
EP1882414
application
6% Cartap 70 sees 105 sees 40% 23% 2.2N 4 mm to 6 7.5% 0.61 Granules as per mm
the
embodiment of
EP2460408
application
8% Cartap 100 sees 215 sees 80% 18% 3.1N 0.1 mm 10% 0.72 Granules as per to 10 mm
the
embodiment of
US6703350
Sulphur 90 % 50 sees 120 sees N.A. 8% N.A. 0.1mm to N.A.
WG as per 2.5 mm
I N282429
BIOEFFICACY RESULTS:
Example 1: Bioefficacy of Cartap hydrochloride granules as per the embodiment of the present invention: The field trials were carried out in the Hissar district of Haryana state in India on rice, to evaluate the effectiveness of Cartap hydrochloride granules prepared as per the embodiment of the present invention as well as Sulphur plus Cartap hydrochloride granules as per the embodiment of the present invention. The experiments were also conducted using Sulphur 90% WG standalone and Cartap hydrochloride 4% Granules standalone used as standards for comparison as well as an untreated control. The treatments also included compositions of Sulphur 70% + Cartap Hydrochloride 4% WP prepared as per the embodiment of 251/MU M/2011. The treatments also included compositions as per the embodiments of EP1882414, EP2460408 and US6703350B 5 which disclose granular compositions of Cartap.
The treatments were carried out following the randomized block design and keeping all the agronomic practices uniform for all the treatments. The treatments were imposed as and when a significant number of stem borer (Scirpophaga incertulas Walker) population per leaf were observed. All the agronomic practices were adopted as per recommendations.
10 The larvae of Scirpophaga incertulas Walker cause dead hearts during vegetative stage and white ear heads during reproductive stage. A rice plant can compensate if dead heart infestation does not exceed 10 per cent, however, the white ear loss is irrepairable. The observation of % white ear head infestation as well as 5 plant damage due to leaf minor was taken. The table 1A and IB represents the observations with respect to white ear head infestation and leaf minor
15 respectively.
The treatments were carried out by broadcasting the compositions twice the on 30th and the 60th days after rice transplantation. To avoid intermixing of treatments about 20 to 30 cm thick false bund boundaries were prepared all around plots having the treatments of granular insecticides. Both the applications and their efficacy were evaluated.
20 The treatments applied were as indicated in the table below:
Table 1A: Efficacy with respect to white ear head
Figure imgf000045_0001
Sulphur 75%+Cartap Hydrochloride 4% G R 7500+400 10000 3.3 3.9 as per the embodiment of the present
invention
Sulphur 75%+Cartap Hydrochloride 6% G R 7500+600 10000 2.7 2.4 as per the embodiment of the present
invention
Sulphur 50% + Cartap Hydrochloride 10000+1500 20000 5.4 5.6 7.5%WP as per the embodiment of
251/MU M/2011
4% Cartap Granules as per the 1000 25000 9.1 8.9 embodiment of EP1882414 application
6% Cartap Granules as per the 1200 25000 8.4 8.6 embodiment of EP2460408 application
8% Cartap Granules as per the 1000 20000 9.5 9.1 embodiment of US6703350
Sulphur 90 % WG 6750 7500 10.2 10.9
Cartap Hydrochloride 4% Granules 750 18750 8.4 8.1 (available commercially)
Untreated check 13.3 13.6
Note: DAT- Days after Transplanting
It was noted that superior efficacy was obtained with respect to control of white ear head with the application of both Treatements 1 and 2 with 4% Cartap hydrochloride granules and 6% Cartap hydrochloride granules with compositions as per the embodiment of the present invention, applied at significantly reduced dosages of application as compared to Treatments 6 and 7 with Cartap 4%, Cartap 6% and Cartap 8% granules prepared as per the embodiments of EP1882414, EP 2460408 and US6703350 and applied at significantly higher dosages of application.
Further Sulphur 75% + Cartap Hydrochloride 4% G R at 7500+400 g.a.i. per hectare (Treatment 3) and Sulphur 75% + Cartap Hydrochloride 6% G R at 7500+600 g.a.i. per hectare (Treatment 4 (provided better control over the white ear head infestation at 75 days after transplanting in comparison to Treatment 5 with Sulphur 50% + Cartap Hydrochloride 7.5% G R at 10000+1500 g.a.i. per hectare as per the embodiment of 251/MU M/2010 and as compared to treatments 8 and 9 with standalone applications of sulphur and Cartap at much higher dosages as compared to 5 Treatment 3 and 4.
Table IB: Efficacy with respect to leaf minor
Figure imgf000047_0001
Sulphur 90 % WG 6750 7500 16.4 15.5 12.7
Cartap Hyrochloride 4% Granules 750 18750 10.6 7.5 6.9 (available commercially)
Untreated check 18.5 15.7 13.2
Note: DAT- Days after Transplanting
As it can be observed from table IB the control of the plant damage caused due to leaf minor was superior for treatment 1 (with 4% Cartap hydrochloride granules); treatment 2 (with 6% Cartap hydrochloride granules); treatment 3 (with Sulphur 75%+Cartap Hydrochloride 4% granules) and treatment 4 (with Sulphur 75%+Cartap Hydrochloride 6% granules) which are with the compositions prepared as per the embodiment of the present invention, applied at significantly reduced dosages of application as compared to stand alone treatments with sulphur (treatment 9) and cartap (treatment 10) as well as compared to treatments 6, 7 and 8 with Cartap 4%, Cartap 6% and Cartap 8% granules prepared as per the embodiments of EP1882414, EP 2460408 and US6703350 and applied at significantly higher dosages of application.
Apart from controlling the larvae of Scirpophaga pests and leaf minor the combined product of sulphur + Cartap Hydrochloride in varying concentrations as per the present invention also displayed a valuable impact on the physiological factors like improved foliage (greenness) in rice and an increase in the number of tillers, contributing to higher yield. Below is a tabular presentation of the yield indicating the number of tillers at 60 DAT (days after transplanting)
TablelB:
Figure imgf000048_0001
2 Sulphur 75%+ Cartap 7500+600 7.21
Hydrochloride 6% G R as
per the embodiment of
the present invention
3 Sulphur 50% + Cartap 10000+1500 6.5
Hydrochloride 7.5%WP as
per the embodiment of
251/MU M/2011
5 Sulphur 90 % WG 6750 5.27
6 Cartap Hydrochloride 4% 750 4.78
Granules
The maximum numbers of tillers were observed with the application of Treatment 2 with Sulphur 75% + Cartap Hydrochloride 6%G R at 7500 + 600 g.a.i. per hectare . The application of Treatment 1 with Sulphur 75% + cartap hydrochloride 4%GR at 7500 + 400 g.a.i. per hectare also showed a significant increase in the number of tillers observed.
The crops also exhibited enhanced chlorophyll content due to the application of sulphur in combination with cartap hydrochloride in varying concentrations.
The above composition in practice serves the purpose of simultaneously managing the damage caused by stem borer and leaf folder and the need of sulphur fertilizer required in the initial stages of plant growth, thereby rendering the composition more economical and beneficial to the end-users when compared to the individual application of Cartap hydrochloride or Sulphur.
The above composition also restricts the undue loading of a carrier such as sand which is present upto the extent of 90% in standalone Cartap hydrochloride composition which is actually a waste. Thus, it can be concluded that the water dispersible granular compositions, according to the embodiments of the invention show significantly enhanced bioefficacy, as compared to conventional formulations and other prior art water dispersible granule formulations, even at reduced dosages of application with an effect sustained over a longer duration of time. From the foregoing, it will be observed that numerous modifications and variations can be effectuated without departing from the true spirit and scope of the novel concepts of the present invention. It is to be understood that no limitation with respect to the specific embodiments illustrated is intended or should be inferred.

Claims

Claims
A stable agrochemical granular composition comprising:
at least one first agrochemical active ingredient, wherein the first agrochemical active comprises at least one of a water soluble active ingredient or a water sensitive active ingredient;
at least one thermostable plasticizer wherein the plasticizer has a melting point greater than 20°C and less than 150°C;
at least one agrochemically acceptable excipient;
wherein the granular composition has a wettability of less than 20 minutes.
The stable agrochemical granular composition of Claim 1, wherein the granular composition has a floatability of less than 99%.
The stable agrochemical granular composition of Claim 1, wherein the granular composition has a floatability of less than 99% over a time period of 10 minutes.
The stable agrochemical granular composition of Claim 1, wherein the granular composition has a disintegration time of less than 30 minutes.
The stable agrochemical granular composition of Claim 1, wherein the composition has a bulk density of less than 1.5 gms/ml.
The stable agricultural granular composition of claim 1, wherein the composition has an attrition resistance of at least 20%.
The stable agrochemical granular composition of claim 1, wherein the water soluble active ingredient has solubility in water of more than 0.1 mg per liter of water.
8. The stable agrochemical granular composition of claim 1, wherein the decomposition of the active comprised in the granular composition is less than 20% under accelerated storage conditions.
The stable agrochemical granular composition of claim 1, wherein the thermostable plasticizer is selected from the group consisting of one or more of surfactants, polyethers, thermoplastic materials, resins, lubricants, protective colloids, water soluble salts, water soluble polymers, nitrogen fertilizers, water soluble co-polymers, block polymers, polyethers, complexing agents, carbohydrates or derivatives.
10. The stable agrochemical granular composition of claim 1, wherein the thermostable plasticizer is selected from one or more of Polyoxyethylene oxide, Vitamin E polyethylene glycol succinate, Macrogolglycerol Hydroxystearate, Polyethylene glycol, Polaxomer (block copolymer of polyoxyethylene-polyoxypropylene), Polyoxyethylene- polyoxypropylene block copolymer, l-phenyl-l,2-ethanediol, Poly(ethylene )adipate, Ethylene Oxide/Propylene Oxide Block Copolymer, ethylene-vinyl acetate copolymers, Copovidone of vinyl-pyrrolidone and vinyl acetate, polyvinyl caprolactam-polyvinyl acetate-polyethylene glycol graft co-polymer, Polyvinyl alcohol (PVA)-polyethylene glycol (PEG) graft co-polymer and Hydroxypropylcellulose.
The stable agrochemical granular composition of claim 1, wherein the first agrochemical active ingredient is selected from one or more of insecticides, fungicides, herbicides, plant growth regulators, nematicides, acaricides, insect growth regulators, safeners, weedicides or other miscellaneous pesticidal actives.
12. The stable agrochemical granular composition of claim 1, wherein the first agrochemical active ingredient is selected from one or more of neonicotinoid insecticides, the oxyphenoxy acid esters, cyclohexanedione oxime herbicides, sulfonyl urea compounds, cloquintocet herbicide safeners, the HPPD-inhibiting herbicides, phenylpyrazoles, nereistoxin analogue insecticides, and organophosphate insecticides.
13. The stable agrochemical granular composition of claim 1, wherein the first agrochemical active ingredient is one or more of cartap hydrochloride, cartap, and pinoxaden.
The stable agrochemical granular composition of claim 1, wherein the secon> agrochemical active ingredient is fipronil.
15. The stable agrochemical granular composition of claim 1, wherein the composition further comprises one or more of fertilizers, second pesticidal active ingredient, macronutrients and micronutrients.
16. The use of the agrochemical granular composition of claim 1, wherein the composition is at least one of a fertilizer composition, a nutrient composition, crop protection composition, pesticicidal composition, a plant strengthener composition, a soil conditioner composition and a yield enhancer composition.
17. A process of preparing a stable granular composition, the process comprising:
a. mixing and blending at least one agrochemical active ingredient wherein the agrochemical active comprises at least one of a water soluble active ingredient or a water sensitive active ingredient; with at least one thermostable polymer to obtain a mixture;
b. heating and cooling the mixture to arrive at the stable agrochemical granular composition;
wherein the granular composition has a wettability of less than 20 minutes.
18. The process of Claim 26, wherein the mixing and blending step further includes adding one or more of agrochemical excipient to the mixture.
19. A method of protection of crop or improving its health or yield, the method comprising treating at least one of a plant, crop, a plant propagation material, a seed, seedling or surrounding soil with a stable granular composition comprising:
i. at least one agrochemical active ingredient, wherein the agrochemical active comprises one or more of a water soluble active ingredient or a water sensitive active ingredient;
ii. at least one thermostable plasticizer; and,
iii. at least one agrochemically acceptable excipient; wherein the granular composition has a wettability of less than 20 minutes. .
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