DESC:FIELD OF THE INVENTION
The present invention relates to a storage stable composition. The invention more specifically relates to a storage stable composition comprising moisture-sensitive agrochemicals.
BACKGROUND AND THE PRIOR ART
There are many agrochemical compositions that exhibit undesirable changes when exposed to a moist environment, during the time of preparation and also upon storage. Depending on the particular agrochemical, the changes can result from hydrolysis, or from reactions with other components of the composition or with the atmosphere. Since manufacturing of agrochemical compositions cannot always be conducted in an environment having a low humidity, there can be significant degradation during the various production operations, prior to packaging a product. After packaging, stability of the products can be affected by transfer of moisture through packaging components, as well as reactions involving components of the package atmosphere. Due to normal fluctuations in the moisture content of the atmosphere, storage of moisture sensitive agrochemicals becomes challenging.
Organophosphorous and chloronicotinyl class of agrochemicals are sensitive to moisture and require utmost attention while developing their composition individually or in combination.
The organophosphorus compound acephate has the IUPAC name O,S-dimethyl acetylphosphoramidothioate and a CAS Number 30560-19-1. Acephate is a systemic insecticide used to control sucking and chewing insects by direct contact or ingestion. Organophosphates such as acephate bind to and inhibit the enzyme acetylcholinesterase (AChE) in nervous system tissues. As a result, the neurotransmitter acetylcholine accumulates and repeatedly activates cholinergic receptors. It is used primarily for control of aphids, including resistant species, in vegetables (e.g. potatoes, carrots, greenhouse tomatoes, and lettuce) and in horticulture (e.g. on roses and greenhouse ornamentals). Acephate is not very stable in conventional pesticidal formulations, such that a vigorous decomposition of acephate in conventional formulations takes place depending on storage conditions, particularly on exposure to moisture.
The Chloronicotinyl insecticides class include nitroimino- or nitroguanidino-compounds, for example, the compounds imidacloprid, acetamiprid, and thiamethoxam. Chloronicotinyl insecticides kill target pests in a similar manner as the natural product nicotine, by acting on the central nervous system, causing irreversible blockage of the postsynaptic nicotinergic acetylcholine receptors.
Imidacloprid is a chloronicotinyl nitroguanidine insecticide, with the IUPAC name (E)-1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolidin-2-ylideneamine and a CAS Number of 138261–41–3. It is a systemic chloronicotinyl insecticide that enters the target pest via ingestion or direct contact. It acts as an antagonist by binding to postsynaptic nicotinic receptors in the insect central nervous system.
Imidacloprid controls sucking insects, soil insects, termites, and some chewing insects, and is effective against all feeding stages. It is used to treat seeds, soil, crops and structures, and is a flea control treatment on domestic pets. Imidacloprid is hygroscopic and is prone to absorb moisture from the surrounding atmosphere.
"Acetamiprid" is E)-N1-[(6-chloro-3-pyridyl)methyl]-N2-cyano-N1-methylacetamidine (IUPAC Name). It is a systemic insecticide for soil and foliar application. It has a strong penetration, readily availability, and long duration. It controls Hemiptera, especially aphids, Thysanoptera and Lepidoptera, by soil and foliar application, on a wide range of crops, especially vegetables, fruits and tea. It is stable in the neutral or slightly acidic medium. It can gradually degrade when pH is 9 at 45?.
As an environment protection guideline to some countries for risk mitigation, composition comprising acephate alone or with other active ingredients is to be packed and sold in water-soluble bags. As acephate is toxic to humans, water soluble bag prohibits direct contact of acephate to the user.
Water soluble bags are now used frequently to store wide variety of agrochemicals. Such water soluble bags offer many advantages, among them being the pre-measurement of the packet contents for a single use; reduction in the degree of inconvenience or hazard in using agrochemicals which are dusty or otherwise undesirable if allowed to come in physical contact with the user. Nevertheless, agrochemical compositions packed in water soluble bags are relatively easy to handle during the mixing process and also results in decreased contamination of the environment.
Water soluble bags are made of water-soluble thermoplastic films with an inherent moisture content of 6.0%-12.0%. It has been observed that water soluble bags are affected by external factors such as temperature, pH and moisture. The water soluble bags experience premature breakage when kept in high humidity place. Similarly, high temperature makes it brittle due to loss of inherent moisture.
To avoid such undesirable conditions, it has now become a common practice to doubly pack the unit doses of agrochemicals, i.e. first packing it in water soluble bags and then in trilaminated pouch. Packing the water soluble bag in trilaminated pouch provide shield to water soluble bag and protect it from exposure to external factors.
It is a well-known fact that organophosphorous compounds and chloronicotinyl compounds experience chemical incompatibility. While organophosphorous compounds like acephate is unstable in alkaline pH, chloronicotinyl compounds are unstable in acidic pH and it is difficult to formulate them together. Acephate degrades rapidly in the presence of moisture. Chloronicotinyl compounds are also hygroscopic and often hydrolyse with increasing acidic pH and temperature. When acephate is combined with chloronicotinyl compounds to form a composition, it accelerates degradation of chloronicotinyl compounds by adding moisture to the composition. When such composition of acephate and chloronicotinyl compounds is packed in water soluble bag, degradation of chloronicotinyl compounds accelerate further. Acephate absorbs moisture from water soluble bag, adding it to the composition and thus accelerating degradation of chloronicotinyl compounds.
In past, researchers tried addressing the compatibility issues of acephate and chloronicotinyl compounds when they are formulated together.
U. S. Application No. 20060008493 disclosed a synergistic composition comprising chloronicotinyl compound and organophosphorous compound, specifically imidacloprid and acephate. The compositions disclosed include a stabilizer, which though is able to impart limited stability and limited shelf life but there is a need to investigate and solve the problem of stability of such compositions, especially under moisture conditions.
US Pat No. 5,140,019 has disclosed methods of prevention of decomposition of a combination of a compound comprising imidacloprid, an organophosphorous compound and compounds selected from polyethylene glycol, propylene glycol, ethylene glycol-propylene glycol co-polymer or a mixture of these compounds. We have found that said combination is unstable with low storage stability as the two active ingredients interact with each other and decompose.
In patent IN241600, disclosed is a storage stable formulation of chloronicotinyl compound and an organophosphorus compound wherein at least one of the active ingredients is provided with a coating of a water soluble polymer i.e. polyethylene glycol. The coating of a water soluble polymer acts as barrier between the mutually incompatible agents, which are in solid form, such as a chloronicotynyle compound and an organophosphorus compound more preferably imidacloprid and acephate respectively. Although disclosed formulation demonstrated storage stability when packed in trilaminated pouch but stability while packaging in water soluble bags remain unaddressed.
In a co-pending patent application 1001/MUM/2007, disclosed is the storage stable formulation of chloronicotinyl compound selected from imidacloprid and an organophosphorus compound selected from acephate and phosphamidon wherein hydrophobic silica is used as compatibility inducing inert stabilizing agent. The compatibility inducing inert stabilizing agent provided an inert environment to both the active ingredients by the use of hydrophobic silica by preventing individual pH sensitivities of imidacloprid and acephate. However, stability of said formulation in water soluble bags remain unaddressed.
It is now understood that besides tackling the compatibility challenges of acephate and chloronicotinyl compounds in the compositions, an added problem comes across while packing and storing such compositions in water soluble bags. Acephate absorbs moisture from the water soluble bags. The added moisture in the composition degrades chloronicotinyl compounds leading to overall degradation of the composition. Therefore, need exists to provide a composition of moisture sensitive acephate and chloronicotinyl compounds having storage stability in water soluble bags and also the process of obtaining the stable composition.
OBJECTS OF THE PRESENT INVENTION
The main objective of the present invention is to provide a storage stable composition of moisture sensitive agrochemicals, namely an organophosphorus compound and a chloronicotinyl compound, which is stable while storing in water soluble bags.
Another objective of the present invention is to provide a process of preparing a storage stable composition of moisture sensitive agrochemicals, namely an organophosphorus compound and a chloronicotinyl compound, which is stable in water soluble bags.
Another objective of the present invention is to provide a storage stable composition comprising of acephate and chloronicotinyl compound which has an improved shelf life.
SUMMARY OF THE INVENTION
In accordance with the above objectives, the invention provides a storage stable composition of moisture sensitive agrochemicals, namely an organophosphorus compound and a chloronicotinyl compound, wherein the composition has the moisture content less than 0.5% by weight of the composition.
Further, the invention provides a process for preparing storage stable composition of moisture sensitive agrochemicals, namely an organophosphorus compound and a chloronicotinyl compound, wherein the composition has the moisture content less than 0.5% by weight of the composition.
Further, the invention provides use of storage stable composition of moisture sensitive agrochemicals, namely an organophosphorus compound and a chloronicotinyl compound, wherein the composition having moisture content less than 0.5% by weight of the composition is used as an insecticidal composition.
DETAILED DESCRIPTION OF THE INVENTION
It is now been found, surprisingly, that by reducing moisture content to less than 0.5%, of the composition comprising an organophosphorus compound and a chloronicotinyl compound, stability of the composition can be achieved and resulting composition of these two otherwise incompatible active ingredients remain unaffected in the presence of inherent moisture of water soluble bags.
As used herein the term ‘composition’ is used interchangeably with the term ‘formulation’ and is intended to refer to the storage stable solid composition made of agrochemicals which are extremely sensitive to moisture.
In accordance with the present invention, the invention provides a storage stable composition of moisture sensitive agrochemicals, namely an organophosphorus compound and a chloronicotinyl compound, wherein the composition has the moisture content less than 0.5% by weight of the composition.
In an embodiment, the invention provides a storage stable composition of moisture sensitive acephate and imidacloprid wherein the composition having moisture content less than 0.5% does not deteriorate in the presence of inherent moisture of water soluble bag.
In an embodiment, the invention provides a storage stable composition of moisture sensitive acephate and acetamiprid wherein the composition having moisture content less than 0.5% does not deteriorate in the presence of inherent moisture of water soluble bag.
According to another embodiment of the present invention, the storage stable composition comprises from about 0.5% to about 95% w/w and preferably from about 10% to about 85% w/w acephate active ingredient of the total weight of the storage stable composition.
In a preferred embodiment of the present invention, the storage stable composition comprises from about 20% to about 75% w/w acephate active ingredient of the total weight of the storage stable composition.
According to another embodiment of the present invention, the storage stable composition comprises from about 0.1% to about 30% w/w and preferably from about 0.2% to about 20% w/w chloronicotinyl compound of the total weight of the storage stable composition.

In another preferred embodiment of the present invention, the storage stable composition comprises from about 1% to about 10% w/w chloronicotinyl compound of the total weight of the storage stable composition.
In an embodiment of the present invention, there is provided a process for preparing storage stable composition of an organophosphorus compound and a chloronicotinyl compound having moisture content less than 0.5% by weight of the composition wherein the process comprising steps of:
• mixing chloronicotinyl compound with inert stabilizing agent and adding other excipients to obtain a homogeneous mixture;

• mixing separately an organophosphorus compound with inert filler and blend to obtain another homogeneous mixture;
• mixing together the two homogeneous mixtures obtained above and blending it to obtain a homogeneous mass;

• granulating the homogeneous mass in a suitable granulator to obtain granules with moisture content less than 0.5% by weight of the composition.

• optionally, drying the granules in a suitable device if moisture content of the finished granules is not less than 0.5% by weight of the composition;
According to another embodiment of the present invention, there is provided a process for preparing storage stable composition of acephate and chloronicotinyl compound having moisture content less than 0.5% by weight of the composition wherein the process comprising steps of:
• mixing chloronicotinyl compound with inert stabilizing agent and adding other excipients to obtain a homogeneous mixture;

• mixing separately acephate with inert filler and blend to obtain another homogeneous mixture;
• mixing together the two homogeneous mixtures obtained above and blending it to obtain a homogeneous mass;

• granulating the homogeneous mixture in a suitable granulator to obtain granules with moisture content less than 0.5% by weight of the composition.

• optionally, drying the granules in a suitable device if moisture content of the finished granules is not less than 0.5% by weight of the composition;

According to another embodiment of the present invention, there is provided a process for preparing storage stable composition of acephate and imidacloprid having moisture content less than 0.5% by weight of the composition wherein the process comprising steps of:
• mixing imidacloprid with inert stabilizing agent and adding other excipients to obtain a homogeneous mixture;

• mixing separately acephate with inert filler and blend to obtain another homogeneous mixture;
• mixing together the two homogeneous mixtures obtained above and blending it to obtain a homogeneous mass;

• granulating the homogeneous mixture in a suitable granulator to obtain granules with moisture content less than 0.5% by weight of the composition.

• optionally, drying the granules in a suitable device if moisture content of the finished granules is not less than 0.5% by weight of the composition;

According to an embodiment of the present invention, the storage stable composition comprises an agriculturally acceptable inert stabilizing agent selected from mineral earth like silica, silica gels, silicates, talc, kaolin, montmorillonite, attapulgite, pumice, sepiolite, bentonite, limestone, lime, chalk, clay, dolomite, diatomaceous earth, and calcite.

According to another embodiment of the present invention, the storage stable composition comprises an agriculturally acceptable inert stabilizing agent selected from silicas (fumed silica and precipitated silica) with low moisture grade.

According to another embodiment of the present invention, the storage stable composition comprises of fumed silica with low moisture grade. Examples of fumed silicas are Aerosil 200 and Aerosil R972.

According to another embodiment of the present invention, the storage stable composition comprises of precipitated silica with low moisture grade. Examples of precipitated silicas are Mfill A-100 and Sipernat.

According to another embodiment of the present invention, the storage stable composition comprises from about 1% to about 20% w/w and preferably from about 0.5% to about 15% w/w inert stabilizing agent of the total weight of the composition. In a preferred embodiment of the present invention, inert stabilizing agent comprises from about 0.1% to about 10% w/w of the total weight of the composition.
According to another embodiment of the present invention, the storage stable composition comprises an agriculturally acceptable inert filler selected from anhydrous calcium sulfate, magnesium sulfate, magnesium oxide, sand, ground plastics, fertilizers like ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, cereal meal, tree bark meal, wood meal, nutshell meal, and cellulose powders.

According to another embodiment of the present invention, the storage stable composition comprises of an agriculturally acceptable inert filler selected from ammonium sulfate, calcium sulfate or magnesium oxide.

According to another embodiment of the present invention, the storage stable composition comprises from about 1% to about 60% w/w and preferably from about 5% to about 50% w/w inert filler of the total weight of the composition.

In a preferred embodiment of the present invention, inert filler comprises from about 10% to about 40% w/w of the total weight of the composition.

According to another embodiment of the present invention, mixing of actives is performed in a suitable mixing device, preferably in a Plough Shear Mixer (PSM).
According to another embodiment of the present invention, the storage stable composition of moisture sensitive acephate and chloronicotinyl compound is subjected to drying in a suitable device to bring down the moisture content of the composition to less than 0.5% by weight of the composition.
Examples of dryers that may be used include air flow band dryers, stirring dryers, fluidized bed dryers, vibration dryers and bed-type dryers. The fluidized bed dryer is preferred.
In one embodiment of the present invention, the composition is subjected to drying in Fluidized Bed Dryer (FBD) at 40°C to 70°C to obtain moisture of the composition to less than 0.5% by weight of the composition.

According to another embodiment of the present invention, compositions of the present invention may be prepared in the form of solid compositions including powders (wettable powders, soluble powders), granulates (including water dispersible granules), aggregates, compressed granulate in the form of a tablet, uncompressed granulates (beads), dusts, baits, pellets and prills.
According to another embodiment of the present invention, granules may be prepared from the storage stable composition comprising acephate and chloronicotinyl compound by granulating the homogeneous powder obtained according to the process described in the present invention.
Examples of the granulation device include basket-type granulators, extrusion granulators such as horizontal extruders, twin dome granulators, single dome granulators and pelletizers, and compression granulators such as roller compactors. An extrusion granulator is preferred.
According to another embodiment of the present invention, granules are prepared by extruding the homogeneous powder in extrusion granulator.
According to another embodiment of the present invention, the granules obtained according to the process described in the present invention undergo size regulation by sieving treatment to remove oversize and undersize granules.
According to another embodiment of the present invention, the storage stable composition of acephate and chloronicotinyl compound in the form of powder has an average particle size of 2- 1500 microns.
According to another embodiment of the present invention, the storage stable composition of acephate and chloronicotinyl compound in the form of granules have an average particle size of 0.8- 1.2 mm.
According to another embodiment of the present invention, the storage stable composition of acephate and chloronicotinyl compound is further comprising of agriculturally acceptable carrier and excipients such as ionic and non-ionic surfactants, binding agent, anticaking agent, disintegrating agent, dyes, emetic agents.

The non-ionic surfactants used may be selected from fatty alcohols having 10-24 carbon atoms with 0-20 EO; fatty acid alkoxylates and triglyceride alkoxylates; fatty acid amide alkoxylates; alkylene oxide adducts of alkynediols; alkyl aryl ethoxylate such as tristrylphenol ethoxylates; polyglycerides and derivatives thereof; preferably alcohol ethoxylate or ethoxylated castor oil.
The binding agent used may be a pyrrolidone derivative.

The anticaking agent used may be selected from the group consisting of a blend of sucrose and starch derivatives.
The disintegrating agent used may be selected from a group consisting of bentonite clay, Zeolite clay, Attapulgite clay, sodium sulphate slats, and aluminium sulphate salts.

The dyes used may be a water soluble dye or a water insoluble dye.

The emetic agent used may be a lignocaine derivative or a formulation of lignocaine derivative.

According to another embodiment of the present invention, there is provided a storage stable composition comprising from about 20% to about 75% by weight of acephate, 1% to about 10% by weight of imidacloprid, from about 0.1% to about 10% by weight of Aerosil R972, from about 1% to about 20% by weight of Mfill A-100, and from about 1% to about 50% by weight of ammonium sulfate,

According to another embodiment of the present invention, there is provided a storage stable composition comprising from about 20% to about 75% by weight of acephate, 1% to about 10% by weight of acetamiprid, from about 0.1% to about 10% by weight of Aerosil R972, from about 1% to about 20% by weight of Mfill A-100, and from about 1% to about 50% by weight of ammonium sulfate, wherein the composition comprises less than 0.5% moisture.

In an embodiment of the present invention, the storage stable composition of moisture sensitive agrochemicals, namely an organophosphorus compound and a chloronicotinyl compound, wherein the composition having moisture content less than 0.5% by weight of the composition is packed in a suitable packaging.
Therefore, in this embodiment, the present invention provides a packaged insecticidal product comprising an insecticidal composition contained within a package, said composition comprising an organophosphorus compound and a chloronicotinyl compound and having moisture content less than 0.5% by weight of the composition.

In an embodiment, the preferred package is a water soluble bag.

Therefore, in this embodiment, the present invention provides a packaged insecticidal product comprising an insecticidal composition contained within a package, wherein said composition comprises an organophosphorus compound and a chloronicotinyl compound and has moisture content less than 0.5%, and wherein said package is a water soluble bag.

In an embodiment, the preferred package is a trilaminated pouch.

Therefore, in this embodiment, the present invention provides a packaged insecticidal product comprising an insecticidal composition contained within a package, wherein said composition comprises an organophosphorus compound and a chloronicotinyl compound and has moisture content less than 0.5%, and wherein said package is a trilaminated pouch.

In an embodiment, the composition of the present invention is contained within a water soluble bag, and the package comprising the composition contained within the water soluble bag is contained within the trilaminated pouch.

Therefore, in this embodiment, the present invention provides a packaged insecticidal product comprising an insecticidal composition contained within a package, wherein said composition comprises an organophosphorus compound and a chloronicotinyl compound and has moisture content less than 0.5%, said composition being placed within a water soluble bag and said water soluble bag containing the composition being placed within a trilaminated pouch.

In an embodiment, the water soluble bag is made of a water soluble polymer selected from polyethylene glycol or a block copolymer comprising polyethylene glycol selected from copolymers with polypropylene oxide, copolymers with polyethylene butylene, and copolymers with polycaprolactone; polyvinylpyrrolidone; polyvinyl alcohol; polyacrylic acid; polyacrylamides; N-(2-hydroxypropyl) methacrylamide; divinyl ether-maleic anhydride; polyoxazoline; polyphosphates; polyphosphazenes; xanthan gums; pectins; chitosan derivatives; dextran; carrageenan; guar gum; cellulose ethers selected from hydroxypropyl methylcellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, and sodium carboxy-methyl cellulose; and starch or starch derivatives.

A packaged insecticidal product, said packaged product comprising:
(a) a composition comprising an organophosphorus compound and a chloronicotinyl compound and having a moisture content less than 0.5%;
(b) a water soluble bag containing said composition, said water soluble bag made of a water soluble polymer selected from polyethylene glycol or a block copolymer comprising polyethylene glycol selected from copolymers with polypropylene oxide, copolymers with polyethylene butylene, and copolymers with polycaprolactone; polyvinylpyrrolidone; polyvinyl alcohol; polyacrylic acid; polyacrylamides; N-(2-hydroxypropyl) methacrylamide; divinyl ether-maleic anhydride; polyoxazoline; polyphosphates; polyphosphazenes; xanthan gums; pectins; chitosan derivatives; dextran; carrageenan; guar gum; cellulose ethers selected from hydroxypropyl methylcellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, and sodium carboxy-methyl cellulose; and starch or starch derivatives.
In an embodiment, the preferred package is a trilaminated pouch having a plurality of layers, said layers being selected from:
(i) at least one first layer of a thermoplastic polymer, said thermoplastic polymer being selected from polyamideimide, polyethersulphone, polyetherimide, polyarylate, polysulphone, polyarylate, polysulphone, polyamide, polymethylmethacrylate, polyvinyl chloride, acrylonitrile butadiene styrene, polystyrene, polyetheretherketone, polytetrafluoroethylene, polyamide 6-6, polyamide 11, polyphenylene sulphide, polyethylene terephthalate, polyoxymethylene, polypropylene, high density polyethylene, low density polyethylene, polypropylene, polystyrene, polymethylmethacrylate, polyvinyl chloride, natural rubber, polydimethyl siloxane, polyoxymethylene, polycarbonate, polyetheretherketone, nylon 6, polyphenylene sulphide, polyethersulphone, polyetherimide, and liquid crystal polymer;
(ii) at least one metallic layer disposed between said thermoplastic polymer layers or deposited on at least one of said thermoplastic polymer layer; and
(iii) at least one second layer of a thermoplastic polymer, said thermoplastic polymer being selected from polyamideimide, polyethersulphone, polyetherimide, polyarylate, polysulphone, polyarylate, polysulphone, polyamide, polymethylmethacrylate, polyvinyl chloride, acrylonitrile butadiene styrene, polystyrene, polyetheretherketone, polytetrafluoroethylene, polyamide 6-6, polyamide 11, polyphenylene sulphide, polyethylene terephthalate, polyoxymethylene, polypropylene, high density polyethylene, low density polyethylene, polypropylene, polystyrene, polymethylmethacrylate, polyvinyl chloride, natural rubber, polydimethyl siloxane, polyoxymethylene, polycarbonate, polyetheretherketone, nylon 6, polyphenylene sulphide, polyethersulphone, polyetherimide, and liquid crystal polymer.

Therefore, in this embodiment, the present invention provides a packaged moisture sensitive product, said packaged product comprising:
(a) a composition comprising an organophosphorus compound and a chloronicotinyl compound and having a moisture content less than 0.5% by weight of the composition;
(b) a trilaminated pouch containing said composition, the trilaminated pouch having a plurality of layers, said layers being selected from:
(i) at least one first layer of a thermoplastic polymer, said thermoplastic polymer being selected from polyamideimide, polyethersulphone, polyetherimide, polyarylate, polysulphone, polyarylate, polysulphone, polyamide, polymethylmethacrylate, polyvinyl chloride, acrylonitrile butadiene styrene, polystyrene, polyetheretherketone, polytetrafluoroethylene, polyamide 6-6, polyamide 11, polyphenylene sulphide, polyethylene terephthalate, polyoxymethylene, polypropylene, high density polyethylene, low density polyethylene, polypropylene, polystyrene, polymethylmethacrylate, polyvinyl chloride, natural rubber, polydimethyl siloxane, polyoxymethylene, polycarbonate, polyetheretherketone, nylon 6, polyphenylene sulphide, polyethersulphone, polyetherimide, and liquid crystal polymer;
(ii) at least one metallic layer disposed between said thermoplastic polymer layers or deposited on at least one of said thermoplastic polymer layer; and
(iii) at least one second layer of a thermoplastic polymer, said thermoplastic polymer being selected from polyamideimide, polyethersulphone, polyetherimide, polyarylate, polysulphone, polyarylate, polysulphone, polyamide, polymethylmethacrylate, polyvinyl chloride, acrylonitrile butadiene styrene, polystyrene, polyetheretherketone, polytetrafluoroethylene, polyamide 6-6, polyamide 11, polyphenylene sulphide, polyethylene terephthalate, polyoxymethylene, polypropylene, high density polyethylene, low density polyethylene, polypropylene, polystyrene, polymethylmethacrylate, polyvinyl chloride, natural rubber, polydimethyl siloxane, polyoxymethylene, polycarbonate, polyetheretherketone, nylon 6, polyphenylene sulphide, polyethersulphone, polyetherimide, and liquid crystal polymer.

In an embodiment, the composition of the present invention is contained within a water soluble bag, and the package comprising the composition contained within the water soluble bag is contained within the trilaminated pouch.

Therefore, in this embodiment, the present invention provides a packaged moisture sensitive product, said packaged product comprising:
(a) a composition comprising an organophosphorus compound and a chloronicotinyl compound and having a moisture content less than 0.5% by weight of the composition;
(b) a water soluble bag containing said composition, said water soluble bag made of a water soluble polymer selected from polyethylene glycol or a block copolymer comprising polyethylene glycol selected from copolymers with polypropylene oxide, copolymers with polyethylene butylene, and copolymers with polycaprolactone; polyvinylpyrrolidone; polyvinyl alcohol; polyacrylic acid; polyacrylamides; N-(2-hydroxypropyl) methacrylamide; divinyl ether-maleic anhydride; polyoxazoline; polyphosphates; polyphosphazenes; xanthan gums; pectins; chitosan derivatives; dextran; carrageenan; guar gum; cellulose ethers selected from hydroxypropyl methylcellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, and sodium carboxy-methyl cellulose; and starch or starch derivatives; and
(c) a trilaminated pouch containing the water soluble bag containing the composition, said trilaminated pouch having a plurality of layers, said layers being selected from:
(i) at least one first layer of a thermoplastic polymer, said thermoplastic polymer being selected from polyamideimide, polyethersulphone, polyetherimide, polyarylate, polysulphone, polyarylate, polysulphone, polyamide, polymethylmethacrylate, polyvinyl chloride, acrylonitrile butadiene styrene, polystyrene, polyetheretherketone, polytetrafluoroethylene, polyamide 6-6, polyamide 11, polyphenylene sulphide, polyethylene terephthalate, polyoxymethylene, polypropylene, high density polyethylene, low density polyethylene, polypropylene, polystyrene, polymethylmethacrylate, polyvinyl chloride, natural rubber, polydimethyl siloxane, polyoxymethylene, polycarbonate, polyetheretherketone, nylon 6, polyphenylene sulphide, polyethersulphone, polyetherimide, and liquid crystal polymer;
(ii) at least one metallic layer disposed between said thermoplastic polymer layers or deposited on at least one of said thermoplastic polymer layer; and
(iii) at least one second layer of a thermoplastic polymer, said thermoplastic polymer being selected from polyamideimide, polyethersulphone, polyetherimide, polyarylate, polysulphone, polyarylate, polysulphone, polyamide, polymethylmethacrylate, polyvinyl chloride, acrylonitrile butadiene styrene, polystyrene, polyetheretherketone, polytetrafluoroethylene, polyamide 6-6, polyamide 11, polyphenylene sulphide, polyethylene terephthalate, polyoxymethylene, polypropylene, high density polyethylene, low density polyethylene, polypropylene, polystyrene, polymethylmethacrylate, polyvinyl chloride, natural rubber, polydimethyl siloxane, polyoxymethylene, polycarbonate, polyetheretherketone, nylon 6, polyphenylene sulphide, polyethersulphone, polyetherimide, and liquid crystal polymer.
Surprisingly, the present inventors have now found that the combination of at least one water soluble polymer layer, at least one first thermoplastic layer, at least one metallic layer and at least one second thermoplastic layer provides surprising mechanical strength to a package intended for a moisture sensitive agrochemical product along with providing the requisite moisture resistance to the packaged agrochemical. More surprisingly, it was found that the increased mechanical strength and the moisture resistance were prejudiced when any one of the water soluble polymer layer, or any of the thermoplastic layers or the metallic layer was absent from the packaging. It was unexpected that the described layers, in combination, provided surprising benefits to a packaged agrochemical product that was otherwise very sensitive to environmental moisture exposure.
The process for preparing such composite laminates is not particularly limiting, and these laminates may be prepared as per the conventional processes known in the art. For example, such laminates may be prepared by compression moulding, extrusion coating, extrusion lamination, tandem extrusion lamination, chemical vapour deposition etc. Such processes are commonly known in the art and are used for preparing the multi-layer laminates of the invention.
According to another embodiment of the present invention, the storage stable composition of moisture sensitive agrochemicals, namely an organophosphorus compound and a chloronicotinyl compound, wherein the composition having moisture content less than 0.5% by weight of the composition is used as an insecticidal composition.
According to another embodiment of the present invention, said storage stable composition of acephate and chloronicotinyl compound having moisture content less than 0.5% by weight of the composition is used to control agricultural pests and hygienic pests.
According to another embodiment of the present invention, said storage stable composition of acephate and chloronicotinyl compound having moisture content less than 0.5% by weight of the composition is used to control agricultural pests damaging plants selected from the group consisting of cotton, paddy, rice forage crops, sugarcane, cole crops, leafy vegetables, tobacco, tomatoes, potatoes, flowering ornamentals, vine crops and fruit trees.
Inventors of the present invention developed the storage stable composition of moisture sensitive acephate and chloronicotinyl compounds. Such stable composition have significant advantages, such as permitting packaging of composition of highly moisture sensitive actives like acephate and imidacloprid in water soluble bags with excellent storage stability. The composition containing less than 0.5% moisture manufactured according to the process described in the present invention does not deteriorate in the presence of inherent moisture of water soluble bags.

Example 1: Acephate 50% w/w and Imidacloprid 5% w/w DF was prepared as follows:
Table 1
Composition Quantity (% w/w)
Acephate Technical (98.0% purity) 52.55
Imidacloprid Technical (95.0% purity) 5.68
Aerosil R 972 5.0
Precipitated Silica (Mfill A-100) 4.95
Ammonium Sulphate (amorphous) q.s. 31.82
Total 100
* Aerosil R 972 is hydrophobic fumed silica;

1) Mixing
Part-A:
Weighed quantity of pre-ground imidacloprid technical was loaded into mixer to which weighed quantity of Aerosil R 972 was added and mixed untill a homogeneous mixture was obtained. Further Mfill A-100 was added and mixed to obtain homogeneous free flowing powder. To this powder, ammonium sulfate was added and continued blending to obtain part-A.
Part-B:
Weighed quantity of acephate technical was separately taken in a blender to which ammonium sulfate anhydrous was added. This mixture was blended thoroughly for about 30 min to obtain a homogeneous mass as part-B.
Part-C:
Finally part-A was blended into part-B and further mixed to get a homogeneous mixture of all the ingredients as part-C.
2. Extrusion:
The premix part-C was extruded using extruder with 1.0 mm diameter sieve at 70°C to obtain granules and kept for drying at room temperature.

3. Drying:
Granules obtained in the above step is kept for drying in Fluidized Bed Dryer (FBD) at 50°C for about 30-40 minutes to obtain moisture content of the finished granules to less than to 0.5% by weight of the composition.

Therefore, the storage stable composition of acephate and imidacloprid is obtained according to the process disclosed in this invention.

Example 2: Acephate 50% w/w and Imidacloprid 1.8% w/w DF was prepared as follows:
Table 1A
Composition Quantity (% w/w)
Acephate Technical (97.0% purity) 52.57
Imidacloprid Technical (95.0% purity) 1.89
Aerosil R 972 0.8
Aerosil 200 10.00
Ammonium Sulphate (anhydrous) q.s. 34.74
Total 100
* Aerosil R 972 is hydrophobic fumed silica; * Aerosil 200 is amorphous fumed silica
Mixing:
• Weighed quantity of pre-ground imidacloprid technical was loaded into a blender to which weighed quantity of Aerosil R972 was added and mixed till a homogeneous mixture was obtained. This was Part-A.

• Weighed quantity of acephate technical was separately taken in a blender to which Aerosil 200 and ammonium sulfate anhydrous was added and blended thoroughly for about 30 min to obtain a homogeneous mass. This was part-B.

• Part A was then added to part-B and blended together to get a homogeneous mixture of all the ingredients. This was part-C.

2. Drying:
The homogeneous mixture thus obtained as part-C was subjected to drying in Fluidized Bed Dryer (FBD) at 50°C for about 30-40 minutes to obtain moisture content of the finished soluble powder less than to 0.5% by weight of the composition.

Therefore, the storage stable composition of acephate and imidacloprid as soluble powder is obtained according to the process disclosed in this invention.

Example 3: Acephate 50% w/w and Imidacloprid 1% w/w DF was prepared as follows:
Table 1B
Composition Quantity (% w/w)
Acephate Technical (97.0% purity) 52.55
Imidacloprid Technical (95.0% purity) 1.05
Aerosil R 972 1.0
MFil-A-100 2.0
Ammonium Sulphate (anhydrous) q.s. 43.40
Total 100
* Aerosil R 972 is hydrophobic fumed silica; * MFil-A-100 is micronized silica

The SP composition including acephate, imidacloprid, aerosol R 972, MFil-A-100 and ammonium sulphate (anhydrous) in a given ratio shown above was prepared as per the process of Example 1.

Example 4: Acephate 50% w/w and Imidacloprid 7% w/w DF was prepared as follows:
Table 1C
Composition Quantity (% w/w)
Acephate Technical (97.0% purity) 52.55
Imidacloprid Technical (95.0% purity) 8.52
Aerosil R 972 1.0
MFil-A-100 2.0
Ammonium Sulphate (anhydrous) q.s. 35.93
Total 100
* Aerosil R 972 is hydrophobic fumed silica; * MFil-A-100 is micronized silica

The SP composition including acephate, imidacloprid, aerosol R 972, MFil-A-100 and ammonium sulphate (anhydrous) in a given ratio shown above was prepared as per the process of Example 1.

AHS STUDY OF ACTIVE INGREDIENTS WHEN COMPOSITION IS DOUBLY PACKED IN WATER SOLUBLE BAG AND TRILAMINATED POUCH
The composition prepared according to the process disclosed in the present invention was tested to determine the percentage of degradation of imidacloprid and acephate in the composition when the composition was packed in double packing.

The composition of Table 1 was packed in water soluble bag which was then placed in a trilaminated pouch and kept for 14 days at 50°C. Degradation of imidacloprid and acephate was studied at 0.32%, 0.5% and 0.59% product moisture (Table 2). It was observed that as the moisture of the composition decreased below 0.5%, degradation of imidacloprid decreased from 6.64% to 1.97% and degradation of acephate decreased from 4.17% to 1.72% resulting into a storage stable composition.

The composition of Table 1 was packed in water soluble bag which was then placed in a trilaminated pouch and further kept for 14 days at 54°C. The degradation of imidacloprid and acephate was studied at 0.32%, 0.5% and 0.59% product moisture. It was observed that as the moisture of the composition decreased below 0.5%, degradation of imidacloprid decreased from 9.61% to 2.76% and degradation of acephate decreased from 5.73% to 3.17% resulting into a storage stable composition.

Similarly, when observations were made after 28 days at 50°C, degradation of imidacloprid decreased from 8.37% to 3.75% and degradation of acephate decreased from 5.26% to 3.42%. Also, when observations were made after 28 days at 54°C, degradation of imidacloprid decreased from 13.75% to 6.82% and degradation of acephate decreased from 9.17 to 6.46%. This resulted into a storage stable composition.

PERCENTAGE DEGRADATION OF THE ACTIVE INGREDIENTS UNDER AHS CONDITIONS WHEN DOUBLY PACKED IN WATER SOLUBLE BAG AND TRILAMINATED POUCH
Table 2# % Moisture Content Active 50°C 54°C
0 Days 14 Days 28 Days 0 Days 14 Days 28 Days
1

0.59
Acephate A.I. 50.38 49.13 44.02 50.38 48.195 44.45
Degradation 2.48 12.62 4.34 11.77
Imidacloprid A.I. 5.64 5.07 4.96 5.64 5.20 4.61
Degradation 10.11 12.06 7.80 18.26
2 0.50 Acephate A.I. 50.12 48.51 47.92 50.12 47.72 45.94
Degradation 4.17 5.26 5.73 9.17
Imidacloprid A.I. 5.21 4.71 4.6 5.21 4.56 4.33
Degradation 6.64 8.37 9.61 13.75
3
0.32
Acephate A.I. 51.29 50.17 48.73 51.29 49.43 47.07
Degradation 1.72 3.42 3.17 6.46
Imidacloprid A.I. 5.063 4.97 4.92 5.063 4.93 4.7
Degradation 1.97 3.75 2.76 6.82

VISUAL INSPECTION OF PACKAGED COMPOSITION
Stability of the composition comprising imidacloprid and acephate was observed by visual inspection.

Two compositions, one having moisture content less than 0.5% and another having moisture content more than 0.5% were prepared according to the process disclosed in the invention. These two compositions were separately packed in double packing, i.e. first in water soluble bag and then in trilaminated pouch.

It was observed that packaging of the composition having moisture content less than 0.5% did not bulge and remained stable. However, packaging of the composition with moisture content of more than 0.5% bulged due to increase in the percentage of degradation of imidacloprid and acephate in the composition. Also, said composition absorbed moisture from water soluble bag, leaving it brittle.

The increase in percentage of degradation observed visually as an increase in volume of air inside packing that resulted into swelling of the overall pack. This swelling of the packing is undesirable because of two reasons. Firstly, swelling of packing indicates degradation of actives in the composition. Secondly, swelling increases volume of the packing which creates problem while stacking for storage or while transporting from one place to another. Also, the swollen packs are more prone to burst. Therefore it was concluded that when moisture content of the composition content is kept below 0.5% by weight of the composition, desirable stability can be achieved and the packaged compositions is easy to handle.

DETERMINATION OF MOISTURE CONTENT (MC) OF THE COMPOSITION AND WATER SOLUBLE BAG
Percentage moisture content of the finished granules obtained according to the process disclosed in the present invention was determined using Karl Fisher method (Table 3). Moisture content was determined at ambient temperature, at 50 °C and at 54 °C for 0, 7, 14 and 28 days. No significant change in the moisture content of the composition and the water soluble bag was observed indicating that the product was stable in said packaging.
Table 3
Ambient Temperature At 50°C At 54°C
%MC by K.F. 0 days 7 days 7 days 14 days 28 days 7 days 14 days 28 days
Composition doubly packed in Trilaminated Pouch and Water Soluble Bag
Composition 0.32 0.33 0.35 0.35 0.36 0.34 0.35 0.35
Water soluble bag 6.59 5.06 4.93 4.48 4.32 4.59 4.22 4.2

Therefore, the storage stable composition prepared according to the process disclosed in the present invention exhibited good stability. The extremely sensitive acephate and chloronicotinyl compound can be formulated together according to the process disclosed in the present invention and same can be stored safely in water soluble bag as well as trilaminated pouch without undesirable degradation of actives. The instant invention is more specifically explained by above example. However, it should be understood that the scope of the present invention is not limited by the examples in any manner. It will be appreciated by any person skilled in this art that the present invention includes aforesaid examples and further can be modified and altered within the technical scope of the present invention.
,CLAIMS:1. A storage stable composition of moisture sensitive agrochemicals comprising an organophosphorus compound and a chloronicotinyl compound wherein, said composition has moisture content less than 0.5% by weight of the composition.

2. The storage stable composition as claimed in claim 1 wherein said organophosphorus compound is acephate.

3. The storage stable composition as claimed in claim 1 wherein, said chloronicotinyl compound is selected from imidacloprid or acetamiprid.

4. The storage stable composition as claimed in claim 1 wherein, said chloronicotinyl compound is imidacloprid.

5. The storage stable composition as claimed in claim 1 wherein said organophosphorus compound is present in an amount from about 0.5% to about 95% w/w by weight of the composition

6. The storage stable composition as claimed in claim 1 wherein said chloronicotinyl compound is present in an amount from about 0.1% to about 30% w/w by weight of the composition.

7. The storage stable composition as claimed in claim 1 wherein said composition having moisture content less than 0.5% by weight of the composition does not deteriorate in the presence of inherent moisture of a water soluble bag.

8. A process for preparing the storage stable composition of moisture sensitive agrochemicals comprising an organophosphorus compound and a chloronicotinyl compound wherein, said composition has the moisture content less than 0.5% by weight of the composition., said process comprising the steps of:

• mixing a chloronicotinyl compound with inert stabilizing agent and adding other excipients to obtain a homogeneous mixture;
• mixing separately an organophosphorus compound with inert filler and blend to obtain another homogeneous mixture;
• mixing together the two homogeneous mixtures obtained above and blending it to obtain a homogeneous mass;
• granulating the homogeneous mass in a suitable granulator to obtain granules with moisture content less than 0.5% by weight of the composition.
• optionally, drying the granules in a suitable device if moisture content of the granules is less than 0.5%;
9. The process as claimed in claim 8 wherein said organophosphorus compound is acephate and said chloronicotinyl compound is Imidacloprid.

10. The storage stable composition claim 1 wherein said compositions are prepared in the form of solid compositions selected from the group comprising wettable powders, soluble powders, granulates, aggregates, compressed granulate in the form of a tablet, uncompressed granulates, beads, dusts, baits, pellets and prills.

11. A storage stable composition of moisture sensitive agrochemicals comprising an organophosphorus compound and a chloronicotinyl compound having moisture content less than 0.5% by weight of the composition wherein said composition is used as an insecticidal composition.

12. The storage stable composition of moisture sensitive agrochemicals as claimed in claim 11 wherein said composition is used as an insecticidal composition to control agricultural pests damaging plants selected from the group consisting of cotton, paddy, rice forage crops, sugarcane, cole crops, leafy vegetables, tobacco, tomatoes, potatoes, flowering ornamentals, vine crops and fruit trees.

13. A packaged insecticidal product comprising an insecticidal composition contained within a package, wherein said composition comprises an organophosphorus compound and a chloronicotinyl compound wherein, said composition has moisture content less than 0.5% by weight of the composition and wherein, said composition is contained within a water soluble bag or trilaminated pouch.

14. A packaged insecticidal product of claim 13 wherein said composition is contained within a water soluble bag and said water soluble bag containing said composition is contained within a trilaminated pouch.

15. A packaged insecticidal product of claim 13 wherein said organophosphorus compound is acephate and said chloronicotinyl compound is imidacloprid.