Abstract: The present invention relates to a synergistic pesticidal composition comprising of bioactive amounts of Dazomet and Clothianidin. The present invention also relates to process for preparing the said composition comprising of bioactive amounts of Dazomet and Clothianidin and with one or more inactive excipients. The present invention also relates to the use of synergistic pesticidal composition of Dazomet and Clothianidin for the control of Nematode, soil hibernating insects (termite & white grub), sucking pests in following crops: Cucumber, Melons, Tomato, Pepper, Eggplant, Pomegranate, Banana, Apple, Oranges, Grape, Papaya and flowers
DESC:
FORM 2
THE PATENTS ACT, 1970
(39 OF 1970)
&
The Patents Rules, 2003
COMPLETE SPECIFICATION
(See section 10; rule 13)
1. Title of the invention – SYNERGISTIC PESTICIDAL COMPOSITION OF DAZOMET AND CLOTHIANIDIN
2. Applicant(s)
(a) NAME: GSP CROP SCIENCE PVT. LTD
(b) NATIONALITY: An Indian Company
(c) ADDRESS: 404, Lalita Complex, 352/3 Rasala Road, Navrangpura,
Ahmedabad-380009, Gujarat, India
3. PREAMBLE TO THE DESCRIPTION
The following specification particularly describes the invention and the manner in which it is to be performed:
FIELD OF THE INVENTION:
The present invention relates to a synergistic pesticidal composition comprising of bioactive amounts of Dazomet and Clothianidin. The present invention also relates to process for preparing the said composition comprising of bioactive amounts of Dazomet and Clothianidin and with one or more inactive excipients. The present invention also relates to the use of synergistic pesticidal composition of Dazomet and Clothianidin for the control of Nematode, soil hibernating insects (termite & white grub), sucking pests in following crops: Cucumber, Melons, Tomato, Pepper, Eggplant, Pomegranate, Banana, Apple, Oranges, Grape, Papaya and flowers.
BACKGROUND OF THE INVENTION
Pesticides are chemicals that may be used to kill fungus, bacteria, insects, plant diseases, snails, slugs, or weeds among others. These chemicals can work by ingestion or by touch and death may occur immediately or over a long period of time.
Insecticides are a type of pesticide that is used to specifically target and kill insects. Some insecticides include snail bait, ant killer, and wasp killer.
An insecticide is a substance used to kill insects. They include ovicides and larvicides used against insect eggs and larvae, respectively. Insecticides are used in agriculture, medicine, industry and by consumers.
Insecticides can be classified by many ways. One of many classifications is as below:
Systemic insecticides are those in which the active ingredient is taken up, primarily by plant roots, and transported (translocated) to locations throughout the plant, such as growing points, where it can affect plant-feeding pests. Systemic insecticides move within the vascular tissues, either through the xylem (water-conducting tissue) or the phloem (food-conducting tissue) depending on the characteristics of the material.
Contact insecticides are toxic to insects when brought into direct contact. Efficacy is often related to the quality of pesticide application, with small droplets (such as aerosols) often improving performance.
Natural insecticides, such as nicotine, pyrethrum and neem extracts are made by plants as defenses against insects. Nicotine-based insecticides are widely used in the US and Canada, but are barred in the European Union.
Plant-incorporated protectants (PIPs) are systemic insecticides produced by transgenic plants. For instance, a gene that codes for a specific Bacillus thuringiensis biocidal protein was introduced into corn and other species. The plant manufactures the protein which kills the insect when consumed.
Inorganic insecticides are contact insecticides that manufactured with metals and include arsenates, copper and fluorine compounds, which are now seldom used, and sulfur, which is commonly used.
Organic insecticides are contact insecticides that comprise the largest numbers of pesticides available for use today.
The mode of action describes how the pesticide kills or inactivates a pest. It provides another way of classifying insecticides. Mode of action is important in understanding whether an insecticide will be toxic to unrelated species, such as fish, birds and mammals.
Insecticidal classes which covers majority of the insecticides are as below:
Organophosphates and carbamates
Organophosphates target the insect's nervous system. Organophosphates interfere with the enzymes acetylcholinesterase and other cholinesterases, disrupting nerve impulses and killing or disabling the insect. Organophosphate insecticides and chemical warfare nerve agents (such as sarin, tabun, soman, and VX) work in the same way. Organophosphates have a cumulative toxic effect to wildlife, so multiple exposures to the chemicals amplify the toxicity.
Carbamate insecticides have similar mechanisms to organophosphates, but have a much shorter duration of action and are somewhat less toxic.
Organochlorides
The best-known organochloride, DDT (Dichlorodiphenyltrichloroethane), was created by Swiss scientist Paul Müller. For this discovery, he was awarded the 1948 Nobel Prize for Physiology or Medicine. DDT was introduced in 1944. It functions by opening sodium channels in the insect's nerve cells. The contemporaneous rise of the chemical industry facilitated large-scale production of DDT and related chlorinated hydrocarbons.
Neonicotinoids
Neonicotinoids are synthetic analogues of the natural insecticide nicotine (with much lower acute mammalian toxicity and greater field persistence). These chemicals are acetylcholine receptor agonists. They are broad-spectrum systemic insecticides, with rapid action (minutes-hours). They are applied as sprays, drenches, seed and soil treatments. Treated insects exhibit leg tremors, rapid wing motion, stylet withdrawal (aphids), disoriented movement, paralysis and death. Imidacloprid may be the most common.
Pyrethroids
Pyrethroid pesticides mimic the insecticidal activity of the natural compound pyrethrum. These compounds are non-persistent sodium channel modulators and are less toxic than organophosphates and carbamates. Compounds in this group are often applied against household pests.
Ryanoids
Ryanoids are synthetic analogues with the same mode of action as ryanodine, a naturally occurring insecticide extracted from Ryaniaspeciosa (Flacourtiaceae). They bind to calcium channels in cardiac and skeletal muscle, blocking nerve transmission.
Plant-incorporated protectants
Transgenic crops that act as insecticides began in 1996 with Bt corn that produces the Cry protein, derived from the bacterium Bacillus thuringiensis, which is toxic to moth larvae such as the European corn borer. The technique has been expanded to include the use of RNA interference RNAi that fatally silences crucial insect genes. RNAi likely evolved as a defense against viruses. Midgut cells in many larvae take up the molecules and help spread the signal. The technology can target only insects that have the silenced sequence, as was demonstrated when a particular RNAi affected only one of four fruit fly species. The technique is expected to replace many other insecticides, which are losing effectiveness due to the spread of pesticide resistance.
Dazomet
Dazomet is chemically known as 3,5-dimethyl-1,3,5-thiadiazinane-2-thioneand having chemical structure as below;
Dazomet is a chemical ingredient which is used to kill pests that inhibit plant growth through gaseous degradation. Dazomet is used as a soil sterilant on a variety of sites such as golf courses, nurseries, turf sites, and potting soils. Dazomet is used for soil sterilization as an alternative to methyl bromide. Although less effective it is still used to kill pests because of its comparatively lower toxicity. Dazomet is applied to wet soil, which causes Dazomet itself to decompose into a gaseous form, which is what actively controls pests. The decomposition of Dazomet releases methyl isothiocyanate (MITC) a gas toxic to pests that would prevent or kill plant growth. Dazomet is also used as insecticide and fungicide in addition to a soil sterilizer.
Clothianidin
Clothianidin was first disclosed inEP0375907. Chemically Clothianidin is known as (E)-1-(2-chloro-1,3-thiazol-5-ylmethyl)-3-methyl-2-nitroguanidine. Chemical structure of Clothianidin is as below;
Clothianidin is an insecticide developed by Takeda Chemical Industries and Bayer AG. Similar to thiamethoxam and imidacloprid, it is a neonicotinoid. Neonicotinoids are a class of insecticides that are chemically similar to nicotine, which has been used as a pesticide since the late 1700s. Clothianidin and other neonicotinoids act on the central nervous system of insects as an agonist of acetylcholine, the neurotransmitter that stimulates nAChR, targeting the same receptor site (AChR) and activating post-synaptic acetylcholine receptors but not inhibiting AChE. Clothianidin and other neonicotinoids were developed to last longer than nicotine, which is more toxic and which breaks down too quickly in the environment.
Clothianidin is an alternative to organophosphate, carbamate, and pyrethroid pesticides. It poses lower risks to mammals, including humans, when compared to organophosphates and carbamates. It has helped prevent insect pests build up resistance to organophosphate and pyrethroid pesticides
The main concern with the use of pesticide is the development of resistance by the pests for that particular pesticide and at the end one has to apply more concentrated formulation of the pesticide. The high amount of pesticide may results in the toxicity to human beings as well as has bad effect on environment.
Previously people have tried many alternatives and option to overcome this problem and as a result developed poly mixture of pesticide, use of non-toxic ingredients and developing novel formulations which provides effective amount of the pesticide and at the required part only.
However the use of poly mixture containing large number of pesticides poses a problem in many was like preparing formulation of multiple pesticides with different chemical properties and behavior and physical properties. It also creates challenge for formulator in term of compatibility and stability of all the pesticide along with used excipients in the formulation.
US2015030501 discloses a solid body of dazomet for use in internal remedial treatments of wood and methods of applying such solid bodies to wooden structures and manufacturing such solid bodies. The solid bodies can be easily transported and inserted into treatment holes in utility poles, wooden pilings, and other wooden structures, delivering a precise, accurate dose of insecticide and fungicide that combats internal decay in the wood.
TW200528028 describes a noxious organism controlling composition enhanced in the controlling effect on noxious insects living in soil and/or seeds and simultaneously enhanced in a controlling effect on infectious disease damage in the soil and/or the seeds. The noxious organism controlling composition contains at least one kind of organic phosphorus compound selected from the group consisting of S-sec-butyl O-ethyl 2-oxo-1,3-thiazolydin-3-ylphosphonothioate, O-ethyl-S-n-propyl(2-cyanoimino-3-ethyl-imydazolidin-1-yl)phosphonothiolate, and S,S-di-sec-butyl O-ethyl phosphorodithioate and at least one kind of bactericidal agent selected from the group consisting of Fluazinam, Benomyl, Tolclofos-methyl, Metalaxyl, Captan, Iprodione, Chlorothalonil, Dazomet, Hymexazole, Flutolanil, and Validamycin as active ingredients
CN103858927 discloses an invention relates to a pesticide composition, its effective component is dazomet and fosthiazate. The mass percentage of dazomet and fosthiazate is 1-100: 100-1, and the dazomet and fosthiazate content in sterilization composition is 1-100%. The pesticide composition is used for preventing and treating nemas and soil borne disease, and the preferable dosage form is a particulate agent. The pesticide composition is used for preventing and treating soil borne disease and nematode diseases on various crops, such as cotton, vegetable, banana, coffee, corn, fruit, cereal, peanut, soybean, decorative plant and sugarcane.
US2013203825 discloses a phosphate-free, highly-concentrated aqueous dispersion composition comprising at least one biocide, sulfosuccinate based surfactant, block copolymer, suspending agent, and optionally an antifoaming agent and desired additives if any. The composition of the present application is significantly stable against heat, cold, transit, storage and dilution for at least 18 months. The preferred biocides of the dispersion composition are 2-meth-4-isothiazolin-3-one (MIT), 1,2-Benzisothiazolin-3-one (BIT), 5-Chloro-2-methyl-4-isothiazolin-3-one (CMIT), 2-Octyl-4-isothiazolin-3-one (Off) 3-Iodo-2-propynylbutyl carbamate (IPBC), oxyfluorfen, thiabendazole, terbutryn, zinc pyrithione (ZnPy), bronopol, folpet, diiiron, dehydroacetic acid (DHA), dazomet and carbendazim alone or in combination. Also disclosed is a process for preparing the dispersion composition and appropriate applications thereof.
CN102870789 discloses pesticides preparations and discloses dazomet coated controlled-release granules. The dazomet coated controlled-release granules comprise the following components in percentage by weight: 1-80% of dazomet, 1-70% of a carrier or a binder, 1-20% of a coating material, 1-10% of a film-forming aid, 0.5-5% of an organic solvent. The dazomet coated controlled-release granules are prepared form dazomet serving as an active ingredient and selected proper film-forming aid, coating material, carrier, binder and the like, have long-lasting and constant prevention effect on nematodes and weeds, is superior to the existing dazomet pesticides, and can be used for effectively protecting crops from pathogenic bacteria, nematodes and weeds.
CN102499248 describes a wettable powder, powder or a microgranule preparation prepared from accessory ingredients, such as a wetting agent, a dispersing agent, fillers and the like, and a pesticide composition containing dazomet and 1,3-dichloropropylene for controlling soil-borne diseases such as Phytoph-thoracapsiciLeonian and the like as well as Meloidogyne. The invention also discloses a method for preventing the soil-borne diseases such as the Phytoph-thoracapsiciLeonian and the like as well as Meloidogyne by using the composition containing the dazomet and the 1,3-dichloropropylene. The dazomet and the 1,3-dichloropropylene are mixed at the ratio of (1:2)-(2:1) to especially perform action on the Phytoph-thoracapsiciLeonian and the Meloidogyne.
US2007203126 relates to synergistic mixtures of o-phenylphenol and/or its sodium salt with tetrahydro-3,5-dimethyl-2H-1,3,5-thiadiazine-2-thione (Dazomet) commonly used in cement admixtures and slurries.
DE3631848 discloses a concentrated solution of dazomet in an amine or polyamine which contains, for example, up to 65% of dazomet and which is liquid at room temperature.
CN1543787 describes a process for preparing dazomet dust free stabilized fine granules from methylamine and carbon sulfide as raw material through the steps of, diluting methylamine with water in reactor, agitating, dropping carbon sulfide and controlling reaction temperature, continuing stirring 1-2h, stewing to obtain oil layer, thus the intermediate compound N-methyl dithiocarbamic acid is prepared, adding into reactor in turn the intermediate compound N-methyl dithiocarbamic acid prepared in the previous step and the water solution of soluble macromolecular compound, surface active agent, stirring, dropping formaldehyde solution and controlling reaction temperature, stewing for filtering, thus dazomet fine granule with 100 mesh average grain diameter can be prepared by drying the filter cake.
CN104082333 discloses an insecticidal composition containing clothianidin. The insecticidal composition comprises following effective ingredients in parts by weight: 0.1-50 parts of clothianidin, 0.1-20 parts of Triflumezopyrim, and further comprises one or more of 0.1-15 parts of a dispersant, 0.1-12 parts of an emulsifying agent, 0.1-4 parts of an anti-freezing agent, 0.1-4 parts of a thickening agent, 0.01-0.5 part of a de-foaming agent, 0.1-15 parts of a wetting agent, 0-10 parts of a binding agent, 0.1-6 parts of a disintegrating agent, 0-3 parts of a film forming agent and the balance being filler or a solvent, totaling 100 parts. The insecticidal composition can be used for preventing and treating various crops pests, such as rice planthopper, sugarcane aphids and stem borers; the insecticidal composition has good synergistic interaction effect, good prevention effect and long lasting period; the application amount of pesticides is reduced; meanwhile, the resistance to clothianidin is slowed down.
CN104068040 relates to a clothianidin and tebufenozide compound insecticidal composition. The clothianidin and tebufenozide compound insecticidal composition has the effective components of clothianidin and tebufenozide of which the weight ratio is 1:(4 to 8) and preferably 1:(5 to 7). The clothianidin and tebufenozide compound insecticidal composition consists of the effective components with different function mechanisms, the acting sites are increased to be conductive to overcoming and delaying production of pest drug resistance, and the insecticidal spectrum is broadened; the drug effect is greatly improved, the prevention time is long, field consumption of the effective components is reduced, the production and use costs are lowered, and pesticide residues and environmental pollution are reduced.
CN104012567 describes a pesticide composition comprising clothianidin and cyflumetofen is disclosed. Effective components comprise the clothianidin and the cyflumetofen. The weight ratio of the clothianidin to the cyflumetofen is 20:1-1:20, preferably 5:1-1:5. Many interior and outdoor experiments show that: the weeding composition pesticide composition has obvious synergistic effects, and can be used for control of various pests in agriculture, especially suitable for control of red spiders, tea lesser leafhoppers, aleyrodid, aphid and scale insects; and the pesticide using amount is reduced, thus reducing the residue amount of pesticides on crops.
CN103918698 relates to a pesticidal composition containing clothianidin and fipronil and application thereof in preventing and treating soil insects. The pesticidal composition comprises the following components in parts by weight: 10.0-40.0 parts of clothianidin and 2.0-10.0 parts of fipronil. The pesticidal composition containing clothianidin and fipronil can fully display the respective advantages of the clothianidin and fipronil, and can be used for preventing and treating wireworm, grub and other soil insects; and the composition of the two effective components has an obvious synergistic action, can achieve the effects of enhancing the preventing and treating effects and postponing the drug effect, has the advantages of quick effect taking and long duration, and is superior to the prior art.
CN103621538 describes synergistic insecticidal composition containing clothianidin and imidaclothiz and applications thereof. The synergistic insecticidal composition employs clothianidin and imidaclothiz as main effective components, wherein, the weight ratio of clothianidin to imidaclothiz is 0.1-50:0.1-50. The composition has high synergistic effects, enlarges the control spectrum, delays drug resistance of insects and can lower drug cost. The composition can be prepared into missible oil, wettable powder, microemulsion, emulsion in water, suspending agents and water dispersion granules, and is used for control of various insects of hemiptera, coleopteran, lepidoptera, hymenoptera and the like with resistance.
Further there are many prior arts which mention different composition of clothianidin either alone or in combination with other ingredients.
However still there is a need for a composition of specific synergistic composition which overcomes some of the existing problems and can be prepared easily without much complex manufacturing process.
Inventors of the present invention have surprisingly found that the synergistic pesticidal composition of Dazomet and Clothianidin as described herein in can provide solution to the above mentioned problems.
SUMMARY OF THE INVENTION
The present invention relates to a synergistic pesticidal composition which comprises of bioactive amounts of Dazomet and Clothianidin.
Further the present invention also relates to process for preparing the synergistic pesticidal composition comprising bioactive amounts of Dazomet and Clothianidin with one or more inactive excipients.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides a synergistic composition comprising bioactive amounts of Dazomet and Clothianidin with one or more inactive excipients.
The pesticidal formulation can be classified as below:
a) Dry - Sprayable
a.1) WP – Wettable powders:
A solid pesticide formulation – micronized to powder form and typically applied as suspended particles after dispersion in water.
a.2) WG or WDG – Water dispersible granule:
A pesticidal formulation consisting of granules to be applied after disintegration and dispersion in water. Water dispersible granules can be formed by a) agglomeration, b) spray drying, or c) extrusion techniques. It can also be termed as water soluble granules (WSG) or soluble granules (SG).
b) Liquid Sprayable
b.1) SL – Soluble Concentrate:
A soluble concentrate is in powder form intended for dilution with water or directly in solution from. In both the case, the end result will be clear solution of the insecticide in the water without any visible un-dissolved particles.
b.2) SC – Suspension Concentrate
A stable suspension of solid pesticide(s) in a fluid usually intended for dilution with water before use. For a good formulation or ideal SC formulation, it should be stable and do not sediment over time.
b.3) EC – Emulsifiable Concentrate
A solution of a pesticide with emulsifying agents in a water insoluble organic solvent which will form an emulsion when added to water. In most of the case it is oil in water type emulsion to make it easy for application. EC formulation should be storage stable without any visible cracking of emulsion.
b.4) ME – Microemulsion
A solution of a pesticide with emulsifying agents in a water insoluble organic solvent which will form a solution/emulsion when added to water. The difference between EC and ME is the particle size of the actives in the final form.
b.5) OD – Oil Dispersion
Oil dispersions (OD) are one type of liquid formulation which is stable suspensions of active ingredients in a water-immiscible fluid which may contain other dissolved active ingredients and is intended for dilution with water before use.
b.6) CS – Capsule Suspension
Suspension of micro-encapsulated active ingredient in an aqueous continuous phase, intended for dilution with water before use.
b.7) SE- Suspension emulsion
A suspension emulsion or suspoemulsion (SE) consists of an organic phase with a dissolved active ingredient and an aqueous suspension phase, in which the active ingredient is dispersed in water.
b.8) Dispersible concentrate (DC)
Dispersible concentrate (DC) is a liquid homogeneous formulation to be applied as a solid dispersion after dilution in water. There are many formulations which contains the part characteristics of EC and part characteristics of DC.
c) Dry – Spreadable Granule
Dry spreadable granules are dry granules which can be applied with a dry spreader to a target area and later when such granules get exposed to water via, for example, rain or irrigation, will not only readily disintegrate, but actively spread on solid substrates so as to achieve disintegration area diameter to original granule diameter ratios.
Dry spreadable granules should possess good hardness and an ability to maintain integrity upon normal, commercial handling in a dry spreading operation and yet be capable of quickly disintegrating or scattering upon what may be a minimal exposure to water, such as, for example, a light rain.
d) GR – Soil applied Granule (SAG) on inert or fertilizer carrier
This formulation is in the form of granules which can be applied on inert carrier or the carrier which is fertilizer.
e) Mixed formulation
e.1) ZC Formulation (Mix of CS and SC)
“ZC formulation” is the international denominations adopted by the FAO (Food and Agricultural Organization of the United Nations) to designate "stable aqueous suspension of microcapsules and solid fine particles"
ZC is a mixed formulation of CS and SC and is a stable aqueous suspension of microcapsules and solid fine particles, each of which contains one or more active ingredients. The formulation is intended for dilution into water prior to spray application. Formulating the active ingredients together eliminates the need for tank mixing, which can lead to incompatibility, and facilitates control of a wider range of pests with fewer applications. Like other aqueous liquid formulations, ZC formulations are easy to handle and measure, dust free, non-flammable and offer good miscibility with water.
One or more of the active ingredients is encapsulated for various purposes, such as to increase the residual biological activity, or to reduce the acute toxicity, or to obtain a physical or chemically stable water-based formulation. The purpose determines whether the “free” active ingredient and the “release rate” are relevant properties of a specific product.
For present invention term composition and formulation can be used interchangeably and covey the same meaning.
The term WDG, DG, WSG and SAG are synonyms and can be used inter changeably and convey the same meaning.
Formulation of the present invention can be in any of the form described above. Preferably the novel composition of the present invention is to be selected from Wettable powders (WP) and Water dispersible Granules (WDG).
Dazomet and Clothianidin which are active ingredients of the present formulation are present in ratio of 100: 1 to 50: 3.
The list of crops which can be protected by the present novel composition are Brinjal (Solanum melongena), Cabbage (Brassica oleracea var. capitata), Caluflower (Brassica oleracea var. botrytis), Okra (Abelmoschus esculentus) , Onion (Allium cepa L.), Tomato (Solanum lycopersicun) , Potato (Solanum tuberosum) , Sweet potato (Ipomoea batatas), Chilly (Capsicum annum), Garlic (Allium sativum), Radish (Raphanus sativus), Carrot (Dacus carota subsp. sativus), Turnip (Brassica rapa subsp rapa), Apple (Melus domestica), Peach, Plum, Banana (Musa spp.), Citrus groups (Citrus spp.), Grape (Vitis vinifera), Guava (Psidium guajava), Litchi (Litchi chinensis), Mango (Mangifera indica), Papaya (Carica papaya), Pineapple (Ananas comosus), Pomegranate (Punica granatum) , Sapota (Manilkara zapota), Tea (Camellia sinensis), Coffea (Coffea Arabica), Turmeric (Curcuma longa), Ginger (Zingiber officinale), Black Pepper (Piper nigrum), Stevia (Stevia rebaudiana), Safed musli (Chlorophytum tuberosum), Coconut (Cocos nucifera), Rose (Rosa spp.), Jasmine (Jasminum spp.), Marigold ( Tagetes spp.), Common daisy (Bellis perennis), Dahlia (Dahlia hortnesis), Tuberose, Areca catechu (betelnut palm), Coffea arabica (arabica coffee), Coffea canephora (robusta coffee), Cucumis anguria (gerkin), Cucumis melo (melon), Cucumis sativus (cucumber), Cardamom (Elettaria cardamomum), Cotton (Gossypium hirsutum), Maize (Zea mays), crop raised in nursery, net house, polyhouse, green house.
The composition of present invention can be applied by any of below listed method;
• Broadcasting by manual or through mechanical or semi or fully automated machine,
• soil incorporation before planting, transplanting, sowing in open field, in net house, in polyhouse, green house etc.,
• Through drip irrigation
• Through fertigation
• Band application in root zone
• Ring application in fruit crops, vegetables and flowers
The present composition of the present invention preferably is active against normally sensitive and resistant species and against all or some stages of development. List of targeted pests are mentioned below;
All plant parasitic nematode includes root knot nematode (Meloidogyne incognita, Meloidogyne javanica, Meloidogyne arenaria, Meloidogyne hapla), Lession nematode (Pratylenchus penetrans, Pratylenchus vulnus, Pratylenchus brachyrus, Pratylenchus zea, Pratylenchus coffee, Pratylenchus scribneri), Cyst nematode (Heterodera glycines, Heterodera schachtii, Heterodera avenae, Heterodera trifolii), Globodera cyst nematode (Globodera rostochiensis, Globodera pallida), Ditylenchus stem and bulb nematode (Ditylenchus dipsaci, . Ditylenchus destructor, Ditylenchus myceliophagus),Tylenchus citrus nematode ( Tylenchus semipenetrans) ,Xiphinema dagger nematode ( Xiphinema index, Radopholus burrowing nematode (Radopholus citrophilis, Radopholus similis), Rotylenchus reniform nematode, Helicotylenchus nematode, Belonolaimus sting nematode. Insects-pests from the phylum Arthropoda, from the class Insecta, from the order Coleoptera, Agriotes spp., Gnathocerus cornutus, Holotrichia spp., Hypothanemus spp., Lachnosterna consanguinea, Lasioderma serricorne, Latheticus oryzae, Lathridius spp., Lema spp., Leptinotarsa decemlineata, Leucopteraspp., Melanotus spp., Melolontha spp., from the order Diptera, for example, Agromyza spp., Asphondylia spp., Bactrocera spp., Contarinia spp., Dacus oleae, Drosophila spp., Liriomyza spp., Musca spp., Tetanops spp., Tipula spp.; from the order Heteroptera, for example, Leptocorisa spp., Leptocorisa varicornis, Lygus spp., Miridae, from the order Homoptera, for example, Acizzia spp., Acyrthosipon spp., Amrasca spp., Aonidiella spp., Aphis spp., Aulacorthum solani, Bemisia tabaci, Brevicoryne brassicae, Carneocephala fulgida, Ceratovacuna lanigera, Coccus spp., Cryptomyzus ribis, Dialeurodes citri, Diaphorina citri, Drosicha spp., Empoasca spp., Geococcus coffeae, Idiocerus spp., Lipaphis erysimi, Macrosiphum spp., Myzus spp., Nephotettix spp., Nettigoniclla spectra, Nilaparvata lugens, Phenacoccus spp., Phylloxera spp., Planococcus spp., Pseudococcus spp., Psylla spp., Pyrilla spp., Rastrococcus spp., Rhopalosiphum spp., Saissetia spp., Sogatella furcifera, Toxoptera spp., Trialeurodes vaporariorum, from the order Thysanoptera, for example, Anaphothrips obscurus, Baliothrips biformis, Drepanothrips reuteri, Enneothrips flavens, Frankliniella spp., Heliothripsspp., Hercinothrips femoralis, Rhipiphorothrips cruentatus, Scirtothrips spp., Taeniothrips cardamomi, Thrips spp.
The diseases controlled are Root rot, black rot, charcoal rot, wilt, soft rot, dry rot, damping off caused by soil born bacteria, fungi. These are Bacterial soft rot, Erwinia carotovora, Pythium rot (Pythium aphanidermatum, Pythium ultimum), Phytophthora rot (Phytophthora megasperma), Plasmodiophora brassicae, Sclerotinia sclerotiorum, Sclerotinia minor, Sclerotium rolfsii, Verticillium spp., Rhizoctonia solani, Fusarium oxysporium,Fusarium solani, Macrophomina phaseolina, Helminthosporium solani.
Many weed are also controlled like grasses, broad leaf weeds. These includes Barnyard grass (Echinochloa spp.), Crabgrass (Digitaria spp.), Goosegrass (Eluesine indica), Foxtail (Setaria verticiliata), Sorghum (Sorghum halepenses), Crow footgrass (Dactyloctenium aegyptium), Brachiaria arvensis, Trianthema spp., Euphorbia spp., Day flower (Commelina benghalensis and Commelina sinensis), Pigweeds (Amaranthus viridis and Amaranthus lividis), Purslane (Portulaca oleracea), Nightshade (Solanum spp.), Spurge (Euphorbia geniculata and Euphorbia hirta), Ragweed (Ambroasia spp.) etc.
The novel composition of the present invention is preferably used as soil sterilization so as to control all soil pests which include soil insects, nematodes, soil fungus and weed seeds.
The synergistic pesticidal composition of the present invention in addition to Dazomet and Clothianidin further comprises inactive excipients including but not limited to dispersant, anti-freezing agent, anti-foam agent, wetting agent, suspension aid, anti-microbial agent, thickener, quick coating agent or sticking agents (also referred to as “stickers” or “binders”) and buffering agent.
A dispersant is a substance which adsorbs onto the surface of particles and helps to preserve the state of dispersion of the particles and prevents them from re-aggregating. Dispersants are added to agrochemical formulations to facilitate dispersion and suspension during manufacture, and to ensure the particles re-disperse into water in a spray tank. They are widely used in wettable powders, suspension concentrates and water-dispersible granules. Surfactants that are used as dispersants have the ability to adsorb strongly onto a particle surface and provide a charged or steric barrier to re-aggregation of particles. The most commonly used surfactants are anionic, non-ionic, or mixtures of the two types. For wettable powder formulations, the most common dispersants are sodium lignosulphonates. For suspension concentrates, very good adsorption and stabilization are obtained using polyelectrolytes, such as sodium naphthalene sulphonate formaldehyde condensates. Tristyrylphenolethoxylate phosphate esters are also used. Nonionics such as alkylarylethylene oxide condensates and EO-PO block copolymers are sometimes combined with anionics as dispersants for suspension concentrates. In recent years, new types of very high molecular weight polymeric surfactants have been developed as dispersants. These have very long hydrophobic ‘backbones’ and a large number of ethylene oxide chains forming the ‘teeth’ of a ‘comb’ surfactant. These high molecular weight polymers can give very good long-term stability to suspension concentrates because the hydrophobic backbones have many anchoring points onto the particle surfaces. Examples of dispersants used herein include but not limited to sodium lignosulphonates; sodium naphthalene sulphonate formaldehyde condensates; tristyrylphenolethoxylate phosphate esters; aliphatic alcohol ethoxylates; alky ethoxylates; EO-PO block copolymers; and graft copolymers or mixtures thereof.
Anti-freezing agent as used herein can be selected from the group consisting of polyethylene glycols, methoxypolyethylene glycols, polypropylene glycols, polybutylene glycols, glycerin and ethylene glycol.
Water-based formulations often cause foam during mixing operations in production. In order to reduce the tendency to foam, anti-foam agents are often added either during the production stage or before filling into bottles. Generally, there are two types of anti-foam agents, namely silicones and non-silicones. Silicones are usually aqueous emulsions of dimethyl polysiloxane while the non-silicone anti-foam agents are water-insoluble oils, such as octanol and nonanol, or silica. In both cases, the function of the anti-foam agent is to displace the surfactant from the air-water interface.
A wetting agent is a substance that when added to a liquid increases the spreading or penetration power of the liquid by reducing the interfacial tension between the liquid and the surface on which it is spreading. Wetting agents are used for two main functions in agrochemical formulations: during processing and manufacture to increase the rate of wetting of powders in water to make concentrates for soluble liquids or suspension concentrates; and during mixing of a product with water in a spray tank or other vessel to reduce the wetting time of wettable powders and to improve the penetration of water into water-dispersible granules. Examples of wetting agents used in wettable powder, suspension concentrate, and water-dispersible granule formulations include but not limited to sodium lauryl sulphate; sodium dioctylsulphosuccinate; alkyl phenol ethoxylates; and aliphatic alcohol ethoxylates or mixtures thereof.
Suspension aid in the present description denotes a natural or synthetic, organic or inorganic material with which the active substance is combined in order to facilitate its application to the plant, to the seeds or to the soil. This carrier is hence generally inert, and it must be agriculturally acceptable, in particular to the plant being treated. The carrier may be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, and the like or mixtures thereof) or liquid (water, alcohols, ketones, petroleum fractions, aromatic or paraffinic hydrocarbons, chlorinated hydrocarbons, liquefied gases, and the like or mixtures thereof).
Biocides / Microorganisms cause spoilage of formulated products. Therefore anti-microbial agents are used to eliminate or reduce their effect. Examples of such agents include, but are not limited to: propionic acid and its sodium salt; sorbic acid and its sodium or potassium salts; benzoic acid and its sodium salt; p-hydroxy benzoic acid sodium salt; methyl p-hydroxy benzoate; and biocide such as sodium benzoate, 1,2-benzisothiazoline-3-one, 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, potassium sorbate, parahydroxy benzoates or mixtures thereof.
Thickeners or gelling agents are used mainly in the formulation of suspension concentrates, emulsions and suspoemulsions to modify the rheology or flow properties of the liquid and to prevent separation and settling of the dispersed particles or droplets. Thickening, gelling, and anti-settling agents generally fall into two categories, namely water-insoluble particulates and water-soluble polymers. It is possible to produce suspension concentrate formulations using clays and silicas. Examples of these types of materials, include, but are limited to, montmorillonite, e.g. bentonite; magnesium aluminum silicate; and attapulgite. Water-soluble polysaccharides have been used as thickening-gelling agents for many years. The types of polysaccharides most commonly used are natural extracts of seeds and seaweeds are synthetic derivatives of cellulose or mixtures thereof. Examples of these types of materials include, but are not limited to, guar gum; locust bean gum; carrageenam; xanthan gum; alginates; methyl cellulose; sodium carboxymethyl cellulose (SCMC); hydroxyethyl cellulose (HEC) or mixtures thereof. Other types of anti-settling agents are based on modified starches, polyacrylates, polyvinyl alcohol and polyethylene oxide or mixtures.
The quick coating agent can be a conventionally available sticker, for example polyesters, polyamides, poly- carbonates, polyurea and polyurethanes, acrylate polymers and copolymers, styrene copolymers, butadiene copolymers, polysaccharides such as starch and cellulose derivatives, vinylalcohol, vinylacetate and vinylpyrrolidone polymers and copolymers, polyethers, epoxy, phenolic and melamine resins, polyolefins and define copolymersand mixtures thereof. Examples of preferred polymers are acrylate polymers such as poly(methacrylate), poly(ethyl methacrylate), poly(methylmethacrylate), acrylate copoylmers and styrene-acrylic copolymers as defined herein below, poly(styrene-co maleic anhydride), cellulosic polymers such as ethyl cellulose, cellulose acetate, cellulose acetatebutyrate, acetylated mono, di, and triglycerides, poly(vinylpyrrolidone), vinyl acetate polymers and copolymers, poly(alkylene glycol), styrene butadiene copolymers, poly(orthoesters), alkyd resins, and mixtures of two or more of these. Polymers that are biodegradable are also useful in the present invention. As used herein, a polymer is biodegradable if is not water soluble, but is degraded over a period of several weeks when placed in an application environment. Examples of biodegradable polymers that are useful in the present invention include biodegradable polyesters, starch, polylactic acid starch blends, polylactic acid, poly(lactic acid-glycolic acid) copolymers, polydioxanone, cellulose esters, ethyl cellulose, cellulose acetate butyrate, starch esters, starch esteraliphatic polyester blends, modified corn starch, polycaprolactone, poly(namylmethacrylate), wood rosin, polyanhydrides, polyvinylalcohol, polyhydroxybutyratevalerate, biodegradable aliphatic polyesters, and polyhydroxybutyrate or mixtures thereof.
Buffering agent as used herein is selected from group consisting of calcium hydroxyapatite, Potassium Dihydrogen Phosphate, Sodium Hydroxide, carbonated apatite, calcium carbonate, sodium bicarbonate, tricalcium phosphate, calcium phosphates, carbonated calcium phosphates, amine monomers, lactate dehydrogenase and magnesium hydroxide.
The solvent for the formulation of the present invention may include water, water-soluble alcohols and dihydroxy alcohol ethers. The water-soluble alcohol which can be used in the present invention may be lower alcohols or water-soluble macromolecular alcohols. The term "lower alcohol", as used herein, represents an alcohol having 1-4 carbon atoms, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, etc. Macromolecular alcohol is not limited, as long as it may be dissolved in water in a suitable amount range, e.g., polyethylene glycol, sorbitol, glucitol, etc. The examples of suitable dihydroxy alcohol ethers used in the present invention may be dihydroxy alcohol alkyl ethers or dihydroxy alcohol aryl ethers. The examples of dihydroxy alcohol alkyl ether include ethylene glycol methyl ether, diethylene glycol methyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol ethyl ether, propylene glycol ethyl ether, dipropylene glycol ethyl ether, etc. The examples of dihydroxy alcohol aryl ethers include ethylene glycol phenyl ether, diethylene glycol phenyl ether, propylene glycol phenyl ether, dipropylene glycol phenyl ether, and the like. Any of the above mentioned solvent can be used either alone or in combination thereof.
The wettable dry granules (WDG) can be applied after disintegration and dispersion in water. Water dispersible granules can be formed by a) agglomeration, b) spray drying, or c) extrusion techniques.
WDG formulations offer a number of advantages in packaging, ease of handling and safety. The WDG are preferably of uniform size and which are free flowing, low dusting and readily disperse in water to form a homogenous solution of very small particles which may pass through conventional spray nozzles. Ideally WDG formulations when dispersed in water under gentle agitation for five minutes have residues of less than 0.01% on a 150 µm sieve screen and less than 0.5% on a 53 µm screen. The granules can usually be measured accurately by volume which is convenient for the end user.
The SC formulation can be prepared by below described method;
STEP-I: Adding anti-microbial agent and gum in water under continuous stirring followed by slow addition. Continuing stirring until homogeneous dispersion is formed.
STEP-II: Mixing anti-freezing agent, dispersant, wetting agent, anti-microbial agent and anti-foaming agent in water for 30 minute until homogeneous solution is formed. Finally add Dazomet and Clothianidin is added slowly under continuous stirring at 30 minute till homogeneous dispersion is obtained. Milling the slurry through bead mill until required particle size is achieved.
Step-III: Adding rest of water, anti-foaming agent and gum solution under continuous stirring to get desired viscosity of the suspension. Continue stirring for about 4 hr to obtain homogeneous formulation.
The process for preparing the present synergistic pesticidal composition can be modified accordingly by any person skilled in the art based on the knowledge of the manufacturing the formulation. However all such variation and modification is still covered by the scope of present invention.
EXAMPLES
Example 1: Wettable powder formulation (WP)
COMPOSITIONS Dazomet 50% + Clothianidin 0.6% WP Dazomet 50% + Clothianidin 0.5% WP Dazomet 40% + Clothianidin 0.5% WP Dazomet 30% + Clothianidin 0.6% WP Dazomet 30% + Clothianidin 0.8% WP
Dazomet (95%) 53.15 53.15 42.60 32.10 32.10
Clothianidin (97%) 0.80 0.70 0.70 0.80 1.00
Sodium salt of Phenol sulphonic acid condensate 3.00 3.00 3.00 3.00 3.00
Sodium alkylnaphthalenesulfonate, formaldehyde condensate 7.00 7.00 7.00 7.00 7.00
Silicone based antifoam 0.50 0.50 0.50 0.50 0.50
Starch 10.00 10.00 10.00 10.00 10.00
Silica 15.00 15.00 15.00 15.00 15.00
China clay 10.55 10.65 21.20 31.60 31.40
TOTAL 100.00 100.00 100.00 100.00 100
Procedure:
Step 1 Charge the required quantity of filler, wetting agent, dispersing agent, and suspending agent, & technical in premixing blender for homogenization for 30 minutes.
Step 2 Pre-blended material is than grinded through Jet mill/ air classifier mills. Finely grinded material is blended in post blender till it becomes homogeneous. (for approx. 1.5 hr)
Step 3 Homogeneous material is analysed. After getting approval from QC dept. material is unloaded into 25 kg. HDPE bag with LDPE liner inside.
Example 2: Water Dispersible Granule formulation (WDG)
COMPOSITIONS Dazomet 50% + Clothianidin 0.6% WDG Dazomet 50% + Clothianidin 0.5% WDG Dazomet 40% + Clothianidin 0.5% WDG Dazomet 30% + Clothianidin 0.6% WDG Dazomet 30% + Clothianidin 0.8% WDG
Dazomet (95%) 53.15 53.15 42.60 32.10 32.10
Clothianidin (97%) 0.80 0.70 0.70 0.80 1.00
Sodium salt of Phenol sulphonic acid condensate 3.00 3.00 3.00 3.00 3.00
Polyacrylate co-polymer 5.00 5.00 5.00 5.00 5.00
Sodium alkylnaphthalenesulfonate, formaldehyde condensate 4.00 4.00 4.00 4.00 4.00
Silicone based antifoam 0.50 0.50 0.50 0.50 0.50
Polyvinyl pyrollidone 1.25 1.25 1.25 1.25 1.25
Starch 10.00 10.00 10.00 10.00 10.00
China clay 22.3 22.4 32.95 43.4 43.15
TOTAL 100.00 100.00 100.00 100.00 100.00
Procedure:
Step 1 Charge the required quantity of filler, wetting agent, dispersing agent, and suspending agent, & technical in premixing blender for homogenization for 30 minutes.
Step 2 Pre-blended material is than grinded through Jet mill/ air classifier mills. Finely grinded material is blended in post blender till it becomes homogeneous. (for approx. 1.5 hr)
Step 3 Homogeneous material is analysed. After getting approval from QC dept. material is unloaded into 25 kg. HDPE bag with LDPE liner inside.
Step 4 Finely grinded powder is mixer with required quantity of water to form extrudable dough.
Step 5 Dough is passed through extruder to get granules of required size.
Step 6 Wet granules are passed through Fluidized bed drier and further graded using vibrating screens.
Step 7 Final product is sent for QC approval.
Step 8 After approval material is packed in required pack sizes.
Example 3: Stability studies
31.) Storage stability Study Data of Dazomet 50% + Clothianidin 0.5% WP (Wettable Powder)
Specification Initial Heat stability study at 54+2 0C for 14 days Cold storage stability at 0+2 0C for 14 days
Parameters
Description Off-white Complies Complies Complies
Dazomet Content 48.50-52.5 50.5 50.3 50.5
Dazomet Suspensibility Mini 70% 95 93 95
Clothianidin Content 0.45-0.60 0.55 0.53 0.55
Clothianidin Suspensibility Mini 70% 95 93 95
pH 5 to 7 6.5 6.5 6.5
Wettability Max 30 s 20 20 20
Wet Sieve (45 micron) Mini 98.5% 99.5 99.6 99.5
Bulk Density 0.45-0.55 0.4 0.4 0.4
Room temperature study
Specification Study Duration
Parameters In House 1st day 6 month 12 months 36 months
Description Off-white Complies Complies Complies Complies
Dazomet Content 48.50-52.5 50.5 50.5 50.5 50.1
Dazomet Suspensibility Mini 70% 95 95 95 93
Clothianidin Content 0.45-0.60 0.55 0.55 0.55 0.53
Clothianidin Suspensibility Mini 70% 95 95 95 93
pH 5 to 7 6.5 6.5 6.5 6.2
Wettability Max 30 s 20 20 20 20
Wet Sieve(45 micron) Mini 98.5% 99.5 99.5 99.5 99.6
Bulk Density 0.45-0.55 0.4 0.4 0.4 0.4
3.2) Storage stability Study of Dazomet 50% + Clothianidin 0.5% WDG (Water Dispersible Granules)
Specification Initial Heat stability study at 54+2 0C for 14 days Cold storage stability at 0+2 0C for 14 days
Parameters In House
Description Off-white Complies Complies Complies
Dazomet Content 48.50-52.5 50.5 50.3 50.5
Dazomet Suspensibility Mini 70% 95 93 95
Clothianidin Content 0.45-0.60 0.55 0.53 0.55
Clothianidin Suspensibility Mini 70% 95 93 95
pH 5 to 7 6.5 6.5 6.5
Wettability Max 30 s 20 20 20
Wet Sieve (45 micron) Mini 98.5% 99.5 99.6 99.5
Bulk Density 0.45-0.55 0.4 0.4 0.4
Moisture Content Max 2.0% 1.5 1.3 1.5
Room temperature study
Specification Study duration
Parameters In house 1st day 6 month 12 months 36 months
Description Off-white Complies Complies Complies Complies
Dazomet Content 48.50-52.5 50.50 50.50 50.50 50.10
Dazomet Suspensibility Mini 70% 95.00 95.00 95.00 93.00
Clothianidin Content 0.45-0.60 0.55 0.55 0.55 0.53
Clothianidin Suspensibility Mini 70% 95.00 95.00 95.00 93.00
pH 5 to 7 6.50 6.50 6.50 6.20
Wettability Max 30 s 20.00 20.00 20.00 20.00
Wet Sieve(45 micron) Mini 98.5% 99.50 99.50 99.50 99.60
Bulk Density 0.45-0.55 0.40 0.40 0.40 0.40
Moisture Content Max 2.0% 1.50 1.50 1.30 1.50
Example 4: Field efficacy trials
Soil hibernating insects, plant parasitic nematodes and soil borne pathogens are very limiting factors in successful cultivation of many field crops, fruits and vegetables in open field as well as protected cultivation. The integrated management practices are being followed to keep these soil pests, plant parasitic nematodes, weeds and soil pathogen under check. Plant parasitic nematodes (PPNs), root know nematodes (RKNs), Meloidogyne spp., are the most important and extremely polyphagous pest species of diverse crops in both tropical and subtropical areas causing massive reductions in crop yield and quality. In interaction with other pathogens like fungi and bacteria it forms a disease complex, causing great yield losses. Worldwide, the genus Meloidogyne have been reported on many host plants species. There is hardly any vegetable crop which is not attacked by the root knot nematodes. The lack of awareness among the farmers about the nematode problem and non-availability of suitable package of practices for managing the root know nematodes are the hindrance for protecting the vegetable crops from root knot nematodes.
The management of RKNs is not easy task under intensive crop cultivation system. In Meloidogyne spp. control programmes, nematicides are usually the most effective means of high levels of RKNs management. The field study was carried out to evaluate the efficacy of ready mix of Dazomet+Clothianidin. The testing samples comprising of Dazomet+Clothianidin were developed and evaluated on cucumber and tomato crop.
Table 1: Sample compositions comprising of Dazomet and Clothianidin, their formulations and test rate
Serial Number Sample Code Type of Formulation A.I.(%) in formulation Formulation per Hectare (g) Active Ingredient/Hectare Ratio of Dazomet : Clothianidin
Dazomet Clothianidin Dazomet Clothianidin
1 DC1 WP 50.0% 0.6% 50000 25000 300 83.33 : 1
2 DC2 WP 50.0% 0.5% 50000 25000 250 100 : 1
3 DC3 WP 40.0% 0.5% 50000 20000 250 80 : 1
4 DC4 WP 30.0% 0.6% 50000 15000 300 50 : 1
5 DC5 WP 30.0% 0.8% 50000 15000 400 37.5 : 1
6 DC6 WDG 50.0% 0.6% 50000 25000 300 83.33 : 1
7 DC7 WDG 50.0% 0.5% 50000 25000 250 100 : 1
8 DC8 WDG 40.0% 0.5% 50000 20000 250 80 : 1
9 DC9 WDG 30.0% 0.6% 50000 15000 300 50 : 1
10 DC10 WDG 30.0% 0.8% 50000 15000 400 37.5 : 1
11 Prior Art Sample 1 Tech + WG 90.0% 50.0% 27778 + 800 25000 400 _
12 Prior Art Sample 2 Tech + WG 90.0% 50.0% 27778 + 600 25000 300 _
13 Prior Art Sample 3 Tech + WG 90.0% 50.0% 16667 + 600 15000 300 _
14 Prior Art Sample 4 Tech 90.0% _ 44444 40000 _ _
15 Prior Art Sample 5 WG _ 50.0% 800 _ 400 _
16 Untreated Control _ _ _ _ _ _ _
Note:
A. I. -Active Ingredient, g- Gram, WP- Wettable Powder, WDG- Water Dispersible Granules, Tech.-Technical form (95% of active ingredient), DC1 to DC10 –ready mix laboratory Samples of Dazomet+Clothianidin
The experiment was conducted in Gujarat state of India on cucumber crop in polyhouse. The design of experiment was non replicated plot with plot size of 10 meter row length and 60 cm width including one untreated check and five sets of prior art samples. The cucumber crop was raised with all standard agronomic practices. The treatments were applied as broadcasting over the raise bed (60 cm width x 10 m length), than incorporated in soil manually and after that it was covered with polythene sheet. Light drip irrigation was done and allowed to remain as such for 8 days. The aeration was done by making hole in polythene sheet after 8 days and then planting of cucumber seed was done on 10th day. The normal agronomic practices were followed to raise the cucumber crop in polyhouse. The previous crop was also cucumber which was heavily infested with root knot nematodes, so plot was with known history of root knot nematode infestation. The observations were recorded at 90 days after sowing to evaluate the direct and indirect effect of treatments on nematode population and on plant growth parameters. The various plant growth parameters like plant height, root length, number of leaves, number of flowers, number of fruits and fruit yield were recorded. The nematode population was also estimated by sampling the plant root, by counting number of galls per root system, number of egg-masses per root system and number of developmental stage of root knot nematode. The RKN population was also estimated in soil by taking soil samples from active root zone area. The field observations were presented in below table.
Table 2- Effect of soil treatment of Dazomet+Clothianidin on vegetative growth of Cucumber in Meloidogyne incognita sick soil
Sample Code Type of Formulation Active Ingredient/Hectare Formulation per Hectare (g) Ratio of Dazomet : Clothianidin Plant Height (cm.) Root length (cm.) No. of leaves/ plant No. of flowers/ plant No. of fruits/ plant Fruit weight (g) /plant
Dazomet Clothianidin
DC1 WP 25000 300 50000 83.33 : 1 322 114 55 53 38 3206
DC2 WP 25000 250 50000 100 : 1 316 108 50 46 32 2614
DC3 WP 20000 250 50000 80 : 1 303 102 49 43 30 2410
DC4 WP 15000 300 50000 50 : 1 278 92 44 41 28 2286
DC5 WP 15000 400 50000 37.5 : 1 292 86 43 37 29 2348
DC6 WDG 25000 300 50000 83.33 : 1 332 118 56 52 36 3080
DC7 WDG 25000 250 50000 100 : 1 318 116 52 48 34 2743
DC8 WDG 20000 250 50000 80 : 1 308 110 50 47 28 2277
DC9 WDG 15000 300 50000 50 : 1 286 91 40 38 23 1928
DC10 WDG 15000 400 50000 37.5 : 1 293 97 42 39 24 2086
Prior Art Sample 1 Tech + WG 25000 400 27778 + 800 _ 228 71 35 29 17 1325
Prior Art Sample 2 Tech + WG 25000 300 27778 + 600 _ 216 65 32 26 14 1126
Prior Art Sample 3 Tech + WG 15000 300 16667 + 600 _ 193 56 30 23 15 1126
Prior Art Sample 4 Tech 40000 _ 44444 _ 162 36 28 21 12 885
Prior Art Sample 5 WG _ 400 800 _ 146 32 31 22 11 820
Untreated Control _ _ _ _ _ 98 28 26 14 7 486
The efficacy results on plant growth parameters shows that both the formulations i.e. Wettable Powder (WP) and Water Dispersible Granules (WDG) of Dazomet+Clothianidin provides excellent protection against root knot nematode as compared to all the prior art samples and untreated check. The shoot length, root length, no. of leaves, no. of flowers, no. of fruits and fruit yield were much higher in all the ready mix treatments of Dazomet+Clothianidin as compared to all the prior art treatments and untreated check.
Table 3- Effect of soil treatment of Dazomet+Clothianidin on population of Meloidogyne incognita on root and soil
Sample Code Type of Formulation Active Ingredient/Hectare Formulation per Hectare (g) Ratio of Dazomet : Clothianidin Roots Soil
Dazomet Clothianidin No. of galls No. of egg masses No. of developmental stages No. of Juvenile stage
DC1 WP 25000 300 50000 83.33 : 1 19 9 20 92
DC2 WP 25000 250 50000 100 : 1 16 8 19 81
DC3 WP 20000 250 50000 80 : 1 24 14 27 97
DC4 WP 15000 300 50000 50 : 1 31 20 30 128
DC5 WP 15000 400 50000 37.5 : 1 20 12 23 131
DC6 WDG 25000 300 50000 83.33 : 1 15 6 18 86
DC7 WDG 25000 250 50000 100 : 1 30 17 35 102
DC8 WDG 20000 250 50000 80 : 1 23 14 26 118
DC9 WDG 15000 300 50000 50 : 1 28 19 27 128
DC10 WDG 15000 400 50000 37.5 : 1 36 23 34 118
Prior Art Sample 1 Tech + WG 25000 400 27778 + 800 _ 78 50 74 168
Prior Art Sample 2 Tech + WG 25000 300 27778 + 600 _ 86 60 90 175
Prior Art Sample 3 Tech + WG 15000 300 16667 + 600 _ 91 68 87 204
Prior Art Sample 4 Tech 40000 _ 44444 _ 112 87 108 236
Prior Art Sample 5 WG _ 400 800 _ 129 104 134 267
Untreated Control _ _ _ _ _ 216 184 173 468
The data on RKN population on root shows that the no. of egg masses and no. of developmental stage were much lower in the ready mix treatments of Dazomet+Clothianidin as compared to all the prior art samples as well as untreated check. The no. of gall per root were also observed lower in all the ready mix treatments of Dazomet+Clothianidin compared to all the prior art samples as well as untreated check. The RKN population in soils from active root zone area was also recorded much lower in the ready mix treatments of Dazomet+Clothianidin as compared to all the prior art samples and untreated check treatment.
Experiment against soil born fungus, Pythium aphanidermatum and Root know nematode in tomato nursery
Another experiment was carried out on Tomato nursery to evaluate the efficacy of wettable powder (WP) and Water Dispersible Powder (WDG) ready mix formulations of Dazomet+Clothianidin.
Design: Non replicated
Plot size: 2 meter x 2 meter raised bed
Application method: The required quantity of treatments were incorporated in moist soil in raised bed and then covered with polythene sheet for one week. The line sowing was done manually on 8th day after removing polythene sheet.
Sowing: 200 tomato seeds were planted per plot.
Other practices were followed as per the standard agronomic practices like fertilizer and watering.
Observations: The germination % was calculated by counting no. of plant at 30 days after sowing. The plant stand includes the number of plant survived after damping off caused by Pythium aphanidermatum and Rhizoctonia solani incidence. For root knot nematode infestation, all survived plant root were assess for gall incidence on rootlets at the time of uprooting at 30 days and the number of healthy and RKN infested plant were calculated.
The observations were presented in the tabular form as below:
Table 4: Effect of soil treatment of Dazomet+Clothianidin on soil borne fungal diseases and root knot nematode in Tomato nursery
Sample Code Type of Formulation Active Ingredient/Hectare Formulation per Hectare (g) Ratio of Dazomet : Clothianidin % Germination Plant stand at 30 DAS No. of Plant infested with RKN at 30 DAS No. of Healthy Seedling at 30 DAS
Dazomet Clothianidin
DC1 WP 25000 300 50000 83.33 : 1 88% 176 3 173
DC2 WP 25000 250 50000 100 : 1 84% 168 5 163
DC3 WP 20000 250 50000 80 : 1 86% 172 7 165
DC4 WP 15000 300 50000 50 : 1 82% 164 10 154
DC5 WP 15000 400 50000 37.5 : 1 80% 160 7 153
DC6 WDG 25000 300 50000 83.33 : 1 89% 178 2 176
DC7 WDG 25000 250 50000 100 : 1 83% 166 4 162
DC8 WDG 20000 250 50000 80 : 1 85% 170 7 163
DC9 WDG 15000 300 50000 50 : 1 82% 164 9 155
DC10 WDG 15000 400 50000 37.5 : 1 81% 162 8 154
Prior Art Sample 1 Tech + WG 25000 400 27778 + 800 _ 75% 150 18 132
Prior Art Sample 2 Tech + WG 25000 300 27778 + 600 _ 72% 144 24 120
Prior Art Sample 3 Tech + WG 15000 300 16667 + 600 _ 70% 140 28 112
Prior Art Sample 4 Tech 40000 _ 44444 _ 66% 132 32 100
Prior Art Sample 5 WG _ 400 800 _ 62% 124 37 87
Untreated Control _ _ _ _ _ 60% 120 46 74
The observation on % seed germination of tomato in nursery shows that seed germination was observed higher in all the ready-mix formulations of Dazomet+Clothianidin. The seedling death (caused by soil born fungus Pythium aphanidermatum and Rhizoctonia solani) were observed negligible in all the ready-mix treatments of Dazomet+Clothianidin as compared to all the prior art samples and untreated check. This good control on soil born fungus contributes to the very good plant stand of tomato seedling at 30 days. The number of plant infested with root knot nematode were also observed very low in all the ready mix treatments of Dazomet+Clothianidin as compared to all the prior art treatments and untreated check. The ready mix of Dazomet+Clothianidin helps the farmer to raise the healthy tomato nursery and also save the highly priced hybrid tomato seeds.
,CLAIMS:CLAIMS
We claim;
1. A synergistic composition comprising of Dazomet and Clothianidin and one or more inactive excipients.
2. The synergistic composition as claimed in claim 1 wherein the ratio of Dazomet and Clothianidin is 100: 1 to 50: 3.
3. The synergistic composition according to claim 1, wherein inactive excipients can be selected from the group consisting of dispersant, anti-freezing agent, anti-foam agent, wetting agent, suspension aid, anti-microbial agent, thickener, quick coating agent or sticking agents and buffering agent.
4. The synergistic composition as claimed in claim 1 or 4 wherein the formulation can be selected from Wettable powder (WP) and Water Dispersible Granules (WDG).
5. The synergistic composition as claimed in any of the preceding claims, wherein the said formulation is used for control of pests in Brinjal (Solanum melongena), Cabbage (Brassica oleracea var. capitata), Caluflower (Brassica oleracea var. botrytis), Okra (Abelmoschus esculentus) , Onion (Allium cepa L.), Tomato (Solanum lycopersicun) , Potato (Solanum tuberosum) , Sweet potato (Ipomoea batatas), Chilly (Capsicum annum), Garlic (Allium sativum), Radish (Raphanus sativus), Carrot (Dacus carota subsp. sativus), Turnip (Brassica rapa subsp rapa), Apple (Melus domestica), Peach, Plum, Banana (Musa spp.), Citrus groups (Citrus spp.), Grape (Vitis vinifera), Guava (Psidium guajava), Litchi (Litchi chinensis), Mango (Mangifera indica), Papaya (Carica papaya), Pineapple (Ananas comosus), Pomegranate (Punica granatum) , Sapota (Manilkara zapota), Tea (Camellia sinensis), Coffea (Coffea Arabica), Turmeric (Curcuma longa), Ginger (Zingiber officinale), Black Pepper (Piper nigrum), Stevia (Stevia rebaudiana), Safed musli (Chlorophytum tuberosum), Coconut (Cocos nucifera), Rose (Rosa spp.), Jasmine (Jasminum spp.), Marigold ( Tagetes spp.), Common daisy (Bellis perennis), Dahlia (Dahlia hortnesis), Tuberose, Areca catechu (betelnut palm), Coffea arabica (arabica coffee), Coffea canephora (robusta coffee), Cucumis anguria (gerkin), Cucumis melo (melon), Cucumis sativus (cucumber), Cardamom (Elettaria cardamomum), Cotton (Gossypium hirsutum), Maize (Zea mays), crop raised in nursery, net house, polyhouse, green house
6. The novel synergistic composition as claimed in any of the preceding claims, wherein the said formulation is used to control root knot nematode (Meloidogyne incognita, Meloidogyne javanica, Meloidogyne arenaria, Meloidogyne hapla), Lession nematode (Pratylenchus penetrans, Pratylenchus vulnus, Pratylenchus brachyrus, Pratylenchus zea, Pratylenchus coffee, Pratylenchus scribneri), Cyst nematode (Heterodera glycines, Heterodera schachtii, Heterodera avenae, Heterodera trifolii), Globodera cyst nematode (Globodera rostochiensis, Globodera pallida), Ditylenchus stem and bulb nematode (Ditylenchus dipsaci, . Ditylenchus destructor, Ditylenchus myceliophagus),Tylenchus citrus nematode ( Tylenchus semipenetrans) ,Xiphinema dagger nematode ( Xiphinema index, Radopholus burrowing nematode (Radopholus citrophilis, Radopholus similis), Rotylenchus reniform nematode, Helicotylenchus nematode, Belonolaimus sting nematode. Insects-pests from the phylum Arthropoda, from the class Insecta, from the order Coleoptera, Agriotes spp., Gnathocerus cornutus, Holotrichia spp., Hypothanemus spp., Lachnosterna consanguinea, Lasioderma serricorne, Latheticus oryzae, Lathridius spp., Lema spp., Leptinotarsa decemlineata, Leucopteraspp., Melanotus spp., Melolontha spp., from the order Diptera, for example, Agromyza spp., Asphondylia spp., Bactrocera spp., Contarinia spp., Dacus oleae, Drosophila spp., Liriomyza spp., Musca spp., Tetanops spp., Tipula spp.; from the order Heteroptera, for example, Leptocorisa spp., Leptocorisa varicornis, Lygus spp., Miridae, from the order Homoptera, for example, Acizzia spp., Acyrthosipon spp., Amrasca spp., Aonidiella spp., Aphis spp., Aulacorthum solani, Bemisia tabaci, Brevicoryne brassicae, Carneocephala fulgida, Ceratovacuna lanigera, Coccus spp., Cryptomyzus ribis, Dialeurodes citri, Diaphorina citri, Drosicha spp., Empoasca spp., Geococcus coffeae, Idiocerus spp., Lipaphis erysimi, Macrosiphum spp., Myzus spp., Nephotettix spp., Nettigoniclla spectra, Nilaparvata lugens, Phenacoccus spp., Phylloxera spp., Planococcus spp., Pseudococcus spp., Psylla spp., Pyrilla spp., Rastrococcus spp., Rhopalosiphum spp., Saissetia spp., Sogatella furcifera, Toxoptera spp., Trialeurodes vaporariorum, from the order Thysanoptera, for example, Anaphothrips obscurus, Baliothrips biformis, Drepanothrips reuteri, Enneothrips flavens, Frankliniella spp., Heliothripsspp., Hercinothrips femoralis, Rhipiphorothrips cruentatus, Scirtothrips spp., Taeniothrips cardamomi, Thrips spp.
7. The novel synergistic composition as claimed in any preceding claims wherein, composition is used to control Root rot, black rot, charcoal rot, wilt, soft rot, dry rot, damping off caused by soil born bacterial, fungi. These are Bacterial soft rot, Erwinia carotovora, Pythium rot (Pythium aphanidermatum, Pythium ultimum), Phytophthora rot (Phytophthora megasperma), Plasmodiophora brassicae, Sclerotinia sclerotiorum, Sclerotinia minor, Sclerotium rolfsii, Verticillium spp., Rhizoctonia solani, Fusarium oxysporium,Fusarium solani, Macrophomina phaseolina, Helminthosporium solani
8. A novel synergistic composition of Dazomet and Clothianidin as claimed in any of the preceding claims and exemplified with working examples as disclosed.
| Section | Controller | Decision Date |
|---|---|---|
| # | Name | Date |
|---|---|---|
| 1 | 583-MUM-2015-FORM-27 [25-09-2024(online)].pdf | 2024-09-25 |
| 1 | 583-MUM-2015-PROOF OF ALTERATION [11-04-2025(online)].pdf | 2025-04-11 |
| 1 | Description(Complete) [19-02-2016(online)].pdf | 2016-02-19 |
| 2 | 583-MUM-2015-FORM-27 [25-09-2024(online)].pdf | 2024-09-25 |
| 2 | 583-MUM-2015-RELEVANT DOCUMENTS [23-06-2022(online)].pdf | 2022-06-23 |
| 2 | Assignment [19-02-2016(online)].pdf | 2016-02-19 |
| 3 | 583-MUM-2015-FORM 18 [28-07-2017(online)].pdf | 2017-07-28 |
| 3 | 583-MUM-2015-RELEVANT DOCUMENTS [23-06-2022(online)].pdf | 2022-06-23 |
| 3 | 583-MUM-2015-RELEVANT DOCUMENTS [28-04-2020(online)].pdf | 2020-04-28 |
| 4 | 583-MUM-2015-RELEVANT DOCUMENTS [28-04-2020(online)].pdf | 2020-04-28 |
| 4 | 583-MUM-2015-FORM-26 [06-04-2018(online)].pdf | 2018-04-06 |
| 4 | 583-MUM-2015-CORRESPONDENCE(IPO)-(CERTIFIED COPY)-(17-2-2020)..pdf | 2020-02-18 |
| 5 | Form-26-GPA-GSP.pdf ONLINE | 2018-08-11 |
| 5 | 583-MUM-2015-REQUEST FOR CERTIFIED COPY [09-02-2020(online)].pdf | 2020-02-09 |
| 5 | 583-MUM-2015-CORRESPONDENCE(IPO)-(CERTIFIED COPY)-(17-2-2020)..pdf | 2020-02-18 |
| 6 | Form-26-GPA-GSP.pdf | 2018-08-11 |
| 6 | 583-MUM-2015-REQUEST FOR CERTIFIED COPY [09-02-2020(online)].pdf | 2020-02-09 |
| 6 | 583-MUM-2015-IntimationOfGrant22-01-2020.pdf | 2020-01-22 |
| 7 | Form-2-PS-PTIN01567-04-DazometClothianidin-Fial-21022015.pdf ONLINE | 2018-08-11 |
| 7 | 583-MUM-2015-PatentCertificate22-01-2020.pdf | 2020-01-22 |
| 7 | 583-MUM-2015-IntimationOfGrant22-01-2020.pdf | 2020-01-22 |
| 8 | 583-MUM-2015-AMMENDED DOCUMENTS [07-01-2020(online)].pdf | 2020-01-07 |
| 8 | 583-MUM-2015-PatentCertificate22-01-2020.pdf | 2020-01-22 |
| 8 | Form-2-PS-PTIN01567-04-DazometClothianidin-Fial-21022015.pdf | 2018-08-11 |
| 9 | 583-MUM-2015-AMMENDED DOCUMENTS [07-01-2020(online)].pdf | 2020-01-07 |
| 9 | 583-MUM-2015-Annexure (Optional) [07-01-2020(online)].pdf | 2020-01-07 |
| 9 | Form 3-PS-PTIN01567-04-Dazomet&Clothianidin.pdf ONLINE | 2018-08-11 |
| 10 | 583-MUM-2015-Annexure (Optional) [07-01-2020(online)].pdf | 2020-01-07 |
| 10 | 583-MUM-2015-FORM 13 [07-01-2020(online)].pdf | 2020-01-07 |
| 10 | Form 3-PS-PTIN01567-04-Dazomet&Clothianidin.pdf | 2018-08-11 |
| 11 | 583-MUM-2015-FORM 13 [07-01-2020(online)].pdf | 2020-01-07 |
| 11 | 583-MUM-2015-Form 3-200315.pdf | 2018-08-11 |
| 11 | 583-MUM-2015-Written submissions and relevant documents (MANDATORY) [07-01-2020(online)].pdf | 2020-01-07 |
| 12 | 583-MUM-2015-ExtendedHearingNoticeLetter-(DateOfHearing-30-12-2019).pdf | 2019-12-04 |
| 12 | 583-MUM-2015-Form 1-200315.pdf | 2018-08-11 |
| 12 | 583-MUM-2015-Written submissions and relevant documents (MANDATORY) [07-01-2020(online)].pdf | 2020-01-07 |
| 13 | 583-MUM-2015-HearingNoticeLetter-(DateOfHearing-04-12-2019).pdf | 2019-11-19 |
| 13 | 583-MUM-2015-ExtendedHearingNoticeLetter-(DateOfHearing-30-12-2019).pdf | 2019-12-04 |
| 13 | 583-MUM-2015-Correspondence-200315.pdf | 2018-08-11 |
| 14 | 583-mum-2015-ABSTRACT [23-09-2019(online)].pdf | 2019-09-23 |
| 14 | 583-MUM-2015-FER.pdf | 2019-03-28 |
| 14 | 583-MUM-2015-HearingNoticeLetter-(DateOfHearing-04-12-2019).pdf | 2019-11-19 |
| 15 | 583-mum-2015-ABSTRACT [23-09-2019(online)].pdf | 2019-09-23 |
| 15 | 583-mum-2015-CLAIMS [23-09-2019(online)].pdf | 2019-09-23 |
| 15 | 583-mum-2015-OTHERS [23-09-2019(online)].pdf | 2019-09-23 |
| 16 | 583-mum-2015-CLAIMS [23-09-2019(online)].pdf | 2019-09-23 |
| 16 | 583-mum-2015-FER_SER_REPLY [23-09-2019(online)].pdf | 2019-09-23 |
| 16 | 583-MUM-2015-FORM 3 [23-09-2019(online)].pdf | 2019-09-23 |
| 17 | 583-mum-2015-FER_SER_REPLY [23-09-2019(online)].pdf | 2019-09-23 |
| 17 | 583-MUM-2015-FORM 3 [23-09-2019(online)].pdf | 2019-09-23 |
| 18 | 583-MUM-2015-FORM 3 [23-09-2019(online)].pdf | 2019-09-23 |
| 18 | 583-mum-2015-OTHERS [23-09-2019(online)].pdf | 2019-09-23 |
| 18 | 583-mum-2015-CLAIMS [23-09-2019(online)].pdf | 2019-09-23 |
| 19 | 583-mum-2015-ABSTRACT [23-09-2019(online)].pdf | 2019-09-23 |
| 19 | 583-MUM-2015-FER.pdf | 2019-03-28 |
| 19 | 583-mum-2015-OTHERS [23-09-2019(online)].pdf | 2019-09-23 |
| 20 | 583-MUM-2015-Correspondence-200315.pdf | 2018-08-11 |
| 20 | 583-MUM-2015-FER.pdf | 2019-03-28 |
| 20 | 583-MUM-2015-HearingNoticeLetter-(DateOfHearing-04-12-2019).pdf | 2019-11-19 |
| 21 | 583-MUM-2015-Form 1-200315.pdf | 2018-08-11 |
| 21 | 583-MUM-2015-ExtendedHearingNoticeLetter-(DateOfHearing-30-12-2019).pdf | 2019-12-04 |
| 21 | 583-MUM-2015-Correspondence-200315.pdf | 2018-08-11 |
| 22 | 583-MUM-2015-Form 1-200315.pdf | 2018-08-11 |
| 22 | 583-MUM-2015-Form 3-200315.pdf | 2018-08-11 |
| 22 | 583-MUM-2015-Written submissions and relevant documents (MANDATORY) [07-01-2020(online)].pdf | 2020-01-07 |
| 23 | 583-MUM-2015-FORM 13 [07-01-2020(online)].pdf | 2020-01-07 |
| 23 | 583-MUM-2015-Form 3-200315.pdf | 2018-08-11 |
| 23 | Form 3-PS-PTIN01567-04-Dazomet&Clothianidin.pdf | 2018-08-11 |
| 24 | Form 3-PS-PTIN01567-04-Dazomet&Clothianidin.pdf ONLINE | 2018-08-11 |
| 24 | Form 3-PS-PTIN01567-04-Dazomet&Clothianidin.pdf | 2018-08-11 |
| 24 | 583-MUM-2015-Annexure (Optional) [07-01-2020(online)].pdf | 2020-01-07 |
| 25 | 583-MUM-2015-AMMENDED DOCUMENTS [07-01-2020(online)].pdf | 2020-01-07 |
| 25 | Form 3-PS-PTIN01567-04-Dazomet&Clothianidin.pdf ONLINE | 2018-08-11 |
| 25 | Form-2-PS-PTIN01567-04-DazometClothianidin-Fial-21022015.pdf | 2018-08-11 |
| 26 | 583-MUM-2015-PatentCertificate22-01-2020.pdf | 2020-01-22 |
| 26 | Form-2-PS-PTIN01567-04-DazometClothianidin-Fial-21022015.pdf | 2018-08-11 |
| 26 | Form-2-PS-PTIN01567-04-DazometClothianidin-Fial-21022015.pdf ONLINE | 2018-08-11 |
| 27 | 583-MUM-2015-IntimationOfGrant22-01-2020.pdf | 2020-01-22 |
| 27 | Form-2-PS-PTIN01567-04-DazometClothianidin-Fial-21022015.pdf ONLINE | 2018-08-11 |
| 27 | Form-26-GPA-GSP.pdf | 2018-08-11 |
| 28 | 583-MUM-2015-REQUEST FOR CERTIFIED COPY [09-02-2020(online)].pdf | 2020-02-09 |
| 28 | Form-26-GPA-GSP.pdf | 2018-08-11 |
| 28 | Form-26-GPA-GSP.pdf ONLINE | 2018-08-11 |
| 29 | 583-MUM-2015-CORRESPONDENCE(IPO)-(CERTIFIED COPY)-(17-2-2020)..pdf | 2020-02-18 |
| 29 | 583-MUM-2015-FORM-26 [06-04-2018(online)].pdf | 2018-04-06 |
| 29 | Form-26-GPA-GSP.pdf ONLINE | 2018-08-11 |
| 30 | 583-MUM-2015-FORM 18 [28-07-2017(online)].pdf | 2017-07-28 |
| 30 | 583-MUM-2015-FORM-26 [06-04-2018(online)].pdf | 2018-04-06 |
| 30 | 583-MUM-2015-RELEVANT DOCUMENTS [28-04-2020(online)].pdf | 2020-04-28 |
| 31 | Assignment [19-02-2016(online)].pdf | 2016-02-19 |
| 31 | 583-MUM-2015-RELEVANT DOCUMENTS [23-06-2022(online)].pdf | 2022-06-23 |
| 31 | 583-MUM-2015-FORM 18 [28-07-2017(online)].pdf | 2017-07-28 |
| 32 | Description(Complete) [19-02-2016(online)].pdf | 2016-02-19 |
| 32 | Assignment [19-02-2016(online)].pdf | 2016-02-19 |
| 32 | 583-MUM-2015-FORM-27 [25-09-2024(online)].pdf | 2024-09-25 |
| 33 | Description(Complete) [19-02-2016(online)].pdf | 2016-02-19 |
| 33 | 583-MUM-2015-PROOF OF ALTERATION [11-04-2025(online)].pdf | 2025-04-11 |
| 1 | Searchstrategy583_28-03-2019.pdf |