Abstract: The present invention relates to a synergistic pesticidal composition comprising at least one plant growth regulator selected from Mepiquat Chloride, Chlormequat Chloride and Paclobutrazol and at least one neonicotinoid insecticide, and process of preparation thereof.
FIELD OF THE INVENTION
The present invention relates to synergistic pesticidal composition comprising bioactive amounts of insecticide and a plant growth regulator. More particularly, the present invention relates to synergistic composition comprising at least one plant growth regulator and at least one neonicotinoid insecticide. The present invention also relates to a process for preparation of such synergistic pesticidal composition for improving the pest control efficacy and boosting the crop yield.
BACKGROUND OF THE INVENTION
Pesticides including insecticides are used widely and frequently in commercial agriculture and have enabled an enormous increase in crop yield and product quality which is economically advantageous to the farmers. Insecticidal compositions that can be applied at as low a dose as possible and be effective in controlling pest species of insects while causing as little harm as possible to beneficial insects and minimal disturbance in the environment are in demand by the farming community. Insects are very destructive to crops and can result in significant loss of crop yield and quality, which results in economic loss to the grower and increased cost to the consumer. Combinations of insecticides are typically used to broaden the spectrum of insect control, to minimize the doses of chemicals used, to retard resistance development and to reduce the cost of treatment through additive effect. Therefore, there is still a need for novel pesticidal composition comprising at least one neonicotinoid insecticide along with a plant growth regulator (PGR) that exhibits synergistically enhanced action, a broader scope of activity at a reduced cost of treatment.
Neonicotinoid insecticide are a broad-spectrum insecticide predominantly used to control sucking and scraping insect pests on major field crops and are additionally used as seed dressing agents in crop production. Neonicotinoids derive their toxicity from agonistically binding to nicotinic acetylcholine receptors (nAChRs) on the post-synaptic nerve membrane and firing nerve impulses in a manner that is uncontrollable and uninterrupted. They act by binding strongly to nicotinic acetylcholine receptors in the central nervous system of insects, causing overstimulation of their nerve cells, paralysis and death.
Chemicals called Plant growth regulators (PGRs) are used to change the way plants grow. For example, plant growth regulators (PGRs) can increase branching, reduce shoot growth, increasing return bloom, get rid of extra fruit, or change the maturity of the fruit. PGR efficacy is influenced by a variety of variables such as how well the chemical is absorbed by the plant, tree vigour and age, dose, timing, cultivar, and weather conditions prior to, during, and after application.
Various prior arts have offered various pesticidal compositions useful for protecting the plants from damage by harmful pests. Some of such prior arts are indicated below:
CN101861875 discloses a synergistic insecticidal composition containing Mepiquat chloride and organophosphorus pesticide, and the organophosphorus pesticide is chlorpyrifos, phoxim, triazophos or profenofos, wherein the weight ratio of the Mepiquat chloride to the organophosphorus pesticide is 1:60 to 10:1.
CN103636618 discloses a pesticidal composition containing Flonicamid and Mepiquat chloride, in 20:1 to 1:20 weight ratio.
US20100325755 discloses a combination comprising at least two active ingredient components, optionally together with one or more customary formulation auxiliaries, wherein component (I) is one or more insecticide(s) selected from the group comprising thiodicarb, clothianidin, imidacloprid, thiamethoxam, acetamiprid, thiacloprid, chlorantraniliprole, beta-cyfluthrin, lambda-cyhalothrin, tefluthrin, fipronil and abamectin and component (II) is one or more plant activator.
CN102450268A discloses paclobutrazol effervescent granules/or effervescent tablets, and a preparation method thereof, wherein the paclobutrazol effervescent granules/or effervescent tablets comprise the following raw materials by mass percent: 0.1-80% of paclobutrazol, 0.5-15% of dispersant, 0.5-8% of wetting agent, 4-60% of disintegrating agent, 0-10% of binding agent and balance of padding. The paclobutrazol effervescent granules/or effervescent tablets provided in the invention are safe for environment, people and livestock and other beneficial organisms, not easy to generate phytotoxicity, accurately measured and convenient to use and have no dust and quick granules disintegrating speed; and with better storage stability and simple preparation technology, the paclobutrazol effervescent granules/or effervescent tablets are suitable for industrial production and agricultural big area promotion.
In order to achieve high crop productivity, it is important to control the plant from damages which can be caused by plant insects & pathogenic (disease-causing) organisms including various types of plant infections. However, there exists a continuous need in the art for improved compositions that not only helps in controlling the insect growth but also optimizes crop geometry, enhances bio-efficacy including increase in plant yield, having reduced phytotoxicity and an improved stability characteristics and economic significance. Therefore, there is a long felt need to develop novel and efficacious pesticidal composition that promotes uniform crop maturity, controls harmful pests, insects in plants and is environmentally safe and can be advantageously formulated.
Combining insecticides with PGR has many benefits over using them alone, including improved and longer insect control, decreased crop damage, fewer use limitations, improved control, decreased crop damage, fewer use limitations, improved control of a wider range of insect pests, and lower costs. The need to control excessive vegetative growth, promote root growth, and prevent crop losses must be addressed. There aren’t any studies done to determine the most-effective and synergistic ratios of a composition that includes at least one plant growth regulator chosen from the Mepiquat Chloride, Chlormequat Chloride and Paclobutrazol, and at least one insecticide from the neonicotinoid class, at a ratio where these actives complement each other’s pesticidal properties in a way that isn’t seen at other ratios. Consequently, there exists a need in the art for a synergistic pesticidal composition comprising of such actives.
Thus, to improve insecticidal bio-efficacy, broad-spectrum activity with better pest management, suppression of excess vegetative growth, optimized crop geometry with uniform crop maturity, and better fruit setting, which leads to improved fruit & vegetable size and weight, increased yield, and decreased pest resistance, it is desirable to develop compositions and processes containing combinations of neonicotinoid insecticide along with plant growth regulators. Thus, there is need for novel pesticidal compositions containing at least one neonicotinoid insecticide and a plant growth regulator (PGR) that exhibit synergistically enhanced action, a broader scope of activity, and a lower treatment cost.
OBJECTIVE OF THE INVENTION:
The prime objective of the present invention is to provide a novel and effective pesticidal composition with high efficacy.
Another objective of the present invention is to provide a novel and effective pesticidal composition for controlling harmful pests in plants.
It is another objective of the present invention is to provide a novel and effective pesticidal composition which can be easily formulated with high stability.
It is another objective of the present invention to provide a novel and effective synergistic composition capable of suppressing excessive vegetative growth, increasing flowering and fruiting and avoiding yield losses.
It is another objective of the invention is to provide a novel process for preparing pesticidal composition that include a synergistic combination of neonicotinoid insecticide and a plant growth regulator.
It is another objective of the present invention is to provide a novel and effective pesticidal composition that is environmentally safe, has broad spectrum bio-efficacy, and is non-toxic in terms of phytotoxicity.
It is another objective of the present invention is to provide a novel and effective pesticidal composition that can optimise crop geometry, improve spray penetration into the crop foliage, and hit the desired targets.
It is another objective of the present invention is to provide a novel and effective pesticidal composition that promotes better fruit setting, resulting in larger and bigger fruits.
It is another objective of the present invention is to provide a novel and effective pesticidal composition that aids in early crop termination of crop and allows for early sowing and planting of succeeding crops.
It is another objective of the present invention is to provide a novel and effective pesticidal composition that promotes uniform and early crop maturity, and increases crop prices for farmers, particularly for vegetable farmers.
It is another objective of the present invention is to provide novel and effective pesticidal composition with improved control effect on plant pests and increased productivity by combining a neonicotinoid insecticide with a PGR.
Yet another objective of the present invention is to provide a method of pest control using a pesticidal composition that includes an insecticide from neonicotinoid class and at least one compound from the class of plant growth regulators.
SUMMARY OF THE INVENTION
Accordingly, the present invention provides a synergistic pesticidal composition comprising synergistic and bio-active amount of a) at least one plant growth regulator or its agrochemically acceptable salts and b) at least one neonicotinoid insecticide or its agrochemically acceptable salts.
In one of the embodiments the present invention provides a synergistic pesticidal composition comprising at least one active insecticidal ingredient, at least one plant growth regulator, with one or more agriculturally acceptable excipients, wherein the active insecticidal ingredient is neonicotinoid insecticide selected from Clothianidin, Dinotefuran, Imidacloprid, Imidaclothiz, Thiamethoxam, Nitenpyram, Nithiazine, Acetamiprid, Cycloxaprid, or Thiacloprid or its agrochemically acceptable salts.
In an embodiment of the present invention, the pesticidal composition comprises:
a) at least one plant growth regulator selected from Mepiquat Chloride, Chlormequat Chloride and Paclobutrazol; and
b) at least one neonicotinoid insecticide selected form Clothianidin, Dinotefuran, Imidacloprid, Imidaclothiz, Thiamethoxam, Nitenpyram, Nithiazine, Acetamiprid, Cycloxaprid and Thiacloprid.
In an embodiment of the present invention, the neonicotinoid insecticide is in range of 0.5 % to 65% by weight of the composition.
In an embodiment of the present invention, the plant growth regulator is in range of 0.5 % to 35% by weight of the composition.
In an embodiment of the present invention, the plant growth regulator is selected from Mepiquat Chloride, Chlormequat Chloride and Paclobutrazol.
In an embodiment of the present invention, the neonicotinoid insecticide is selected form Clothianidin, Dinotefuran, Imidacloprid, Imidaclothiz, Thiamethoxam, Nitenpyram, Nithiazine, Acetamiprid, Cycloxaprid and Thiacloprid.
In an embodiment of the present invention, the agriculturally acceptable excipients are selected from group comprising surfactants/dispersing agents, polymers, anti-freezing agent, wetting agents, anti-foaming agents, colorants, pigments, protective colloids, adhesives, binder/structuring agents, biocides/anti-microbial agent, thickeners, emulsifiers, buffering agent, fillers, diluents/solvents, quick coating agents or sticking agents, stabilizers, sequestering agents penetration agents, preservatives, adjuvants and solvents or a combination thereof
In an embodiment of the present invention, the composition comprises of:
a. Clothianidin or its agrochemically acceptable salts in an amount in the range from 0.5 to 65% by weight of the composition;
b. at least one plant growth regulator or its agrochemically acceptable salts in an amount in the range from 0.5 % to 35% by weight of the composition; and
c. at least one agriculturally acceptable excipients.
In an embodiment of the present invention, the composition comprises of:
a. dinotefuran or its agrochemically acceptable salts in an amount in the range from 0.5 to 65% by weight of the composition;
b. at least one plant growth regulator or its agrochemically acceptable salts in an amount in the range from 0.5 % to 35% by weight of the composition; and
c. at least one agriculturally acceptable excipients.
In an embodiment of the present invention, the composition comprises of:
a. Clothianidin or its agrochemically acceptable salts in an amount in the range from 0.5 to 65% by weight of the composition;
b. Mepiquat Chloride or its agrochemically acceptable salts in an amount in the range from 0.5 % to 35% by weight of the composition; and
c. at least one agriculturally acceptable excipients.
In another embodiment of the present invention is provided, a method for pest control comprising applying to the plant or portion thereof or soil, a pesticidal effective amount of the composition.
In an embodiment of the present invention is provided, method of improving vigour or yield of the plant comprising, treating a plant or portion thereof or soil, a pesticidal effective amount of the composition.
In one embodiment of the present invention, the present pesticidal composition controls various pests in cereals, field crops, vegetables, fruits, oil seeds, turf, grasses, potatoes, grapes, cotton, ornamentals, and pulses, horticulture and forestry, Veterinary, etc.
In another embodiment of the present invention, the present pesticidal composition is applied as a foliar spray, soil drenching, seed dressing, application as paste to the targeted plants/ trees, broadcasting, etc.
In yet another embodiment of the present invention, the present pesticidal composition is used as a soil application to rice, sugarcane, potato, ground nut etc.
In yet another embodiment of the present invention, the present pesticidal composition is applied as a foliar spray to cotton, wheat, soyabean, pulses and vegetables including but not limited to okra, tomato, sugar beet, egg-plants, lettuce, iceberg lettuce, pepper, cucumber, squash, melon, bean, dry-beans, peas, leek, garlic, onion, cabbage, carrot, tuber such as sugar cane, tobacco, coffee, turf and forage, cruciferous, cucurbits, grapevines, pepper, fodder beet, oil seed rape, pansy, impatiens, petunia and geranium, etc.
In another embodiment of the present invention, the present pesticidal composition is used against but not limited to sucking pests including aphids, leafhoppers, thrips, whitefly, flies, bugs, and mites.
In further embodiment of the present invention, pesticidal composition of the present invention further comprises protective colloids, adhesives, thickeners, thixotropic agents, penetration agents, stabilisers, sequestering agents. More generally, the active materials can be combined with any solid or liquid additive, which complies with usual formulation techniques.
In yet another embodiment of the present invention, the composition can be formulated as one or more of Capsule suspension (CS), Dispersible concentrate (DC), Dustable powder (DP), Powder for dry seed treatment (DS), Emulsifiable concentrate (EC), Emulsifiable granule (EG), Emulsion water-in-oil (EO), Emulsifiable powder (EP), Emulsion for seed treatment (ES), Emulsion oil-in-water (EW), Flowable concentrate for seed treatment (FS), Granules (GR), Micro-emulsion (ME), Oil-dispersion (OD), Oil miscible flowable concentrate (OF), Oil miscible liquid (OL), Oil dispersible powder (OP), Suspension concentrate (SC), Suspension concentrate for direct application (SD), Suspo-emulsion (SE), Water soluble granule (SG), Soluble concentrate (SL), Spreading oil (SO), Water soluble powder (SP), Water soluble tablet (ST), Ultra-low volume (ULV) suspension, Tablet (TB), Ultra-low volume (ULV) liquid, Water dispersible granules (WG), Wettable powder (WP), Water dispersible powder for slurry seed treatment (WS), Water dispersible tablet (WT), a mixed formulation of CS and SC (ZC) or a mixed formulation of CS and SE (ZE) and a mixed formulation of CS and EW (ZW).
DETAILED DESCRIPTION OF THE INVENTION
Embodiments, of the present disclosure, will now be described herein. Embodiments are provided so as to thoroughly and fully convey the scope of the present disclosure to the person skilled in the art. Numerous details are set forth, relating to specific components, and methods, to provide a complete understanding of embodiments of the present disclosure. It will be apparent to the person skilled in the art that the details provided in the embodiments should not be construed to limit the scope of the present disclosure. In some embodiments, well-known processes, well-known additional excipients, and well-known techniques are not described in detail. Discussed below are some representative embodiments of the present invention. The invention in its broader aspects is not limited to the specific details and representative methods.
All technical and scientific terms used herein have the same meanings as commonly understood by someone ordinarily skilled in the art to which the present subject matter belongs.
The terminology used, in the present disclosure, is only for the purpose of explaining a particular embodiment and such terminology shall not be considered to limit the scope of the present disclosure. As used in the present disclosure, the forms "a,” "an," and "the" may be intended to include the plural forms as well, unless the context clearly suggests otherwise. Thus, for example, reference to a composition containing “a compound” includes a mixture of two or more compounds. It should also be noted that the term “or” is generally employed in its sense including “and/or” unless the content clearly dictates otherwise. The terms "comprises," "comprising," “including,” and “having,” are open ended transitional phrases and therefore specify the presence of stated features, integers, steps, operations, elements, but do not forbid the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. The particular order of steps disclosed in the method and process of the present disclosure is not to be construed as necessarily requiring their performance as described or illustrated. It is also to be understood that additional or alternative steps may be employed.
Variations or modifications to the composition of this invention, within the scope of the invention, may occur to those skilled in the art upon reviewing the disclosure herein. Such variations or modifications are well within the spirit of this invention.
The expression of various quantities in terms of “% w/w” or “%” means the percentage by weight, relative to the weight of the total solution or composition unless otherwise specified.
The term “active ingredient” (a.i.) or “active agent” used herein refers to that component of the composition responsible for control and killing of pest.
The term “synergistic”, as used herein, refers to the combined action of two or more active agents blended together and administered conjointly that is greater than the sum of their individual effects.
“Bioactive amounts” as mentioned herein means that amount which, when applied for treatment of crops, is sufficient to give effect in such treatment.
“Crop geometry” as mentioned refers to the shape of the space available for individual plants. It influences crop yield through its influence on light interception, rooting pattern and moisture extraction pattern.
The term seed treatment comprises all suitable seed treatment techniques known in the art, such as, but not limited to, seed dressing, seed coating, seed dusting, seed soaking, seed film coating, seed multilayer coating, seed encrusting, seed dripping, and seed pelleting.
The term "health of a plant" or "plant health" is defined as a condition of the plant and/or its products. As a result of the improved health; yield, plant vigour, quality and tolerance to abiotic or biotic stress is increased. It is noteworthy that the health of a plant when applying the composition according to the present invention, is increased independently of the pesticidal properties of the active ingredients used; because the increase in health is not based upon the reduced pest pressure but instead on complex physiological and metabolic reactions which result for example in an activation of the plant's own natural defence system. As a result, the health of a plant is increased even in the absence of pest pressure.
According to the present invention, "increased yield" of a plant, in particular of an agricultural, silvicultural and/or horticultural plant means that the yield of a product of the respective plant is increased by a measurable amount over the yield of the same product of the plant produced under the same conditions, but without the application of the mixture according to the invention.
In one embodiment of the present invention, the plant growth regulator is Mepiquat Chloride or Chlormequat Chloride or Paclobutrazol.
In a preferred embodiment of the present invention, the plant growth regulator is Mepiquat Chloride.
In another embodiment of the present invention, the plant growth regulator is used in an amount of about 0.5-35% weight of the total composition.
In one embodiment of the present invention, the neonicotinoid insecticide is used in an amount of about 0.5-65% weight of the total composition.
In further embodiment of the present invention, the neonicotinoid insecticide is selected from Clothianidin, Dinotefuran, Imidacloprid, Imidaclothiz, Thiamethoxam, Nitenpyram, Nithiazine, Acetamiprid, Cycloxaprid and Thiacloprid
In a preferred embodiment of the present invention, the neonicotinoid insecticide is Clothianidin.
In accordance with an embodiment of the invention, there is provided a synergistic pesticidal composition comprising active ingredients present in the weight ratios as given below; and one or more agrochemically acceptable excipients.
Plant Growth Regulator Neonicotinoid
insecticide
Mepiquat Chloride
Chlormequat Chloride
Paclobutrazol Clothianidin
Dinotefuran,
Imidacloprid
Imidaclothiz, Thiamethoxam Nitenpyram
Nithiazine
Acetamiprid
Cycloxaprid
Thiacloprid
0.5-35% 0.5-65%
Mepiquat Chloride was first disclosed in DE2207575. Chemically Mepiquat Chloride is known as 1,1-dimethylpiperidinium chloride (CAS REG No. 24307-26-4). Chemical structure of Mepiquat Chloride is as below:
Mepiquat Chloride
Mepiquat (IUPAC name: N,N-dimethylpiperidinium) is a widely accepted PGR for cotton plants and is typically applied to cotton plants in the form of a salt, such as mepiquat chloride or mepiquat pentaborate, by foliar application. U.S. Patent Nos. 5,478,796; 5,627,134; 5,650,372; 5,654,255; 5,869,424; 5,935,906; 6,224,734; 6,232,270; 6,248,694; 6,288,009; 6,376,425 and 6,465,394 teach various mepiquat formulations.
Chlormequat Chloride was first disclosed in US3301902. Chemically Chlormequat Chloride is known as 2-chloro-N, N, N-trimethylethanaminium chloride (CAS REG No. 999-81-5). Chemical structure of Chlormequat Chloride is as below:
Chlormequat Chloride
Chlormequat Chloride (IUPAC name: (2-chloroethyl) trimethylammonium chloride)) is a plant growth regulator, inhibiting the action of the gibberellic acid, resulting in shortening and strengthening of stems in plants and reduced branching and foliage in certain species of shrubs and trees.Paclobutrazol (PBZ) was first disclosed in US4243405 (PBZ). Chemically PBZ is known as (2RS,3RS)-1-(4-chlorophenyl)-4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl) pentan-3-ol (CAS REG. No. 76738-62-0). Chemical structure of PBZ is as below;
Paclobutrazol
PBZ is a plant growth retardant and triazole fungicide. It is a known antagonist of the plant hormone gibberellin. It acts by inhibiting gibberellin biosynthesis, reducing inter nodal growth to give stouter stems, increasing root growth, causing early fruit set and increasing seed set in plants such as tomato and pepper. PBZ has also been shown to reduce frost sensitivity in plants. Moreover, PBZ can be used as a chemical approach for reducing the risk of lodging in cereal crops (Kamran et. al 2017). PBZ is used by arborists to reduce shoot growth and has been shown to have additional positive effects on trees and shrubs. Among those are improved resistance to drought stress, darker green leaves, higher resistance against fungi and bacteria, and enhanced development of roots. Cambial growth, as well as shoot growth, has been shown to be reduced in some tree species.
Neonicotinoids are a broad-spectrum insecticide predominantly used to control sucking and scraping insect pests on major field crops and are additionally used as seed dressing agents in crop production. Neonicotinoids derive their toxicity from agonistically binding to nicotinic acetylcholine receptors (nAChRs) on the post-synaptic nerve membrane and firing nerve impulses in a manner that is uncontrollable and uninterrupted. Popularity of neonicotinoids is due to their advertised high toxicity to insects and low toxicity to vertebrates. Additionally, neonicotinoids have gained popularity by their ability to systemically protect plants while reducing application inputs for farmers. Chemical structure of some of such insecticides are provided below:
Clothianidin was first disclosed in EP0375907. Chemically Clothianidin is known as (E)-1-(2-chloro-1,3-thiazol-5-ylmethyl)-3-methyl-2-nitroguanidine (CAS REG No. 210880-92-5). Chemical structure of Clothianidin is as below:
Clothianidin
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 synergistic composition has very advantageous curative and preventive properties for protecting cultivated plants. As has been mentioned, said active ingredient composition is used to inhibit or destroy the insects and pathogens that occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops or useful plants, while at the same time those parts of plants which grow later are also protected from attack by such pests. Active ingredient composition has the special advantage of being highly active against pests from the time of crop establishment till fruiting.
The composition according to the invention can be applied to any and all developmental stages of pests, such as egg, larva, pupa, and adult. The pests may be controlled by contacting the target pest, its food supply, habitat, breeding ground or its locus with a pesticidal effective amount of the composition of the present invention.
The composition of the present invention control insects pests selected from the following orders: Lepidoptera, for example Agrotis ipsilon, Anticarsia gemmatalis, Chilo partellus, Cnaphalocrosis medinalis, Cydia pomonella, Diaphania nitidalis, Earias insulana, Elasmopalpus lignosellus, Heliothis armigera, Heliothis virescens, Heliothis zea, Hellula undalis, Hyphantria cunea, Hyponomeuta malinellus, Leucoptera coffeella, Leucoptera scitella, Ostrinia nubilalis, Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris bras-sicae, Plutella xylostella, Sitotroga cerealella, Sesamia inferans, Sparganothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni, beetles (Coleoptera), for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscu-rus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Aphthona euphoridae, Apogonia aerea, Athous haemorrhoidalis, Atomaria linearis, Blasto-phagus piniperda, Blitophaga undata, Brahmina coriacea , Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata, Cetonia aurata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Ctenicera ssp., Diabrotica longicornis, Diabrotica semipunctata, Diabrotica 12-punctata Diabrotica speciosa, Diabrotica virgifera, Epila-chna varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, White grub species, Holotrichia consanguinea , Holotrichia serrata, Holotrichia longipennis, Hylobius abietis, Hypera brunneipennis, Hypera postica, Ips typographus, Lema bilineata, Lema melanopus, Lepidiota stigma, Leptinotarsa decemlineata, Limonius califomicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, Oberea (Obereopsis) brevis, Oulema oryzae, Ortiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon cochleariae, Phyllobius pyri, Phyllotreta chrysocephala, Phyllophaga sp., Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus and Sito-philus gran aria, flies, (Diptera), e.g. Atherigona orientalis, Atherigona soccata, Athalia lugen proxima, Dacus cucurbi-tae, Dacus oleae, Glossina palpalis, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hylemyia platura, Hypoderma lineata, Leptoconops torrens, Leaf miner, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mansonia titillanus, Mayetiola destructor, Oscinella frit, Phorbia brassicae, Prosimulium mixtum, Rhagoletis cerasi, Sarcophaga sp., Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, and Tabanus similis, Tipula oleracea, and Tipula paludosa, thrips (Thysanoptera), e.g. Dichromothrips corbetti, Dichromothrips ssp , Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Scirtothrips dorsalis, Thrips oryzae, Thrips palmi and Thrips tabaci, termites (Isoptera), e.g. Calotermes flavicollis, Coptotermes formosanus, Heterotermes aureus, Leucotermes flavipes, Microtermes spp., Odontotermes, Reticulitermes flavipes, Reticulitermes virginicus, Reticulitermes lucifugus and Termes natalensis; true bugs (Hemiptera), e.g. Acrosternum hilare, Amrasca biguttula biguttula, Amrasca devastans, Blissus leucopterus, Dysdercus cingulatus, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridu-la, Piesma quadrata, Solubea insularis, Thyanta perditor, Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis crassivora, Aphis grossulariae, Aphis schneideri, Aphis spiraecola, Aphis sambuci, Acyrtho-siphon pisum, Aulacorthum solani, Bemisia argentifolii, Bemisia tabaci, Brachycaudus cardui, Brachy-caudus helichrysi, Brachycaudus persicae, Brachycaudus prunicola, Brevicoryne brassicae, Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordmannianae, Dreyfusia piceae, Dysaphis radicola, Dysaulacorthum pseudosolani, Dysaphis plantaginea, Dysaphis pyri, Empoasca fabae, Hyalopterus pruni, Hyperomyzus lactucae, Macrosiphum avenae, Macrosiphum euphorbiae, Ma-crosiphon rosae, Megoura viciae, Melanaphis pyrarius, Metopolophium dirhodum, My-zus persicae, Myzus ascalonicus, Myzus cerasi, Myzus varians, Nasonovia ribis-nigri, Nilaparvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla mail, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Rhopalosi-phum padi, Rhopalosiphum insertum, Sappaphis mala, Sappaphis mail, Schizaphis graminum, Schizoneura lanuginosa, Sitobion avenae, Trialeurodes vaporariorum, Toxoptera aurantiia d, Viteus vitifolii, Cimex lectularius, Cimex hemipterus, Reduvius senilis, Triatoma spp., and Arilus critatus, Trialeurodes vaporariorum, Amrasca biguttula, Empoasca spp., Myzus spp., Nephotettix spp., Nilaparvata spp., Planococcus spp., Pseudococcus spp., Psylla spp., Rhopalosiphum spp., Sitobion spp., Amritodus atkinsoni, Idioscopus spp., ants, bees, wasps, sawflies (Hymenoptera), e.g. Athalia rosae, Atta cephalotes, Atta capiguara, Atta cephalotes, Atta laevigata, Atta robusta, Atta sexdens, Atta texana, Crematogaster spp., Hoplocampa minuta, Hoplocampa testudinea, Monomorium pha-raonis, Solenopsis geminata, Solenopsis invicta, Solenopsis richteri, Solenopsis xyloni, Pogonomyrmex barbatus, Pogonomyrmex californicus, Pheidole megacephala, Dasy-mutilla occidentalis, Bombus spp. Vespula squamosa, Paravespula vulgaris, Paraves-pula pennsylvanica, Paravespula germanica, Dolichovespula maculata, Vespa crabro, Polistes rubiginosa, Camponotus floridanus, and Linepithema humile, crickets, grasshoppers, locusts (Orthoptera), e.g. Acheta domestica, Gryllotalpa gryllo-talpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femurrubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Schistocerca americana, Schistocerca gregaria, Dociostaurus maroccanus, Tachycines asynamorus, Oedaleus senegalensis, Zonozerus variegatus, Hieroglyphus daganensis, Kraussaria angulifera, Calliptamus italicus, Chortoicetes terminifera, and Locustana pardalina, plant parasitic nematodes such as root-knot nematodes, Meloidogyne arenaria, Meloidogyne incognita, Meloidogyne javanica; cyst nematodes, Globodera rostochiensis, Heterodera avenae; seed gall nematodes, Anguina funesta, Anguina tritici and other Anguina species; stem and foliar nematodes, Aphelenchoides besseyi, sting nematodes, Belonolaimus longicaudatus and other plant parasitic nematode species including whitefly and leafhoppers.
Suitable targets for seed treatment are one or more of various crop seeds, fruit species, vegetables, spices and ornamental seed, for example corn/maize (sweet and field), durum wheat, soybean, groundnut, wheat, barley, oats, rye, triticale, bananas, rice, cotton, sunflower, potatoes, pasture, alfalfa, grasses, turf, sorghum, rapeseed, Brassica spp., sugar beet, egg-plants, tomato, lettuce, iceberg lettuce, pepper, cucumber, squash, melon, bean, dry-beans, peas, leek, garlic, onion, cabbage, carrot, tuber such as sugar cane, tobacco, coffee, turf and forage, cruciferous, cucurbits, grapevines, pepper, fodder beet, oil seed rape, pansy, impatiens, petunia and geranium.
The composition of the present invention is effective for management of insect or pests selected from one or more of Cotton (Gossypium spp.), Paddy (Oryza sativa), Wheat (Triticumaestavum), Barley (Hordeumvulgare), Maize (Zea mays), Sorghum (Sorghum bicolor), Sugarcane (Saccharum officinarum) , Sugarbeet (Beta vulgaris), Soybean (Glycin max), Peanut (Arachis hypogaea), Sunflower (Helianthus annuus) , Mustard (Brassica juncea), Rape seed (Brassica napus), Linseed (Linum usitatissimum), Sesame (Sesamum indicum), Castor (Ricinus communis), Green gram (Vigna radiate), Black gram (Vigna mungo), Chickpea (Cicer aritinum), Cowpea (Vigna unguiculata), Redgram (Cajanus cajan), Frenchbean (Phaseolus vulgaris), Indian bean (Lablab purpureus), Horse gram (Macrotyloma uniflorum), Field pea (Pisum sativum), Cluster bean (Cyamopsis tetragonoloba), Lentils (Lens culinaris), Brinjal (Solanum melongena), Cabbage (Brassica oleracea var. capitata), Cauliflower (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), Cucumber (Cucumis sativus), Muskmelons (Cucumis melo), Watermelon (Citrullus lanatus), Bottle gourd (Lagenaria siceraria), Bitter gourd (Momordica charantia), Radish (Raphanus sativus), Carrot (Dacuscarota subsp. sativus), Turnip (Brassica rapa subs prapa), Apple (Melus domestica), Banana (Musa spp.), Citrus groups (Citrus spp.), Grape (Vitis vinifera), Guava (Psidium guajava), Litchi (Litchi chinensis), Mango (Mangifera indica), Papaya (Carica papaya), Pineapple (Ananas comosus), Pomegranate (Punica granatum) , Sapota (Manilkara zapota), Tea (Camellia sinensis), Coffea (Coffea Arabica), Turmeric (Curcuma longa), Ginger (Zingiber officinale), Cumin (Cuminum cyminum), Fenugreek (Trigonella foenum-graecum), Fennel (Foeniculum vulgare), Coriander (Coriandrum sativum), Ajwain (Trachyspermum ammi), Psyllium (Plantago ovate), Black Pepper (Piper nigrum), Stevia (Stevia rebaudiana), Safedmusli (Chlorophytum tuberosum), Drum stick (Moringa oleifera), Coconut (Coco nucifera), Mentha ( Mentha spp.), Rose (Rosa spp.), Jasmine (Jasminum spp.), Marigold ( Tagetes spp.), Common daisy (Bellis perennis), Dahlia (Dahlia hortnesis), Gerbera (Gerbera jamesonii), Carnation (Dianthus caryophyllus) or GMO form thereof.
Increased yield is characterized, among others, by the following improved properties of the plant: increased plant weight, increased plant height, increased biomass such as higher overall fresh weight (FW), increased number of flowers per plant, higher grain yield, more tillers or side shoots (branches), larger leaves, increased shoot growth, increased protein content, increased oil content, increased starch content, increased pigment content, increased leaf are index.
In another embodiment of the present invention is provided, a process for preparation of the said composition, wherein, the composition can be one or more of Capsule suspension (CS), Dispersible concentrate (DC), Powder for dry seed treatment (DS), Emulsifiable concentrate (EC), Emulsion, water in oil (EO), Emulsion for foliar spray (ES), Emulsion, oil in water (EW), Flowable suspension/concentrate for foliar spray (FS), Granule/ soil applied (GR), Controlled (Slow or Fast) release granules (CR), Jambo balls or bags (bags in water soluble pouch), Solution for foliar spray (LS), Micro-emulsion (ME), Oil dispersion (OD), Oil miscible flowable concentrate (oil miscible suspension (OF), Oil miscible liquid (OL), Suspension concentrate (= flowable concentrate) (SC), Suspo-emulsion (SE), Water soluble granule (SG), Soluble concentrate (SL), Water soluble powder (SP), Water dispersible granule (WG or WDG), Wettable powder (WP), Water dispersible powder for slurry treatment (WS), A mixed formulation of CS and SC (ZC), a mixed formulation of CS and SE (ZE), A mixed formulation of CS and EW (ZW).
In another embodiment of the present invention, the composition comprises of:
a) at least one plant growth regulator selected from Mepiquat Chloride, Chlormequat Chloride and Paclobutrazol; and
b) at least one neonicotinoid insecticide selected form Clothianidin, Dinotefuran, Imidacloprid, Imidaclothiz, Thiamethoxam, Nitenpyram, Nithiazine, Acetamiprid, Cycloxaprid and Thiacloprid.
The composition of the present invention surprisingly results in a synergistic effect. The composition of the present invention has surprisingly improved plant yield.
The composition of the present invention in addition to bioactive amounts of active ingredients, further comprises inactive agriculturally acceptable excipients including but not limited to surfactants/dispersing agents, polymers, anti-freezing agent, wetting agents, anti-foaming agents, colorants, pigments, binder/structuring agents, biocides/anti-microbial agent, thickeners, emulsifiers, buffering agent, fillers, diluents/solvents, quick coating agents or sticking agents, preservatives, adjuvants and solvents or a combination thereof.
In another embodiment of the present invention, the thickeners are selected from the group comprising thickeners are selected from the group comprising silicates such metal silicates, aluminum magnesium silicate sodium carboxy methyl cellulose, methyl cellulose, ethyl cellulose, poly vinyl alcohol, sodium alginate, sodium poly acrylate, xanthan gum, welan gum, gum arabic, montmorillonite, lingo sulfonates, hydroxy methyl cellulose, dextrin, starch, Bentonite Clay, Polysaccharides or combinations thereof.
In another embodiment of the present invention, the anti-freezing agent is selected from the group comprising polyethylene glycols, methoxy polyethylene glycols, propylene glycol, polypropylene glycols, polybutylene glycols, Mono ethylene glycol, glycerin, ethylene glycol, Glycerin, Diethylene glycol or combinations thereof.
In another embodiment of the present invention, anti-foaming agent is selected from the group comprising silicone oils, or mineral oils, Fatty acid ester; potassium sorbate, and parahydroxy benzoates, silicon emulsion based anti-foam agents, Siloxane polyalkylene oxide, Polydimethyl Siloxane, tri siloxane ethoxylates or combinations thereof.
In another embodiment of the present invention, wetting agent is selected from the group comprising Tristyrylphenol ethoxylate nonionic emulsifier, Mixture of non-ionic surfactants & Alkoxylated Alcohol/Block copolymer, sodium lauryl sulphate; sodium dioctyl sulphosuccinate; Tristyrylphenol ethoxylate non-ionic emulsifier/ mixture of non-ionic surfactants and alkoxylated Alcohol/Block copolymer, ionic surfactant mixtures, anionic surfactants, alkyl phenol ethoxylates, aliphatic alcohol ethoxylates and the salts or combinations thereof.
In another embodiment of the present invention, dispersing agent is selected from the group comprising Tristyrylphenol Ethoxylate Amine salt of phosphate tristyryl phenol ethylated /Acrylic Copolymer/ Ethoxylated Tristryl phenol Sulphate,Naphthalene sulfonic acid,sodium salt condensate with formaldehyde,Ethoxylated oleyl cetyl alcohol, Polyalkelene glycol ether or combinations thereof.
In yet another embodiment of the present invention, the polymers are selected from the group comprising polyvinyl alcohols, polyvinylpyrrolidone, gel-forming carraagheenans, water-soluble gelatine and casein, superabsorbent polymers such polyacrylamides and polyacrylates based polymers, semi-synthetic or fully-synthetic peptide/protein-based superabsorbent polymers such as collagen-based synthetic polymers, elastin-like polypeptides, polyaspartic acid, polyaspartates, polyglutamic acid, polyglutamate, Semi-synthetic or fully-synthetic polysaccharide: carboxymethyl starch , sulfoethyl starch, carboxymethyl cellulose, sulfoethyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, methylcellulose, chitosan, acrylonitrile, acrylic acid, methacrylic acid, acrylamide, methacrylamide, 2-acrylamido-2-methyl- propanesulfonic acid (AMPS), vinyl sulfonic acid, ethyl acrylate, and potassium acrylate or combinations thereof.
In yet another embodiment of the present invention, the adjuvant is selected from the group comprising Silicone Ethoxylated Oil, Polyvinyl Pyrrolidon, Poly vinyl Alcohol,Blend of poly terpene resin or combination thereof; the diluent/solvents are selected from the group comprising lactose, glucose, fructose, maltose, sucrose, in the anhydrous or hydrate forms, urea, water soluble or dispersible polymers, water soluble inorganic salts, Demineralized (DM) water, Vegetable Oil or combination thereof; and filer is selected from the group comprising Silicon Dioxide, China –Clay, Kaolin, Talc, starch or combination thereof.
In yet another embodiment of the present invention, the biocide/anti-microbial agent is selected from the group comprising Benzisothiazolin-3-one / Formaldehyde/Sodium benzoate/Sodium o-phenyl phenate, 5-chloro-2-methyl-4-isothiazolin-3-one & 2-methyl-4-isothiazolin-3-one or combination thereof.
The process for preparing the present novel synergistic composition can be modified accordingly by any person skilled in the art based on the knowledge of manufacturing of the formulation. However, all such variation and modification are still covered by the scope of present invention.
In another embodiment of the present invention provides a stable compositions of the synergistic combination of at least one plant growth regulator selected from Mepiquat Chloride, Chlormequat Chloride and Paclobutrazol; and at least one insecticide selected from neonicotinoid class of insecticides.
The present invention is illustrated by the experiments as exemplified below.
Examples
Example 1:
Sr. No.
Recipe % w/w
1. Mepiquat Chloride Technical 0.5-35%
2. Clothianidin Technical 0.5-65%
3. Dispersing Agent- Tristyrylphenol Ethoxylate Amine
salt of phosphate tristyryl phenol ethylated /Acrylic
Copolymer/ Ethoxylated Tristryl phenol Sulphate,Naphthalene sulfonic acid,sodium salt condensate with formaldehyde,Ethoxylated oleyl cetyl alcohol, Polyalkelene glycol ether 0.5-10%
4. Wetting Agent- Tristyrylphenol ethoxylate nonionic
emulsifier/ Mixture of non-ionic surfactants
& Alkoxyleted Alcohol/Block copolymer, 0.5-10%
5. Antifoaming Agent-Siloxane polyalkyleneoxide 0.01-2%
6. Antifreezing Agent- Glycol,Propylene Glycol,Mono ethylene glycol,Glycerin 5%
7. Filler- Silicon Dioxide/China -
Clay/Kaolin/Talc/starch 0.1-5%
8. Anti-bacterial – Benzisothiazolin-3-one / Formaldehyde 0.01-1%
9. Polysaccharides/carboxymethyl cellulose/Bentonite Clay 0.01-3%
10. DM water Q.s to make 100
Total 100
A stable Suspension Concentrate (SC) of Mepiquat Chloride and Clothianidin according to the present invention was prepared as follows:
SC (Suspension Concentrate)
Sr. No. Component Composition
1 2 3 4 5
1. Mepiquat Chloride 5 1 2 3 1
2. Clothianidin 50 25 0.5 30 30
3. Acrylic Copolymer 3.00 3.00 3.00 3.00 3.00
4. Naphthalene sulfonic acid, sodium salt condensate with formaldehyde 4.00 4.00 4.00 4.00 4.00
5. Block copolymer 1.00 1.00 1.00 1.00 1.00
6. Silicone Antifoam 0.50 0.50 0.50 0.50 0.50
7. Benzisothiazoline 0.10 0.10 0.10 0.10 0.10
8. Glycol 5.00 5.00 5.00 5.00 5.00
9. Polysaccharides 0.10 0.10 0.10 0.10 0.10
10. DM water QS to Make 100 QS to Make 100 QS to Make 100 QS to Make 100 QS to Make 100
Example 2:
Sr. No. Recipe % w/w
1. Mepiquat Chloride Technical 5.00%
2. Clothianidin Technical 20%
3. Dispersing Agent- Tristyrylphenol Ethoxylate Amine
salt of phosphate 3%
4. Wetting Agent- Block copolymer, 2%
5. Antifoaming Agent-Siloxane polyalkyleneoxide 0.20%
6. Antifreezing Agent- Propylene Glycol 5%
7. Filler- China -Clay 1%
8. Anti-bacterial – Benzisothiazolin-3-one 0.10%
9. Polysaccharides 0.10%
10. DM water Q.s to make 100
Total 100
Process: Required quantity of water, biocide, and defoamer followed by addition of gum powder are homogenized with stirring to obtain a gum solution (Gum Solution should be made 12-18 hour prior to use). Required quantity of DM water, wetting agent, dispersing agent & suspending agents, colourant/dye was added into the charged vessel followed by homogenization for a period of ranging between 45 – 60 minutes using high shear homogeniser to obtain a homogenized slurry. Technical and other remaining adjuvants excluding ‘antifreeze & thickeners’ were added into the homogenized slurry to obtain a uniform slurry. Half of the quantity of required antifoam agent was added into the slurry. The uniform slurry mixture was then passed through appropriate particle size reduction equipment (Dyno-Mill) until the granule material of the desired particle size was achieved. Remaining half of the quantity of required antifoam agent along with the antifreeze agent was added to the granule material as obtained. Gum solution as obtained in the first step was then added to obtain the suspension concentrate.
A stable Flowable Slurry of Mepiquat Chloride and Clothianidin according to the present invention was prepared as follows:
FS (Flowable Slurry)
Sr. No. Component Composition
1 2 3 4 5
1. Mepiquat Chloride 5 0.5 2 3 1
2. Clothianidin 50 25 0.5 30 30
3. Acrylic Copolymer 3.00 3.00 3.00 3.00 3.00
4. Naphthalene sulfonic acid,sodium salt condensate with formaldehyde 4.00 4.00 4.00 4.00 4.00
5. Block copolymer 1.00 1.00 1.00 1.00 1.00
6. Silicone Antifoam 0.50 0.50 0.50 0.50 0.50
7. Benzisothiazoline 0.10 0.10 0.10 0.10 0.10
8. Glycol 5.00 5.00 5.00 5.00 5.00
9. Polysaccharides 0.10 0.10 0.10 0.10 0.10
10. DM water QS to Make 100 QS to Make 100 QS to Make 100 QS to Make 100 QS to Make 100
Example 3:
Sr. No. Recipe % w/w
1. Mepiquat Chloride Technical 25.00%
2. Clothianidin Technical 5%
3. Dispersing Agent- Tristyrylphenol Ethoxylate Amine
salt of phosphate 3%
4. Wetting Agent- Block copolymer, 2%
5. Antifoaming Agent-Siloxane polyalkyleneoxide 0.20%
6. Antifreezing Agent- Propylene Glycol 5%
7. Filler- China -Clay 1%
8. Anti-bacterial – Benzisothiazolin-3-one 0.10%
9. Polysaccharides 0.10%
10. DM water Q.s to make 100
Total 100
Process: Required quantity of water, biocide, and defoamer followed by addition of gum powder are homogenized with stirring to obtain a gum solution (Gum Solution should be made 12-18 hour prior to use). Required quantity of DM water, wetting agent, dispersing agent and suspending agents, colourant/dye was added into the charged vessel followed by homogenization for a period of ranging between 45 – 60 minutes using high shear homogeniser to obtain a homogenized slurry. Technical and other remaining adjuvants excluding ‘antifreeze & thickeners’ were added into the homogenized slurry to obtain a uniform slurry. Half of the quantity of required antifoam agent was added into the slurry. The uniform slurry mixture was then passed through appropriate particle size reduction equipment (Dyno-Mill) until the granule material of the desired particle size was achieved. Remaining half of the quantity of required antifoam agent along with the antifreeze agent was added to the granule material as obtained. Gum solution as obtained in the first step was then added to obtain the flowable slurry.
A stable Granule (GR) formulation of Mepiquat Chloride and Clothianidin according to the present invention was prepared as follows:
GR (Granule)
Sr. No. Component Composition
1 2 3 4 5
1. Mepiquat Chloride 1 5 2 3 0.5
2. Clothianidin 5 2 0.5 2 10
3. Sodium Polycarboxylate 3.00 3.00 3.00 3.00 3.00
4. Sodium Lauryl Sulfate 4.00 4.00 4.00 4.00 4.00
5. Pigment blue 0.10 0.10 0.10 0.10 0.10
6. Polyvinyl pyrrolidone 0.50 0.50 0.50 0.50 0.50
7. China Clay 5.00 5.00 5.00 5.00 5.00
8. DM water 1.00 2.00 1.00 2.00 1.00
9. Sand QS to Make 100 QS to Make 100 QS to Make 100 QS to Make 100 QS to Make 100
Example 4:
Sr. No. Recipe % w/w
1. Mepiquat Chloride Technical 5.00%
2. Clothianidin Technical 0.50%
3. Dispersing Agent- Calcium Ligno sulphate 3%
4. Pigment Blue 0.20%
5. Filler- China -Clay 5%
6. Sticking agent-Polyvinyl pyrrolidone 0.10%
7. DM water 1%
8. Sand Q.s to make 100
Total 100
Process: Required quantity of filler, wetting agent, dispersing agent, and suspending agent, & technical was mixed in a premixing blender for homogenization for a period of 30 minutes to obtain a pre-blended material. The pre-blended material as obtained in the first step was blended through Jet mill/ air classifier mills followed by blending in post blender for a period of ~1.5 hour to obtain a homogeneous mixture. Then required quantity of sand was charged in the granulator, later DM water sticking agent and remaining material was added till it became homogeneous. The finely grinded material was then completely coated on sand and the resulting formulation was blended for 30 minutes to obtain the granule formulation.
A stable Water Dispersible Granule (WG) formulation of Mepiquat Chloride and Clothianidin according to the present invention was prepared as follows:
WG (Water Dispersible Granule)
Sr. No. Component Composition
1 2 3 4 5
1. Mepiquat Chloride 5 35 2 3 0.5
2. Clothianidin 65 25 0.5 30 30
3. Sodium Polycarboxylate 3.00 3.00 3.00 3.00 3.00
4. Sodium Lauryl Sulfate 4.00 4.00 4.00 4.00 4.00
5. Sodium alkyl naphthalene sulfonate blend 1.00 1.00 1.00 1.00 1.00
6. Sodium alkylnaphthalenesulfonate, formaldehyde condensate 0.50 0.50 0.50 0.50 0.50
7. Silicone based antifoam 0.10 0.10 0.10 0.10 0.10
8. Starch 5.00 5.00 5.00 5.00 5.00
9. Lactose anhydrous 0.10 0.10 0.10 0.10 0.10
10. China Clay QS to Make 100 QS to Make 100 QS to Make 100 QS to Make 100 QS to Make 100
Example 5:
Sr. No. Recipe % w/w
1. Mepiquat Chloride Technical 35.00%
2. Clothianidin Technical 30.00%
3. Dispersing Agent-Sodium Polycarboxylate 3.00
4. Wetting Agent-Sodium Lauryl Sulfate 4.00
5. Dispersing Agent Sodium alkyl naphthalene sulfonate blend 1.00
6. Antifoam-Polydimethyl Siloxane 0.10
7. Filler-China Clay QS to Make 100
Process: Required quantity of filler, wetting agent, dispersing agent, and suspending agent, & technical was mixed in a premixing blender for homogenization for a period of 30 minutes to obtain a pre-blended material. The pre-blended material as obtained in the first step was blended through Jet mill/ air classifier mills followed by blending in post blender for a period of ~1.5 hour to obtain a homogeneous mixture. Required quantity of water (qs) was then added to make a dough. The dough was then passed through the extruder to obtain granules of required size. Wet granules as obtained were passed through the fluidised bed drier followed by grading using vibrating screens to obtain the water dispersible granules.
A stable Wettable Powder (WP) of Mepiquat Chloride and Clothianidin according to the present invention was prepared as follows:
WP ( Wettable Powder)
Sr. No. Component Composition
1 2 3 4 5
1. 2 Mepiquat Chloride 15 35 10 0.5 20
2. 3 Clothianidin 65 25 0.5 30 30
3. 4 Sodium Polycarboxylate 3.00 3.00 3.00 3.00 3.00
4. 5 Sodium Lauryl Sulfate 4.00 4.00 4.00 4.00 4.00
5. 6 Sodium alkyl naphthalene sulfonate blend 1.00 1.00 1.00 1.00 1.00
6. 7 Sodium alkylnaphthalenesulfonate, formaldehyde condensate 0.50 0.50 0.50 0.50 0.50
7. 8 Silicone based antifoam 0.10 0.10 0.10 0.10 0.10
8. 9 Starch 5.00 5.00 5.00 5.00 5.00
9. 10 Lactose anhydrous 0.10 0.10 0.10 0.10 0.10
10. 11 China Clay QS to Make 100 QS to Make 100 QS to Make 100 QS to Make 100 QS to Make 100
Example 6:
Sr. No. Recipe % w/w
1. Mepiquat Chloride Technical 15.00%
2. Clothianidin Technical 65.00%
3. Dispersing Agent-Sodium ligno sulfonate 3.00
4. Wetting Agent-Sodium Lauryl Sulfate 4.00
5. Dispersing Agent Sodium alkyl naphthalene sulfonate blend 1.00
6. Antifoam-Polydimethyl Siloxane 0.10
7. Filler-China Clay QS to Make 100
Process: Required quantity of filler, wetting agent, dispersing agent, and suspending agent, & technical were charged in premixing blender for homogenization for a period of 30 minutes to obtain a pre-blended material. The pre-blended material was grinded through Jet mill/ air classifier mills followed by blending in post blender for a period of ~1.5 hr to obtain a homogeneous material. The homogenous material as obtained was unloaded and analysed.
A stable Oil Dispersion (OD) of Mepiquat Chloride and Clothianidin according to the present invention was prepared as follows:
OD(Oil Dispersion)
Sr. No. Component Composition
1 2 3 4 5
1. Mepiquat Chloride 35 20 5 10 20
2. Clothianidin 10 25 5 20 10
3. Ethoxylated oleyl cetyl alcohol 3.00 3.00 3.00 3.00 3.00
4. Polyalkelene glycol ether 4.00 4.00 4.00 4.00 4.00
5. Polyvinylpyrrolidone 1.00 1.00 1.00 1.00 1.00
6. Calcium alkyl benzen sulfonate 3.00 3.00 3.00 3.00 3.00
7. Castor oil ethoxylates 2.00 2.00 2.00 2.00 2.00
8. Silicone based antifoam 0.10 0.10 0.10 0.10 0.10
9. Propylene glycol 5.00 5.00 5.00 5.00 5.00
10. Soyabean Oil QS to Make 100 QS to Make 100 QS to Make 100 QS to Make 100 QS to Make 100
Example 7:
Sr. No. Recipe % w/w
1. Mepiquat Chloride Technical 35.00%
2. Clothianidin Technical 5%
3. Dispersing Agent- Tristyrylphenol Ethoxylate Amine
salt of phosphate 3%
4. Dispersing Agent-Ethoxylated oleyl cetyl alcohol 3.00
5. Sticking Agent-Polyvinylpyrrolidone 1.00
6. Emulsifier-Calcium alkyl benzen sulfonate 5.00
7. Emulsifier-Castor oil ethoxylates 4.00
8. Antifoam-Polydimethyl Siloxane 0.00
9. Antifreezing Agent- Propylene Glycol 0.00
10. Vegetable Oil-Soyabean Oil Q.s to make 100
Total 100
Process: Required quantity of vegetable oil was charged in a vessel and polyvinyl pyrrolidone was added and mixed well for 30 minutes using high shear homogenizer. Required quantity of wetting agent, dispersing agent & suspending agents were added and homogenised for 45 – 60 minutes using high shear homogeniser. Then all the technicals were added and again homogenised for further 30 minutes. This homogenised material was passed through horizontal bead mill to get required particle size. After completion of grinding cycles, the sample was analysed for particle size.
Evaluation of synergistic effect of pesticidal composition of the present invention
A synergistic effect of two or more products exists whenever the action of an active ingredient combination is greater than the sum of the actions of the individual components. Synergism was calculated by using Colby’s method (Weeds, vol. 15 No. 1 (Jan 1967), pp. 20-2.
The synergistic action expected for a given combination of two active components can be calculated as follows:
XY
E = (X + Y) – ---------
100
Where:
E represents expected percentage of pesticidal control for the combination of the two or three active ingredients at defined doses (for example equal to x, y and z, respectively).
X is the percentage of pesticidal control observed by the compound (Mepiquat chloride in present case) at a defined dose (equal to x).
Y is the percentage of pesticidal control observed by the compound (Clothianidin in present case) at a defined dose (equal to y).
When the percentage of pesticidal control observed for the combination is greater than the expected percentage, there is a synergism effect.
Observed control (%)
Ratio = -----------------------------
Expected control (%)
Ratio of O/E > 1, synergism observed
The present invention is illustrated by way of examples, the examples are meant for illustrative purposes and should not be construed as limiting.
Experiment for Synergistic activity of combination product of present invention:
Example 8:
Field experiment for synergistic activity of Mepiquat chloride (a plant growth regulator) and Clothianidin (a translaminar and systemic insecticide) for the control of whitefly (Bemisia tabaci) and leafhopper (Amrasca biguttula biguttula) in cotton crop and effect on fruiting bodies formation (squares and bolls) due to suppression of vegetative growth and subsequently resulting in higher reproductive growth of the crop by Mepiquat chloride was conducted at farmer field, Sonipat (Haryana).
To evaluate the synergistic effect, cotton (Variety: RCH 776 BG II) crop was sown in 4 m x 5 m plots maintaining 30 cm x 50 cm plant distance with three replications and in Randomized Block Design (RBD) during July to December, 2021. The treatments were applied as foliar spray in the form of SC formulation @ 150 ml/ha on initiation of pest incidence and repeat application was done at 15 days interval. The active components were applied at 4-5 doses in different binary combinations. Solo components were also taken for comparison. The treatment details are as under:
T1 – Mepiquat chloride + Clothianidin (0.5%+65%)
T2 – Mepiquat chloride + Clothianidin (10%+50%)
T3 – Mepiquat chloride + Clothianidin (15%+30%)
T4 – Mepiquat chloride + Clothianidin (15%+10%)
T5 – Mepiquat chloride + Clothianidin (35%+0.5%)
T6 – Mepiquat chloride (0.5%)
T7 – Mepiquat chloride (10%)
T8 – Mepiquat chloride (15%)
T9 – Mepiquat chloride (35%)
T10 – Clothianidin (0.5%)
T11 – Clothianidin (10%)
T12 – Clothianidin (30%)
T13 – Clothianidin (50%)
T14 – Clothianidin (65%)
T15 – Untreated check
The treatments T1 to T14 were applied as foliar spray and in T15 control treatment only water was sprayed. The application was done by knapsack sprayer fitted with hollow cone nozzle and 500 lit water/ha. The observations for whitefly and leafhopper control were recorded before first spray and at 3, 7 and 14 days after each spray by observing three leaves of randomly selected ten random plants per plot. The observations on fruiting bodies formation (squares and bolls) were recorded before first spray and 14 days after each spray on 10 plants per plot.
Based on the data recorded per cent reduction in whitefly and leafhopper population and per cent increase in fruiting bodies formation were also calculated over control. Based on the per cent reduction in whitefly and leafhopper population at 14 days after second spray and per cent increase in fruiting bodies formation 14 days after second spray the Expected control was calculated and compared with Observed control. The results of the trial have been presented here under in Table 1 to 3.
Table 1: Synergistic effect of composition of the present invention (Mepiquat chloride + Clothianidin) against whitefly in cotton crop
S. No. Treatment Formulation Observed per cent control Expected per cent control Colby Ratio
T1 Mepiquat chloride + Clothianidin 0.5% + 65% 60.23 4.45 13.532
T2 Mepiquat chloride + Clothianidin 10% + 50% 62.50 4.58 13.645
T3 Mepiquat chloride + Clothianidin 15% + 30% 63.64 4.64 13.700
T4 Mepiquat chloride + Clothianidin 15% + 10% 55.68 4.74 11.741
T5 Mepiquat chloride + Clothianidin 35% + 0.5% 43.18 4.74 9.105
T6 Mepiquat chloride 0.5% 10.23 -
T7 Mepiquat chloride 10% 12.50 -
T8 Mepiquat chloride 15% 15.91 -
T9 Mepiquat chloride 35% 17.05 -
T10 Clothianidin 0.5% 19.32 -
T11 Clothianidin 10% 20.45 -
T12 Clothianidin 30% 23.86 -
T13 Clothianidin 50% 29.55 -
T14 Clothianidin 65% 36.36 -
T15 Untreated control - - - -
Table 2: Synergistic effect of composition of the present invention (Mepiquat chloride + Clothianidin) against leafhopper in cotton crop
S. No. Treatment Formulation Observed per cent control Expected per cent control Colby Ratio
T1 Mepiquat chloride + Clothianidin 0.5% + 65% 56.55 7.24 7.816
T2 Mepiquat chloride + Clothianidin 10% + 50% 60.69 7.20 8.428
T3 Mepiquat chloride + Clothianidin 15% + 30% 63.45 7.26 8.734
T4 Mepiquat chloride + Clothianidin 15% + 10% 56.55 7.33 7.717
T5 Mepiquat chloride + Clothianidin 35% + 0.5% 26.90 7.30 3.687
T6 Mepiquat chloride 0.5% 9.66 -
T7 Mepiquat chloride 10% 15.17 -
T8 Mepiquat chloride 15% 15.86 -
T9 Mepiquat chloride 35% 20.00 -
T10 Clothianidin 0.5% 26.21 -
T11 Clothianidin 10% 29.66 -
T12 Clothianidin 30% 31.03 -
T13 Clothianidin 50% 33.10 -
T14 Clothianidin 65% 37.93 -
T15 Untreated control - - - -
Table 3: Synergistic effect of composition of the present invention (Mepiquat chloride + Clothianidin) on increasing the fruiting bodies formation in cotton crop
S. No. Treatment Formulation Observed per cent increase Expected per cent increase Colby Ratio
T1 Mepiquat chloride + Clothianidin 0.5% + 65% 49.38 39.76 1.242
T2 Mepiquat chloride + Clothianidin 10% + 50% 51.50 39.45 1.305
T3 Mepiquat chloride + Clothianidin 15% + 30% 52.91 39.80 1.329
T4 Mepiquat chloride + Clothianidin 15% + 10% 51.15 39.62 1.291
T5 Mepiquat chloride + Clothianidin 35% + 0.5% 53.44 40.31 1.326
T6 Mepiquat chloride 0.5% 18.34 -
T7 Mepiquat chloride 10% 21.69 -
T8 Mepiquat chloride 15% 25.75 -
T9 Mepiquat chloride 35% 26.63 -
T10 Clothianidin 0.5% 13.93 -
T11 Clothianidin 10% 10.05 -
T12 Clothianidin 30% 11.29 -
T13 Clothianidin 50% 13.05 -
T14 Clothianidin 65% 18.52 -
T15 Untreated control - - - -
It is clearly evident from the data shown in above Tables 1, 2 and 3 for per cent reduction in whitefly and leafhopper population and per cent increase in fruiting bodies formation in cotton crop that the binary composition of the present invention comprising Mepiquat chloride and Clothianidin T1 to T5 are highly synergistic for both the insect pest control and in increasing the fruiting bodies (squares and bolls) formation with > 1 Colby’s Ratio. The binary composition of one plant growth regulator and one insecticide are thus highly effective to control whitefly and leafhopper population and in increasing the fruiting bodies formation as compared to solo formulations of Mepiquat chloride and Clothianidin (T6 to T14).
Experiment for Bio-efficacy evaluation of combination product of present invention:
For the binary composition based on Mepiquat chloride (a plant growth regulator) and Clothianidin (a translaminar and systemic insecticide) evaluation under field conditions, the basic test composition as Mepiquat chloride 15% WDG and Clothianidin 10% WDG were manufactured specifically by the inventor. For binary composition, Mepiquat chloride 15% + Clothianidin 10% WDG was used. The solo formulations of Mepiquat chloride 15% WDG and Clothianidin 10% WDG were used for comparison. The solo formulation of Mepiquat chloride 5% AS and Clothianidin 50% WDG available in the market were also used for better comparison.
Example 9: Evaluation of the composition of the present invention on cotton
The synergistic composition of the present invention Mepiquat chloride 15% + Clothianidin 10% WDG @ 200, 240 and 300 g/ha along with different solo formulations were evaluated on cotton crop variety RCH 776 BG II. The experiment was conducted at a farmer field, Sonipat following Randomized Block Design (RBD) with three replications and maintaining a distance of 30 cm x 50 cm between plants and rows. The application of treatments was started with the initiation of insect pests, whitefly (Bemisia tabaci) and leafhopper (Amrasca biguttula biguttula) incidence on the crop in experimental plots by knapsack sprayer fitted with hollow cone nozzle and 500 lit water/ha.
The observations were recorded for the following objectives.
Objectives:
1. Bio-efficacy evaluation against whitefly control on cotton crop
2. Bio-efficacy evaluation against leafhopper control in cotton crop
3. Bio-efficacy evaluation for fruiting bodies formation
4. Bio-efficacy evaluation based on per cent reduction in whitefly population
5. Bio-efficacy evaluation based on per cent reduction in leafhopper population
6. Bio-efficacy evaluation based on per cent increase in fruiting bodies formation
7. Bio-efficacy evaluation based on cotton yield
8. Effect on natural enemies
9. Phytotoxicity evaluation on cotton crop
10. Economics of treatments based on Cost: Benefit Ratio
Treatment details:
T1 - Mepiquat chloride 15% + Clothianidin 10% WDG @ 200 g/ha
T2 - Mepiquat chloride 15% + Clothianidin 10% WDG @ 240 g/ha
T3 - Mepiquat chloride 15% + Clothianidin 10% WDG @ 300 g/ha
T4 - Mepiquat chloride 15% WDG @ 200 g/ha
T5 - Mepiquat chloride 15% WDG @ 240 g/ha
T6 - Mepiquat chloride 15% WDG @ 300 g/ha
T7 - Clothianidin 10% WDG @ 200 g/ha
T8 - Clothianidin 10% WDG @ 240 g/ha
T9 - Clothianidin 10% WDG @ 300 g/ha
T10 – Mepiquat chloride 5% AS @ 1250 ml/ha
T11 – Clothianidin 50% WDG @ 50 g/ha
T12 – Untreated control
T13 - Mepiquat chloride 15% + Clothianidin 10% WDG @ 600 g/ha
(For phytotoxicity evaluation)
Methodology:
The treatments T1 to T11 and T13 were applied as foliar spray and in T12 control treatment only water was sprayed. Further repeat application was done at 15 days interval. However, in the treatment T10 only one spray was done as per CIB&RC recommendation. The observations for whitefly and leafhopper population were recorded before first spray and at 3, 7 and 14 days after each spray by observing three leaves of randomly selected ten random plants per plot. The observations on fruiting bodies formation were recorded before first spray and 14 days after each spray on 10 plants per plot.
Based on the data recorded, per cent reduction in whitefly and leafhopper population and per cent increase in fruiting bodies formation were calculated over control. The crop yield was recorded plot wise at each harvest and cumulative yield expressed as q/ha. The observations for impact of treatments on natural ebonies were recorded before first spray and at 3 and 7 days after each spray and for phytotoxicity symptoms on cotton at 1, 3, 7 and 10 days after each spray. Based on treatment application cost, market price of produce and net profit, the Cost: Benefit Ratio was calculated for the economics of treatments. The data were subjected to statistically analysis of variance. Results are presented in Tables 4 to 12.
Results:
The results for whitefly and leafhopper control and fruiting bodies formation recorded during the experimental period and per cent reduction in whitefly population and per cent increase in fruiting bodies formation over control are summarized in Table 4 to 8. The data on yield is presented in Table 9. The observations recorded for natural enemies and phytotoxicity symptoms are presented in Tables 10 to 12.
Table 4: Field bio-efficacy evaluation of Mepiquat chloride 15% + Clothianidin 10% WDG against whitefly population on cotton crop
S. No. Treatment A.I. dose (g/ha) Formu lation dose (ml or g/ha) Whitefly population/plant
Before spray Days after I spray Days after II spray
3 7 14 3 7 14
T1 Mepiquat chloride 15% + Clothianidin 10% WDG 30 + 20 200 4.13 (2.03) 1.83 (1.35) 1.33 (1.15) 1.63 (1.28) 1.20 (1.08) 0.73 (0.85) 0.47 (0.67)
T2 Mepiquat chloride 15% + Clothianidin 10% WDG 36 + 24 240 4.53 (2.12) 1.50 (1.22) 1.00 (0.99) 1.27 (1.12) 0.97 (0.98) 0.57 (0.75) 0.33 (0.57)
T3 Mepiquat chloride 15% + Clothianidin 10% WDG 45 + 30 300 4.37 (2.09) 1.43 (1.18) 0.93 (0.95) 1.13 (1.06) 0.80 (0.88) 0.40 (0.62) 0.27 (0.51)
T4 Mepiquat chloride 15% WDG 30 200 4.70 (2.17) 4.40 (2.09) 4.07 (2.02) 4.63 (2.15) 4.77 (2.18) 4.23 (2.06) 2.50 (1.58)
T5 Mepiquat chloride 15% WDG 36 240 3.97 (1.99) 4.27 (2.07) 3.87 (1.97) 4.43 (2.10) 4.57 (2.14) 4.20 (2.05) 2.37 (1.54)
T6 Mepiquat chloride 15% WDG 45 300 3.80 (1.95) 4.13 (2.03) 3.80 (1.95) 4.37 (2.09) 4.43 (2.10) 4.10 (2.02) 2.30 (1.52)
T7 Clothianidin 10% WDG 20 200 4.20 (2.05) 2.63 (1.62) 2.13 (1.46) 2.63 (1.62) 2.40 (1.55) 1.53 (1.24) 1.07 (1.03)
T8 Clothianidin 10% WDG 24 240 4.77 (2.18) 2.43 (1.56) 1.93 (1.39) 2.40 (1.55) 2.07 (1.44) 1.13 (1.06) 0.70 (0.84)
T9 Clothianidin 10% WDG 30 300 4.40 (2.10) 2.17 (1.47) 1.67 (1.29) 2.10 (1.45) 1.67 (1.29) 1.07 (1.03) 0.67 (0.81)
T10 Mepiquat chloride 5% AS 62.5 1250 4.63 (2.15) 4.33 (2.08) 4.17 (2.04) 4.60 (2.14) 4.60 (2.14) 4.20 (2.05) 2.63 (1.62)
T11 Clothianidin 50% WDG 25 50 4.63 (2.15) 2.33 (1.53) 1.83 (1.35) 2.37 (1.54) 1.80 (1.34) 1.20 (1.09) 0.73 (0.85)
T12 Untreated control - - 4.47 (2.11) 5.07 (2.25) 5.63 (2.37) 6.10 (2.47) 6.63 (2.58) 5.30 (2.30) 4.03 (2.01)
S Em ± 0.06 0.07 0.06 0.05 0.06 0.05 0.06
CD (P=0.05) NS 0.20 0.16 0.14 0.19 0.16 0.16
Figures in parentheses are square root transformed values (x + 0.5) NS – Non significant
Table 5: Field bio-efficacy evaluation of Mepiquat chloride 15% + Clothianidin 10% WDG based on whitefly population reduction on cotton crop
S. No. Treatment A.I. dose (g/ha) Formu lation dose (ml or g/ha) Per cent reduction in whitefly population
Days after I spray Days after II spray
3 7 14 3 7 14
T1 Mepiquat chloride 15% + Clothianidin 10% WDG 30 + 20 200 63.82 76.33 73.22 81.91 86.16 89.43
T2 Mepiquat chloride 15% + Clothianidin 10% WDG 36 + 24 240 70.39 82.25 79.23 85.43 89.31 91.74
T3 Mepiquat chloride 15% + Clothianidin 10% WDG 45 + 30 300 71.71 83.43 81.42 87.94 92.45 93.39
T4 Mepiquat chloride 15% WDG 30 200 13.16 27.81 24.04 28.14 20.13 38.02
T5 Mepiquat chloride 15% WDG 36 240 15.79 31.36 27.32 31.16 20.75 41.32
T6 Mepiquat chloride 15% WDG 45 300 18.42 32.54 28.42 33.17 22.64 42.98
T7 Clothianidin 10% WDG 20 200 48.03 62.13 56.83 63.82 71.07 73.55
T8 Clothianidin 10% WDG 24 240 51.97 65.68 60.66 68.84 78.62 82.64
T9 Clothianidin 10% WDG 30 300 57.24 70.41 65.57 74.87 79.87 83.47
T10 Mepiquat chloride 5% AS 62.5 1250 14.47 26.04 24.59 30.65 20.75 34.71
T11 Clothianidin 50% WDG 25 50 53.95 67.46 61.20 72.86 77.36 81.82
T12 Untreated control - - - - - - - -
Table 6: Field bio-efficacy evaluation of Mepiquat chloride 15% + Clothianidin 10% WDG against leafhopper population on cotton crop
S. No. Treatment A.I. dose (g/ha) Formu lation dose (ml or g/ha) Leafhopper population/plant
Before spray Days after I spray Days after II spray
3 7 14 3 7 14
T1 Mepiquat chloride 15% + Clothianidin 10% WDG 30 + 20 200 3.57 (1.89) 1.43 (1.20) 1.30 (1.14) 1.53 (1.24) 1.03 (1.01) 0.80 (0.89) 0.60 (0.79)
T2 Mepiquat chloride 15% + Clothianidin 10% WDG 36 + 24 240 3.93 (1.98) 1.13 (1.06) 0.97 (0.98) 1.20 (1.09) 0.77 (0.86) 0.57 (0.74) 0.40 (0.63)
T3 Mepiquat chloride 15% + Clothianidin 10% WDG 45 + 30 300 4.13 (2.03) 1.03 (1.00) 0.80 (0.89) 0.97 (0.98) 0.60 (0.76) 0.43 (0.65) 0.30 (0.54)
T4 Mepiquat chloride 15% WDG 30 200 3.97 (1.99) 4.03 (2.01) 4.07 (2.01) 4.33 (2.08) 4.13 (2.03) 3.67 (1.91) 2.67 (1.63)
T5 Mepiquat chloride 15% WDG 36 240 3.60 (1.90) 3.90 (1.97) 3.87 (1.96) 4.13 (2.03) 3.93 (1.98) 3.50 (1.87) 2.53 (1.59)
T6 Mepiquat chloride 15% WDG 45 300 3.63 (1.90) 3.70 (1.92) 3.77 (1.94) 4.07 (2.01) 3.87 (1.97) 3.43 (1.85) 2.47 (1.57)
T7 Clothianidin 10% WDG 20 200 3.70 (1.92) 2.30 (1.52) 1.77 (1.33) 2.33 (1.53) 1.90 (1.38) 1.47 (1.21) 1.03 (1.01)
T8 Clothianidin 10% WDG 24 240 4.07 (2.01) 2.00 (1.41) 1.63 (1.28) 2.10 (1.45) 1.70 (1.30) 1.27 (1.12) 0.70 (0.84)
T9 Clothianidin 10% WDG 30 300 3.87 (1.97) 1.83 (1.35) 1.33 (1.15) 1.80 (1.34) 1.47 (1.21) 1.07 (1.03) 0.67 (0.81)
T10 Mepiquat chloride 5% AS 62.5 1250 4.10 (2.02) 3.93 (1.98) 4.03 (2.01) 4.30 (2.07) 4.17 (2.04) 3.60 (1.90) 2.73 (1.65)
T11 Clothianidin 50% WDG 25 50 3.93 (1.98) 2.10 (1.45) 1.70 (1.30) 2.07 (1.44) 1.77 (1.33) 1.30 (1.14) 0.77 (0.87)
T12 Untreated control - - 3.90 (1.97) 4.83 (2.20) 5.53 (2.35) 5.80 (2.41) 5.27 (2.29) 4.57 (2.14) 4.10 (2.02)
S Em ± 0.05 0.06 0.06 0.05 0.05 0.05 0.05
CD (P=0.05) NS 0.17 0.16 0.14 0.16 0.14 0.13
Figures in parentheses are square root transformed values (x + 0.5) NS – Non significant
Table 7: Field bio-efficacy evaluation of Mepiquat chloride 15% + Clothianidin 10% WDG based on leafhopper population reduction on cotton crop
S. No. Treatment A.I. dose (g/ha) Formu lation dose (ml or g/ha) Per cent reduction in leafhopper population
Days after I spray Days after II spray
3 7 14 3 7 14
T1 Mepiquat chloride 15% + Clothianidin 10% WDG 30 + 20 200 70.34 76.51 73.56 80.38 82.48 88.55
T2 Mepiquat chloride 15% + Clothianidin 10% WDG 36 + 24 240 76.55 82.53 79.31 85.44 87.59 90.24
T3 Mepiquat chloride 15% + Clothianidin 10% WDG 45 + 30 300 78.62 85.54 83.33 88.61 90.51 92.68
T4 Mepiquat chloride 15% WDG 30 200 16.55 26.51 25.29 21.52 19.71 34.96
T5 Mepiquat chloride 15% WDG 36 240 19.31 30.12 28.74 25.32 23.36 38.21
T6 Mepiquat chloride 15% WDG 45 300 23.45 31.93 29.89 26.58 24.82 39.84
T7 Clothianidin 10% WDG 20 200 52.41 68.07 59.77 63.92 67.88 74.80
T8 Clothianidin 10% WDG 24 240 58.62 70.48 63.79 67.72 72.26 82.93
T9 Clothianidin 10% WDG 30 300 62.07 75.90 68.97 72.15 76.64 83.74
T10 Mepiquat chloride 5% AS 62.5 1250 18.62 27.11 25.86 20.89 21.17 33.33
T11 Clothianidin 50% WDG 25 50 56.55 69.28 64.37 66.46 71.53 81.30
T12 Untreated control - - - - - - - -
Table 8: Field bio-efficacy evaluation of Mepiquat chloride 15% + Clothianidin 10% WDG based on fruiting bodies formation in cotton crop
S. No. Treatment A.I. dose (g/ha) Formulation dose (ml or g/ha) Number of fruiting bodies formed/plant Per cent increase in fruiting bodies formation
Before spray 14 days after I spray 14 days after II spray 14 days after I spray 14 days after II spray
T1 Mepiquat chloride 15% + Clothianidin 10% WDG 30 + 20 200 14.60 (3.82) 25.73 (5.07) 36.33 (6.03) 40.36 51.39
T2 Mepiquat chloride 15% + Clothianidin 10% WDG 36 + 24 240 13.67 (3.70) 26.97 (5.19) 38.07 (6.17) 47.09 58.61
T3 Mepiquat chloride 15% + Clothianidin 10% WDG 45 + 30 300 15.13 (3.89) 27.63 (5.26) 39.00 (6.24) 50.73 62.50
T4 Mepiquat chloride 15% WDG 30 200 14.00 (3.74) 22.87 (4.78) 31.63 (5.62) 24.73 31.81
T5 Mepiquat chloride 15% WDG 36 240 14.67 (3.82) 23.40 (4.84) 32.23 (5.68) 27.64 34.31
T6 Mepiquat chloride 15% WDG 45 300 13.07 (3.61) 24.40 (4.94) 33.00 (5.74) 33.09 37.50
T7 Clothianidin 10% WDG 20 200 14.40 (3.79) 23.70 (4.87) 32.60 (5.71) 29.27 35.83
T8 Clothianidin 10% WDG 24 240 14.17 (3.76) 24.57 (4.96) 33.57 (5.79) 34.00 39.86
T9 Clothianidin 10% WDG 30 300 14.47 (3.80) 25.40 (5.04) 34.50 (5.87) 38.55 43.75
T10 Mepiquat chloride 5% AS 62.5 1250 14.80 (3.85) 24.43 (4.94) 32.33 (5.69) 33.27 34.72
T11 Clothianidin 50% WDG 25 50 14.03 (3.74) 25.07 (5.01) 35.10 (5.92) 36.73 46.25
T12 Untreated control - - 13.67 (3.70) 18.33 (4.27) 24.00 (4.90) - -
S Em ± 0.11 0.10 0.07
CD (P=0.05) NS 0.29 0.19
Figures in parentheses are square root transformed values (x + 0.5) NS – Non significant
Table 9: Field bio-efficacy evaluation of Mepiquat chloride 15% + Clothianidin 10% WDG based on cotton yield and Cost: Benefit Ratio
S. No. Treatment A.I. dose (g/ ha) Formulation dose (ml or g/ha) Yield (q/ha) Per cent increase in yield over control C : B Ratio
T1 Mepiquat chloride 15% + Clothianidin 10% WDG 30 + 20 200 20.95 (4.58) 44.48 1 : 4.32
T2 Mepiquat chloride 15% + Clothianidin 10% WDG 36 + 24 240 21.78 (4.67) 50.23 1 : 4.90
T3 Mepiquat chloride 15% + Clothianidin 10% WDG 45 + 30 300 22.43 (4.74) 54.71 1 : 5.27
T4 Mepiquat chloride 15% WDG 30 200 17.87 (4.23) 23.22 1 : 1.75
T5 Mepiquat chloride 15% WDG 36 240 18.23 (4.27) 25.75 1 : 2.00
T6 Mepiquat chloride 15% WDG 45 300 18.58 (4.31) 28.16 1 : 2.20
T7 Clothianidin 10% WDG 20 200 19.97 (4.47) 37.70 1 : 3.42
T8 Clothianidin 10% WDG 24 240 20.48 (4.52) 41.26 1 : 3.75
T9 Clothianidin 10% WDG 30 300 20.60 (4.54) 42.07 1 : 3.70
T10 Mepiquat chloride 5% AS 62.5 1250 18.68 (4.32) 28.85 1 : 1.18
T11 Clothianidin 50% WDG 25 50 20.12 (4.48) 38.74 1 : 3.90
T12 Untreated control - - 14.50 (3.80) - -
S Em ± 0.06
CD (P=0.05) 0.18
Figures in parentheses are square root transformed values (x + 0.5)
Table 10: Effect of Mepiquat chloride 15% + Clothianidin 10% WDG on natural enemies (spiders) in cotton crop
S. No. Treatment A.I. dose (g/ha) Formulation dose (ml or g/ha) Spiders population/ plant
Before spray Days after I spray Days after II spray
3 7 3 7
T1 Mepiquat chloride 15% + Clothianidin 10% WDG 30 + 20 200 3.40 (1.83) 3.23 (1.80) 3.17 (1.78) 2.57 (1.60) 2.20 (1.48)
T2 Mepiquat chloride 15% + Clothianidin 10% WDG 36 + 24 240 3.20 (1.79) 3.17 (1.78) 3.33 (1.83) 2.80 (1.67) 2.43 (1.56)
T3 Mepiquat chloride 15% + Clothianidin 10% WDG 45 + 30 300 3.37 (1.83) 2.87 (1.69) 3.00 (1.73) 2.53 (1.59) 2.27 (1.50)
T4 Mepiquat chloride 15% WDG 30 200 3.27 (1.79) 3.03 (1.74) 3.03 (1.74) 2.50 (1.58) 2.00 (1.41)
T5 Mepiquat chloride 15% WDG 36 240 3.10 (1.75) 2.90 (1.70) 2.80 (1.67) 2.47 (1.57) 1.90 (1.37)
T6 Mepiquat chloride 15% WDG 45 300 3.23 (1.80) 2.93 (1.71) 3.03 (1.74) 2.57 (1.60) 2.13 (1.46)
T7 Clothianidin 10% WDG 20 200 3.30 (1.81) 3.10 (1.76) 3.23 (1.80) 2.77 (1.66) 2.10 (1.44)
T8 Clothianidin 10% WDG 24 240 3.00 (1.73) 2.83 (1.68) 2.77 (1.66) 2.33 (1.53) 1.83 (1.35)
T9 Clothianidin 10% WDG 30 300 2.93 (1.69) 2.97 (1.72) 2.97 (1.72) 2.53 (1.59) 2.03 (1.42)
T10 Mepiquat chloride 5% AS 62.5 1250 3.03 (1.73) 2.77 (1.66) 3.10 (1.76) 2.60 (1.61) 1.97 (1.39)
T11 Clothianidin 50% WDG 25 50 3.20 (1.78) 3.00 (1.73) 2.93 (1.71) 2.37 (1.54) 1.87 (1.36)
T12 Untreated control - - 3.17 (1.78) 3.17 (1.78) 3.40 (1.84) 2.93 (1.71) 2.50 (1.58)
S Em ± 0.12 0.05 0.05 0.04 0.07
CD (P=0.05) NS NS NS NS NS
Figures in parentheses are square root transformed values (x + 0.5) NS – Non significant
Table 11: Effect of Mepiquat chloride 15% + Clothianidin 10% WDG on natural enemies (coccinellids) in cotton crop
S. No. Treatment A.I. dose (g/ha) Formulation dose (ml or g/ha) Coccinellids population/ plant
Before spray Days after I spray Days after II spray
3 7 3 7
T1 Mepiquat chloride 15% + Clothianidin 10% WDG 30 + 20 200 3.47 (1.86) 2.83 (1.68) 2.87 (1.69) 2.40 (1.55) 1.97 (1.40)
T2 Mepiquat chloride 15% + Clothianidin 10% WDG 36 + 24 240 3.33 (1.82) 3.03 (1.74) 2.97 (1.72) 2.43 (1.55) 2.03 (1.42)
T3 Mepiquat chloride 15% + Clothianidin 10% WDG 45 + 30 300 3.43 (1.85) 2.77 (1.66) 2.70 (1.64) 2.23 (1.49) 1.90 (1.37)
T4 Mepiquat chloride 15% WDG 30 200 3.50 (1.86) 2.87 (1.69) 2.57 (1.60) 2.17 (1.46) 1.77 (1.32)
T5 Mepiquat chloride 15% WDG 36 240 3.83 (1.95) 2.73 (1.65) 2.63 (1.62) 2.07 (1.43) 1.57 (1.25)
T6 Mepiquat chloride 15% WDG 45 300 3.30 (1.81) 2.77 (1.66) 2.80 (1.67) 2.23 (1.49) 1.73 (1.31)
T7 Clothianidin 10% WDG 20 200 3.37 (1.83) 2.80 (1.67) 2.90 (1.70) 2.40 (1.54) 1.87 (1.36)
T8 Clothianidin 10% WDG 24 240 3.73 (1.93) 2.77 (1.66) 3.13 (1.77) 2.13 (1.46) 1.60 (1.25)
T9 Clothianidin 10% WDG 30 300 3.37 (1.82) 2.67 (1.63) 2.80 (1.67) 2.10 (1.43) 1.70 (1.29)
T10 Mepiquat chloride 5% AS 62.5 1250 3.33 (1.82) 2.73 (1.65) 2.77 (1.66) 2.17 (1.46) 1.87 (1.37)
T11 Clothianidin 50% WDG 25 50 3.27 (1.80) 2.83 (1.68) 2.70 (1.64) 2.07 (1.44) 1.67 (1.29)
T12 Untreated control - - 3.63 (1.91) 3.03 (1.74) 3.10 (1.76) 2.47 (1.56) 2.10 (1.44)
S Em ± 0.11 0.06 0.08 0.11 0.09
CD (P=0.05) NS NS NS NS NS
Figures in parentheses are square root transformed values (x + 0.5) NS – Non significant
Table 12: Phytotoxicity evaluation of Mepiquat chloride 15% + Clothianidin 10% WDG on cotton crop
S. No. Treatment A.I. dose (g/ ha) Formu-lation dose (ml or g/ha) Phytotoxicity parameters observed*
(mean data recorded at 1, 3, 7 and 10 days after each spray)
L W N V E H
T1 Mepiquat chloride 15% + Clothianidin 10% WDG 30 + 20 200 0 0 0 0 0 0
T2 Mepiquat chloride 15% + Clothianidin 10% WDG 36 + 24 240 0 0 0 0 0 0
T3 Mepiquat chloride 15% + Clothianidin 10% WDG 45 + 30 300 0 0 0 0 0 0
T4 Mepiquat chloride 15% WDG 30 200 0 0 0 0 0 0
T5 Mepiquat chloride 15% WDG 36 240 0 0 0 0 0 0
T6 Mepiquat chloride 15% WDG 45 300 0 0 0 0 0 0
T7 Clothianidin 10% WDG 20 200 0 0 0 0 0 0
T8 Clothianidin 10% WDG 24 240 0 0 0 0 0 0
T9 Clothianidin 10% WDG 30 300 0 0 0 0 0 0
T10 Mepiquat chloride 5% AS 62.5 1250 0 0 0 0 0 0
T11 Clothianidin 50% WDG 25 50
T12 Untreated control - - 0 0 0 0 0 0
T13 Mepiquat chloride 15% + Clothianidin 10% WDG 90 + 60 600 0 0 0 0 0 0
L – Leaf injury on tips/ surface, W – Wilting, N – Necrosis, V – Vein clearing, E – Epinasty, H – Hyponasty
*Based on 0-10 scale where: 0=0%, 1=1-10%, 2=11-20%, 3=21-30%, 4=31-40%, 5=41-50%, 6=51-60%, 7=61-70%, 8=71-80%, 9=81-90%,10=91-100%
From the example, it can be clearly seen that the composition of the present invention is superior for controlling the whitefly and leafhopper population at 3, 7 and 14 days after each spray (Table 4 to 7). Also, the number of fruiting bodies formation increased when observed at 14 days after first and second spray (Table 8). Thus, the effectiveness of binary composition on cotton crop was superior over solo component comprising Mepiquat chloride 15% WDG and Clothianidin 10% WDG at different dosage levels. Other registered formulated product available in the market, Mepiquat chloride 5% AS and Clothianidin 50% WDG evaluated were also less effective to binary combination products. The yield of cotton also improved in the binary combination of Mepiquat chloride 15% + Clothianidin 10% WDG as compared to solo components (Table 9). One of the reasons of higher crop yield is due to better control of insect pests and improved fruiting bodies formation. The Cost: Benefit Ratio revealed that binary composition of present invention: Mepiquat chloride 15% + Clothianidin 10% WDG @ 240 g/ha and 300 g/ha were most economical with higher Cost: Benefit Ratio as compared to solo treatments (Table 9).
The disclosed composition Mepiquat chloride 15% + Clothianidin 10% WDG showed no adverse impact on the natural enemies (spiders and coccinellids) most prevailing in the cotton crop ecosystem being the population significantly at par with control and solo treatments before first spray and at 3 and 7 days after each spray (Table 10 and 11). Mepiquat chloride 15% + Clothianidin 10% WDG applied @ 200, 240, 300 and 600 g/ha also showed no phytotoxicity to the cotton crop when observed at 1, 3, 7 and 10 days after each spray (Table 12).
It is evident from the above tables of examples that the composition of the present invention Mepiquat chloride 15% + Clothianidin 10% WDG resulted in efficient control of whitefly and leafhopper population and in increasing the fruiting bodies formation with higher yield as compared to the reference standard products solo formulations of Mepiquat chloride 15% WDG and Clothianidin 10% WDG and also market available solo formulation of these products (Mepiquat chloride 5% AS and Clothianidin 50% WDG). The Cost: Benefit Ratio also showed that binary composition Mepiquat chloride 15% + Clothianidin 10% WDG @ 240 and 300 g/ha was most economical with higher Cost: Benefit Ratio as compared to solo treatments. Further, the composition of present invention is resulted synergistic.
From the above investigations, it will be observed that numerous modifications and variations can be effectuated without departing from the true spirit and scope of the novel concepts of the present invention. It is to be understood that no limitations with respect to the specific embodiments illustrated is intended or should be inferred. It should be understood that all such modifications and improvements have been deleted herein for the sake of conciseness and readability but are properly within the scope of the following claims.
We Claim:
1. A synergistic pesticidal composition comprising at least one neonicotinoid insecticide, at least one plant growth regulator, with one or more agriculturally acceptable excipients, wherein the neonicotinoid insecticide is selected from Clothianidin, Dinotefuran, Imidacloprid, Imidaclothiz, Thiamethoxam, Nitenpyram, Nithiazine, Acetamiprid, Cycloxaprid, and Thiacloprid or its agrochemically acceptable salts.
2. The synergistic pesticidal composition as claimed in claim 1, wherein the neonicotinoid insecticide is in range of 0.5 % to 65% by weight of the composition.
3. The synergistic pesticidal composition as claimed in claim 1, wherein the plant growth regulator is in range of 0.5 % to 35% by weight of the composition.
4. The synergistic pesticidal composition as claimed in claim 1, wherein the plant growth regulator is selected from Mepiquat Chloride, Chlormequat Chloride and Paclobutrazol or its agrochemically acceptable salts.
5. The synergistic pesticidal composition as claimed in claim 1, wherein the agriculturally acceptable excipients are selected from the group comprising surfactants/dispersing agents, polymers, anti-freezing agent, wetting agents, anti-foaming agents, colorants, pigments, protective colloids, adhesives, binder/structuring agents, biocides/anti-microbial agent, thickeners, emulsifiers, buffering agent, fillers, diluents/solvents, quick coating agents or sticking agents, stabilizers, sequestering agents penetration agents, preservatives, adjuvants and solvents or a combination thereof.
6. The synergistic pesticidal composition as claimed in claim 1, wherein the composition is in form selected from Capsule suspension (CS), Dispersible concentrate (DC), Dustable powder (DP), Powder for dry seed treatment (DS), Emulsifiable concentrate (EC), Emulsifiable granule (EG), Emulsion water-in-oil (EO), Emulsifiable powder (EP), Emulsion for seed treatment (ES), Emulsion oil-in-water (EW), Flowable concentrate for seed treatment (FS), Granules (GR), Micro-emulsion (ME), Oil-dispersion (OD), Oil miscible flowable concentrate (OF), Oil miscible liquid (OL), Oil dispersible powder (OP), Suspension concentrate (SC), Suspension concentrate for direct application (SD), Suspo-emulsion (SE), Water soluble granule (SG), Soluble concentrate (SL), Spreading oil (SO), Water soluble powder (SP), Water soluble tablet (ST), Ultra-low volume (ULV) suspension, Tablet (TB), Ultra-low volume (ULV) liquid, Water dispersible granules (WG), Wettable powder (WP), Water dispersible powder for slurry seed treatment (WS), Water dispersible tablet (WT), a mixed formulation of CS and SC (ZC) or a mixed formulation of CS and SE (ZE) and a mixed formulation of CS and EW (ZW).
7. The synergistic pesticidal composition as claimed in claim 1, wherein the composition comprises of:
d. Clothianidin or its agrochemically acceptable salts in an amount in the range from 0.5 to 65% by weight of the composition;
e. at least one plant growth regulator or its agro chemically acceptable salts in an amount in the range from 0.5 % to 35% by weight of the composition; and
f. at least one agriculturally acceptable excipients.
8. The synergistic pesticidal composition as claimed in claim 1, wherein the composition comprises of:
a. Dinotefuran or its agrochemically acceptable salts in an amount in the range from 0.5 to 65% by weight of the composition;
b. at least one plant growth regulator or its agro chemically acceptable salts in an amount in the range from 0.5 % to 35% by weight of the composition; and
c. at least one agriculturally acceptable excipients.
9. A method for pest control comprising applying to the plant or portion thereof or soil, a pesticidal effective amount of the composition as claimed in any one of the claims 1 – 8.
10. A method of improving vigour or yield of the plant comprising, treating a plant or portion thereof or soil, a pesticidal effective amount of the composition as claimed in any one of the claims 1 – 8.
11. The method as claimed in claim 9 or 10, wherein the plant is selected from the group consisting of cereals, field crops, seeds, oil seeds, pulses, fruits, tree nuts, vegetables, turf grasses, potatoes, tomatoes, grapes cotton, ornamentals, horticulture, forestry and veterinary,
12. A process for preparing a stable synergistic pesticidal composition as claimed in claims 1-11.
| # | Name | Date |
|---|---|---|
| 1 | 202111038280-STATEMENT OF UNDERTAKING (FORM 3) [24-08-2021(online)].pdf | 2021-08-24 |
| 2 | 202111038280-PROVISIONAL SPECIFICATION [24-08-2021(online)].pdf | 2021-08-24 |
| 3 | 202111038280-POWER OF AUTHORITY [24-08-2021(online)].pdf | 2021-08-24 |
| 4 | 202111038280-FORM FOR SMALL ENTITY(FORM-28) [24-08-2021(online)].pdf | 2021-08-24 |
| 5 | 202111038280-FORM FOR SMALL ENTITY [24-08-2021(online)].pdf | 2021-08-24 |
| 6 | 202111038280-FORM 1 [24-08-2021(online)].pdf | 2021-08-24 |
| 7 | 202111038280-EVIDENCE FOR REGISTRATION UNDER SSI(FORM-28) [24-08-2021(online)].pdf | 2021-08-24 |
| 8 | 202111038280-EVIDENCE FOR REGISTRATION UNDER SSI [24-08-2021(online)].pdf | 2021-08-24 |
| 9 | 202111038280-DECLARATION OF INVENTORSHIP (FORM 5) [24-08-2021(online)].pdf | 2021-08-24 |
| 10 | 202111038280-COMPLETE SPECIFICATION [24-08-2022(online)].pdf | 2022-08-24 |
| 11 | 202111038280-COMPLETE SPECIFICATION [24-08-2022(online)]-1.pdf | 2022-08-24 |
| 12 | 202111038280-MSME CERTIFICATE [09-11-2023(online)].pdf | 2023-11-09 |
| 13 | 202111038280-FORM28 [09-11-2023(online)].pdf | 2023-11-09 |
| 14 | 202111038280-FORM 18A [09-11-2023(online)].pdf | 2023-11-09 |
| 15 | 202111038280-FER.pdf | 2023-11-14 |
| 16 | 202111038280-FORM 3 [30-04-2024(online)].pdf | 2024-04-30 |
| 17 | 202111038280-FER_SER_REPLY [10-05-2024(online)].pdf | 2024-05-10 |
| 18 | 202111038280-CLAIMS [10-05-2024(online)].pdf | 2024-05-10 |
| 19 | 202111038280-US(14)-HearingNotice-(HearingDate-10-07-2024).pdf | 2024-06-04 |
| 20 | 202111038280-Correspondence to notify the Controller [27-06-2024(online)].pdf | 2024-06-27 |
| 21 | 202111038280-US(14)-ExtendedHearingNotice-(HearingDate-30-07-2024).pdf | 2024-07-09 |
| 22 | 202111038280-Correspondence to notify the Controller [27-07-2024(online)].pdf | 2024-07-27 |
| 23 | 202111038280-Correspondence to notify the Controller [27-07-2024(online)]-1.pdf | 2024-07-27 |
| 24 | 202111038280-Written submissions and relevant documents [13-08-2024(online)].pdf | 2024-08-13 |
| 25 | 202111038280-Written submissions and relevant documents [15-08-2024(online)].pdf | 2024-08-15 |
| 26 | 202111038280-Retyped Pages under Rule 14(1) [16-08-2024(online)].pdf | 2024-08-16 |
| 27 | 202111038280-2. Marked Copy under Rule 14(2) [16-08-2024(online)].pdf | 2024-08-16 |
| 28 | 202111038280-PatentCertificate29-08-2024.pdf | 2024-08-29 |
| 29 | 202111038280-IntimationOfGrant29-08-2024.pdf | 2024-08-29 |
| 1 | SearchHistoryE_13-11-2023.pdf |