DESC:FIELD OF THE INVENTION
[0001] The present disclosure relates to technical field of agricultural insecticide. In particular, the present disclosure relates to a new and improved formulation comprising a combination of Lambda-cyhalothrin and Fipronil as active ingredients, along with one or more agrochemical excipients, for protecting agricultural crops from various insects, and to method of preparing such formulation.

BACKGROUND OF THE INVENTION
[0002] Background description includes information that may be useful in understanding the present invention. It is not an admission that any of the information provided herein is prior art or relevant to the presently claimed invention, or that any publication specifically or implicitly referenced is prior art.
[0003] Lambda-cyhalothrin (CAS Registry No. 91465-08-6) is a mixture of isomers of cyhalothrin, and is an environmental protection agency (EPA)-registered insecticide that is similar to the pyrethroid cyhalothrin and particularly useful as an insecticide. Lambda-cyhalothrin is a colorless-to-beige solid with a mild odour, having low water solubility and low volatility. Lambda-cyhalothrin has the following chemical structure:

[0004] Lambda-cyhalothin is obtained from cyhalothrin, which is produced as a mixture of four isomers in approximately equal amounts, the two isomers constituting lambda-cyhalothrin and the epimers of these two isomers, that is R-a-cyano-3-phenoxybenzyl 1R,3R-3-(Z-2-chloro-3,3,3-trifluoroprop-1-en-1-yl)-2,2-cyclopropane carboxylate and its enantiomer, respectively. Lambda-cyhalothrin, its preparation and its insecticidal use is described inter alia in EP Patent Publication No. 0107296.

[0005] Like other pyrethroids, Lambda-cyhalothrin repels insects and affects a large variety of insects that consume or otherwise come into contact with the chemical. A large number of products contain Lambda-cyhalothrin as active ingredient, including indoor and outdoor insecticides, such as agricultural insecticides for crops; insecticides for home, hospital, and other closed environments; greenhouse, ornamental plant and lawn insecticides; termite treatments; and animal treatments.
[0006] PCT Publication No. WO2013133731 teaches an agrochemical formulation for the control of insects, which comprises a combined formulation of microencapsulated Lambda-cyhalothrin with suspended particles of Imidacloprid. In the WO2013133731, the two insecticides, Lambda- cyhalothrin and Imidacloprid are combined in a ZC formulation.US Patent Publication No. 9072302 discloses a pesticidal composition comprising a combination of Lambda-cyhalothrin and Diafenthiuron for protecting agricultural crops and plants from pests and insects such as, white flies, affids, lepidoptera, jassids etc. US9072302 discloses that the combination of Lambda-cyhalothrin and Diafenthiuron can be prepared in the form of emulsion concentrates, wettable powders, suspoemulsions, microemulsions, capsulated suspension, water dispersible granules, ZC composition, pellets, seed dressings or emulsions for seed treatment, broadcast granules, gel and emulsion in water or oil dispersions.
[0007] Fipronil is a broad use insecticide that belongs to the phenyl-pyrazole chemical family. Fipronil selectively acts by blocking GABA-gated chloride channels of neurons in central nervous system and causes neural excitation and convulsions in insects, resulting in death. Fipronil was discovered and developed by Rhone-Poulenc between 1985 and 1987 and placed on the market in 1993. It is mostly used to control ants, beetles, cockroaches, fleas, ticks, termites, mole crickets, thrips, rootworms, weevils, and other insects. The preparation and use of Fipronil was described for example in EP Patent Publication No. 0295117. Fipronil is chemically known as (RS)-5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-(trifluoromethylsulfinyl) pyrazole-3-carbonitrile (CAS Registry No. 120068-37-3), and is represented by the following structural formula:

[0008] Fipronil formulations and Fipronil/S-methoprene co-formulations to combat dog and cat parasites, such as, fleas and ticks are disclosed in US Patent Publication No. 20130116295A1.US Patent Publication No. 20150173360 discloses a composition comprising a synergistic combination of Fipronil and Bifenthrin for use in controlling agricultural insects in a crop or locus thereof, and a method of controlling agricultural insects in a crop employing the composition. US20150173360 teaches that the insecticidal composition containing Fipronil and Bifenthrin can be employed in the form of twin pack, or as emulsion concentrates, suspension concentrates, soluble concentrates, suspoemulsion, oil dispersions, water dispersible granules, water soluble granules and wettable powders.US Patent Publication No. 20100144819 teaches a composition comprising a combination of Fipronil and Bifenthrin, and a method of controlling of non-crop pests, such as cockroaches and spiders using said composition. The composition disclosed in this reference is in the form of simple solution, dispersible solution, wettable powders, water-soluble or water-dispersible granules, free flowing dusts, emulsifiable concentrates, suspension concentrates or micro-encapsulation.
[0009] US Patent Publication No. 20110039907 discloses a composition comprising a mixture of Fipronil and Lambda-cyhalothrin for controlling non-crop pest, namely ant. In this patent reference, the insecticide mixture is formulated in the form of liquid or granules. When the composition is in the form of granules, the Fipronil and Lambda-cyhalothrin insecticides are present in separate granules or prills. Alternatively, the Fipronil and Lambda-cyhalothrin insecticides are co-formulated so that both insecticides are present in the same granules or prills.
[0010] Previous research efforts and achievements notwithstanding, there is a continuing need for new and improved insecticide formulations for agricultural use with higher insecticidal activity, as well as other advantageous properties.
[0011] All publications herein are incorporated by reference to the same extent as if each individual publication or patent application were specifically and individually indicated to be incorporated by reference. Where a definition or use of a term in an incorporated reference is inconsistent or contrary to the definition of that term provided herein, the definition of that term provided herein applies and the definition of that term in the reference does not apply.

OBJECTS OF THE INVENTION
[0012] It is an object of the present disclosure to provide a new and improved agrochemical formulation for protecting agricultural crops from attack by insects.
[0013] It is another object of the present disclosure to provide an insecticide formulation that exhibits excellent insecticidal activities against various agricultural insects.
[0014] It is another object of the present disclosure to provide an agricultural insecticide formulation that has improved safety while maintaining insecticidal efficacy.
[0015] It is another object of the present disclosure to provide an agricultural insecticide formulation that controls environmental damage and imparts protection against a wider variety of insect pests.
[0016] It is another object of the present disclosure to provide a new and improved agricultural insecticide formulation which is more affordable by general public.
[0017] The other objects and preferred embodiments and advantages of the present invention will become more apparent from the following description of the present invention when read in conjunction with the accompanying examples and figures, which are not intended to limit scope of the present invention in any manner.

SUMMARY OF THE INVENTION
[0018] This summary is provided to introduce a selection of concepts in a simplified form that are further described below in Detailed Description section. This summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used as an aid in determining the scope of the claimed subject matter.
[0019] The present invention relates to agricultural insecticide. Specifically, the present invention relates to a new and improved formulation comprising a combination of Lambda-cyhalothrin and Fipronil, along with one or more agrochemical excipients.
[0020] According to one aspect of the present disclosure, there is provided an agrochemical ZC formulation comprising Lambda-cyhalothrin in combination with Fipronil, along with one or more agrochemical excipients, for use in protectingagricultural crops from attack by insects.

[0021] According to another aspect of the present disclosure, the ZC formulation comprises microencapsulated Lambda-cyhalothrin and suspension concentrate of Fipronil along with one or more agrochemical excipients.
[0022] According to another aspect of the present disclosure, the insecticide formulation of the present disclosure can be used to control insects that attack agricultural crops, such as but not limited to chilli, cotton, onion and tomato.
[0023] According to yet another aspect of the present disclosure, the insecticide formulation shows excellent insecticidal effects against various agricultural insects, such as but not limited to thrips, sucking pests and pink bollworm.
[0024] According to still another aspect of the present disclosure, ZC formulation comprising Lambda-cyhalothrin in combination with Fipronil exhibits synergistic effect when compared to the individual use of the mentioned insecticides.
[0025] According to another aspect of the present disclosure, there is provided a method of preparing an agrochemical ZC formulation comprising Lambda-cyhalothrin and Fipronil comprising the steps of:
a) preparing an oil phase by mixing molten Lambda-cyhalothrinwith aromatic hydrocarbon solvent followed by addition of one or more capsule forming agents;
b) preparing an aqueous phase by combining water, an emulsifier, a dispersing agent, biocide and an antifreeze agent;
c) dispersing the oil phase into the aqueous phaseat an elevated temperature using a high shear mixer to form an emulsion;
d) optionally quenching the emulsion with an aqueous ammonia solution;
e) maintaining the emulsion under stirring for a time period ranging from 30 minutes to 5 hours;
f) adjusting the pH in the range of 4.5 to 6.5 and cooling the emulsion to room temperature to obtain microencapsulated Lambda-cyhalothrin;
g) preparing a slurry by combining Fipronil, water, a stabilizing agent, a wetting agent, an antifreeze agent, biocide and a defoamer;
h) wet milling the slurry in a bead mill to form a suspension concentrate of Fipronil;
i) mixing the microencapsulated Lambda-cyhalothrin and the suspension concentrate of Fipronil to form a mix; and
j) adding an adjuvant, water and a viscosity modifier to the mix to obtain the ZC formulation.
[0026] According to another aspect of the present disclosure, there is provided a method of protecting agricultural crops against attack by insects. The method includes applying or spraying an insecticidally effective amountof a ZC formulation comprising microencapsulated Lambda-cyhalothrin and suspension concentrate of Fipronil on crops.
[0027] Other aspects of the invention will be set forth in the description which follows, and in part will be apparent from the description, or may be learnt by the practice of the invention.

BRIEF DESCRIPTION OF DRAWINGS THE INVENTION
[0028] The following drawings form part of the present specification and are included to further illustrate aspects of the present disclosure. The disclosure may be better understood by reference to the drawings in combination with the detailed description of the specific embodiments presented herein.
Figure 1: Flow chart illustrating preparation of Fipronil suspension concentrate (SC).
Figure 2: Flow chart illustrating preparation of microencapsulated Lambda-cyhalothrin (CS).
Figure 3: Flow chart illustrating preparation of ZC formulation comprising Lambda cyhalothrin CS and Fipronil SC.

DETAILED DESCRIPTION
[0029] The following is a detailed description of embodiments of the disclosure. The embodiments are in such detail as to clearly communicate the disclosure. However, the amount of detail offered is not intended to limit the anticipated variations of embodiments; on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the present disclosure as defined by the appended claims.
[0030] All publications herein are incorporated by reference to the same extent as if each individual publication or patent application were specifically and individually indicated to be incorporated by reference. Where a definition or use of a term in an incorporated reference is inconsistent or contrary to the definition of that term provided herein, the definition of that term provided herein applies and the definition of that term in the reference does not apply.
[0031] Reference throughout this specification to “one embodiment” or “an embodiment” means that a particular feature, structure or characteristic described in connection with the embodiment is included in at least one embodiment. Thus, the appearances of the phrases “in one embodiment” or “in an embodiment” in various places throughout this specification are not necessarily all referring to the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
[0032] In some embodiments, the numbers expressing quantities of ingredients, properties such as concentration, reaction conditions, and so forth, used to describe and claim certain embodiments of the invention are to be understood as being modified in some instances by the term “about.”Accordingly, in some embodiments, the numerical parameters set forth in the written description and attached claims are approximations that can vary depending upon the desired properties sought to be obtained by a particular embodiment. In some embodiments, the numerical parameters should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of some embodiments of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as practicable. The numerical values presented in some embodiments of the invention may contain certain errors necessarily resulting from the standard deviation found in their respective testing measurements.
[0033] As used in the description herein and throughout the claims that follow, the meaning of “a,” “an,” and “the” includes plural reference unless the context clearly dictates otherwise. Also, as used in the description herein, the meaning of “in” includes “in” and “on” unless the context clearly dictates otherwise.
[0034] Unless the context requires otherwise, throughout the specification which follow, the word “comprise” and variations thereof, such as, “comprises” and “comprising” are to be construed in an open, inclusive sense that is as “including, but not limited to.”
[0035] The recitation of ranges of values herein is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range. Unless otherwise indicated herein, each individual value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g. “such as”) provided with respect to certain embodiments herein is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention otherwise claimed. No language in the specification should be construed as indicating any non-claimed element essential to the practice of the invention.
[0036] Groupings of alternative elements or embodiments of the invention disclosed herein are not to be construed as limitations. Each group member can be referred to and claimed individually or in any combination with other members of the group or other elements found herein. One or more members of a group can be included in, or deleted from, a group for reasons of convenience and/or patentability. When any such inclusion or deletion occurs, the specification is herein deemed to contain the group as modified thus fulfilling the written description of all Markush groups used in the appended claims.
[0037] The description that follows, and the embodiments described therein, is provided by way of illustration of an example, or examples, of particular embodiments of the principles and aspects of the present disclosure. These examples are provided for the purposes of explanation, and not of limitation, of those principles and of the disclosure.
[0038] It should also be appreciated that the present disclosure can be implemented in numerous ways, including as a system, a method or a device. In this specification, these implementations, or any other form that the invention may take, may be referred to as processes. In general, the order of the steps of the disclosed processes may be altered within the scope of the invention.
[0039] The headings and abstract of the invention provided herein are for convenience only and do not interpret the scope or meaning of the embodiments.
[0040] The following discussion provides many example embodiments of the inventive subject matter. Although each embodiment represents a single combination of inventive elements, the inventive subject matter is considered to include all possible combinations of the disclosed elements. Thus if one embodiment comprises elements A, B, and C, and a second embodiment comprises elements B and D, then the inventive subject matter is also considered to include other remaining combinations of A, B, C, or D, even if not explicitly disclosed.
[0041] Various terms as used herein are shown below. To the extent a term used in a claim is not defined below, it should be given the broadest definition persons in the pertinent art have given that term as reflected in printed publications and issued patents at the time of filing.
[0042] As used herein, the term “control” or “controlling” is intended to include all activities and properties tending to kill agricultural insects; or inhibit or otherwise interfere with normal life cycle of insects (e.g., reduced mobility, appetite and/or reproductive capability); or to repel agricultural insects from a host or area.
[0043] As used herein, the term “protection” or “protecting” refers to avoiding, or minimizing the amount of attack on a plant or plant part by an undesired insect to a point where it no longer poses a threat to plant vitality, selective plant death, quality loss and/or reduced yields.
[0044] As used herein, the expressions "CS ", "SC" and "ZC" are the international denominations adopted by the FAO (Food and Agricultural Organization of the United Nations) to designate "capsule suspension", "suspension concentrate" and "stable aqueous suspension of microcapsules and solid fine particles", respectively.
[0045] The present invention relates to agricultural insecticide. Specifically, the present invention relates to a new and improved formulation comprising a combination of Lambda-cyhalothrin and Fipronil, along with one or more agrochemical excipients.
[0046] According to one embodiment of the present disclosure, there is provided an agrochemical ZC formulation comprising Lambda-cyhalothrin in combination with Fipronil, along with one or more agrochemical excipients, for use in protecting agricultural crops from attack by insects.
[0047] According to another embodiment of the present disclosure, the ZC formulation comprises microencapsulated Lambda-cyhalothrin and suspension concentrate of Fipronil along with one or more agrochemical excipients.
[0048] Lambda-cyhalothrin is a known skin irritant. In the present invention, Lambda-cyhalothrin is used in encapsulated formulation, making it safe for application. Due to encapsulation, Lambda-cyhalothrin is released slowly and provides effective bio-efficacy.
[0049] According to another embodiment of the present disclosure, the ZC formulation comprises microencapsulated Lambda-cyhalothrin and suspension concentrate of Fipronil along with one or more agrochemical excipients, wherein the agrochemical excipient is selected from capsule forming agent, emulsifier, dispersing agent, anti-freeze, biocide, stabilizing agent, wetting agent, defoamer, adjuvant, viscosity modifier or the like. However, those skilled in the art will appreciate that it is possible to utilize additional agrochemical excipients without departing from the scope of the present invention.
[0050] In various embodiments, the ZC formulation can include Lambda-cyhalothrin at a concentration in the range of 5% to 15% (w/w), and Fipronil at a concentration in the range of 5% to 25% (w/w) based on total weight of the formulation.
[0051] In one embodiment, the capsule forming agent is isocyanate selected from methylene diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, bifunctional monomer of tetraalkyl xylene diisocyanate, cyclohexane diisocyanate, 1,12-dodecane diisocyanate, 1,4-tetramethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, polymethylene polyphenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, dianisidine diisocyanate, bitolylene diisocyanate, naphthalene-1,4-diisocyanate, ,diphenylene 4,4'-diisocyanate, xylylene-1,3-diisocyanate, bis(4-isocyanatophenyl)methane, bis(3-methyl-4-isocyanatophenyl)methane, 4,4'-diphenylpropane diisocyanate and the like. The capsule forming agent can be a single isocyanate or a combination thereof.
[0052] In a preferred embodiment, the capsule forming agent is isocyanate selected from but not limited to methylene diisocyanate, toluene diisocyanate or a combination thereof.
[0053] In a preferred embodiment, the capsule forming agentsare methylene diisocyanate and toluene diisocyanate.
[0054] In another embodiment, the isocyanate may preferably be present in an amount from 0.1% to 2.0% (w/w) based on total weight of the ZC formulation.
[0055] In an embodiment, the emulsifier can beionic emulsifier, non-ionic emulsifier or a combination thereof. Ionic emulsifiers can be selected from calcium alkylaryl sulfonates, such as calcium dodecylbenzenesulfonate and the like whereas non-ionic emulsifiers can be selected from fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide/ethylene oxide condensates, alkyl polyethers, sorbitan esters (sorbitan fatty acid esters, polyoxyethylene sorbitan esters, polyoxyethylene sorbitan fatty acid esters), cetostearyl alcohol ethoxylates,lauryl myristyl alcohol ethoxylates, cetyl alcohol ethoxylateand the like.
[0056] In a preferred embodiment, the emulsifier is non-ionic, selected from cetostearyl alcohol ethoxylate, lauryl myristyl alcohol ethoxylates orcetyl alcohol ethoxylate.
[0057] In another embodiment, the emulsifier may preferably be present in an amount from 0.1% to 2.0% (w/w) based on total weight of the ZC formulation.

[0058] In an embodiment, the dispersing agent can be selected from but not limited to sodium lignosulfonate, polymethylacrylate polyethylene glycol graft copolymer or a combination thereof.
[0059] In another embodiment, the dispersing agent may preferably be present in an amount from 0.1% to 2.0% (w/w) based on total weight of the ZC formulation.
[0060] In an embodiment, antifreeze agent can be selected from propylene glycol, ethylene glycol, urea, calcium chloride sodium nitrate, magnesium chloride, ammonium sulfateand the like.
[0061] In a preferred embodiment, antifreeze agent is propylene glycol.
[0062] In another embodiment, the antifreeze agent may preferably be present in an amount from 1.0% to 10.0% (w/w) based on total weight of the ZC formulation.
[0063] In an embodiments, biocide can be selected from but not limited to 1,2-benzisothiazolin-3-one, 2-methyl- isothiazolin-3-one and the like.
[0064] In a preferred embodiment, biocide is 1,2-benzisothiazolin-3-one.
[0065] In another embodiment, the biocide may preferably be present in an amount from 0.05% to 1.0% (w/w) based on total weight of the ZC formulation.
[0066] In an embodiment, the stabilizing agent can bepolymethyl methacrylate-polyethylene glycol graft copolymer, polyethylene glycol, ethylene glycol-propylene glycol copolymers, mono-poly(oxyethylene)-substituted propylene glycol, di-(polyoxyethylene)-substituted propylene glycol, mono-poly(oxyethylene)-substituted glycerol, di-(polyoxyethylene)-substituted glycerol, and tri-(polyoxyethylene)-substituted glycerol, polyoxyethylated sorbitol, and polyoxyethylated glucose, polyvinyl pyrrolidone and poly(N-vinyl caprolactam), vinyl polymers having pending carboxylic acid, sulfonic acid or phosphonic acid groups, polystyrene sulfonate, polymers of carboxyvinyl monomers such as acrylic acid, methacrylic acid, and/or esters thereof.
[0067] In a preferred embodiment, the stabilizing agent ispolymethyl methacrylate-polyethylene glycol graft copolymer.
[0068] In another embodiment, the stabilizing agent may preferably be present in an amount from 1.0% to 5.0% (w/w) based on total weight of the ZC formulation.
[0069] In an embodiment, the wetting agent is polyoxyethylene alkyl ether.

[0070] In another embodiment, the wetting agent may preferably be used in an amount from0.5% to 5.0% (w/w) based on total weight of the ZC formulation.
[0071] In an embodiment, the defoamer is a liquid defoamer selected from polydimethyl siloxane, polydimethyl silicone oil and the like.
[0072] In another embodiment, the defoamer may preferably be used in an amount from 0.05% to 1.0% (w/w) based on total weight of the ZC formulation.
[0073] In an embodiment, the adjuvant is organosilicone, preferably polyalkyleneoxide modified heptamethyltrisiloxane.
[0074] In another embodiment, the adjuvant may preferably be used in an amount from 1.0% to 5.0% (w/w) based on total weight of the ZC formulation.
[0075] In an embodiment, the viscosity modifierisxanthan gum.
[0076] In another embodiment, the viscosity modifier may preferably be used in an amount from 0.05 to 1.0% (w/w) based on total weight of the ZC formulation.
[0077] According to still another embodiment of the present disclosure, ZC formulation comprising Lambda-cyhalothrin in combination with Fipronil exhibits synergistic effect when compared to the individual use of the mentioned insecticides.
[0078] According to one embodiment of the present disclosure, there is provided a method of preparing an agrochemical ZC formulation comprising Lambda-cyhalothrin and Fipronil. The process for preparing the present agrochemical ZC formulation can be modified accordingly by any person skilled in the art based on the knowledge of the manufacturing the formulation. However all such variation and modification is still covered by the scope of present invention.
[0079] According to another embodiment of the present disclosure, there is provided a method of preparing an agrochemical ZC formulation comprising Lambda-cyhalothrin and Fipronil comprising the steps of:
a) preparing Fipronil SC;
b) preparing lambda-cyhalothrin CS; and
c) mixing Fipronil SC and Lambda-cyhalothrin CS to obtain ZC formulation.
[0080] The process for preparation of Fipronil SC is depicted in the form of flow diagram as shown in Figure 1. The details of the same are described in Step-1 of Example 4. The process for preparation of Lambda-cyhalothrin is depicted in the form of flow diagram as shown in Figure 2.The details of the same are described inStep-2 of Example 4. The process for preparation of ZC formulation is depicted in the form of flow diagram as shown in Figure 3.The details of the same are described in Step-3 of Example 4.
[0081] According to another embodiment of the present disclosure, there is provided a method of preparing an agrochemical ZC formulation comprising Lambda-cyhalothrin and Fipronil comprising the steps of:
a) preparing an oil phase by mixing molten Lambda-cyhalothrin with aromatic hydrocarbon solvent followed by addition of one or more capsule forming agents;
b) preparing an aqueous phase by combining water, an emulsifier, a dispersing agent, biocide and an antifreeze agent;
c) dispersing the oil phase into the aqueous phase at an elevated temperature using a high shear mixer to form an emulsion;
d) optionally quenching the emulsion with an aqueous ammonia solution;
e) maintaining the emulsion under stirring for a time period ranging from 30 minutes to 5 hours;
f) adjusting the pH in the range of 4.5 to 6.5 and cooling the emulsion to room temperature to obtain microencapsulated Lambda-cyhalothrin;
g) preparing a slurry by combining Fipronil, water, a stabilizing agent, a wetting agent, an antifreeze agent, biocide and a defoamer;
h) wet milling the slurry in a bead mill to form a suspension concentrate of Fipronil;
i) mixing the microencapsulated Lambda-cyhalothrin and the suspension concentrate of Fipronil to form a mix; and
j) adding an adjuvant, water and a viscosity modifier to the mix to obtain the ZC formulation.
[0082] In certain preferred embodiments, the amount of Lambda-cyhalothrin used in the process of the present disclosure can range from 5% to 15% (w/w) based on total weight of the ZC formulation, and the amount of Fipronilcan range from 5% to 25% (w/w) based on total weight of the ZC formulation.
[0083] In an embodiment, the isocyanate used in step a) of the disclosed process can be methylene diisocyanate, toluene diisocyanate or a combination thereof. The isocyanate may preferably be used in an amount from0.1% to 2.0% (w/w) based on total weight of the ZC formulation.
[0084] In an embodiment, the emulsifier used in step b) of the disclosed process can be ionic emulsifier, non-ionic emulsifier or a combination thereof, preferably non-ionic emulsifier selected from cetostearyl alcohol ethoxylate, lauryl myristyl alcohol ethoxylates orcetyl alcohol ethoxylate. The emulsifier may preferably be used in an amount from0.1% to 2.0% (w/w) based on total weight of the ZC formulation.
[0085] In an embodiment, the dispersing agent used in step b) of the disclosed process can be sodium lignosulfonate. The dispersing agent may preferably be used in an amount from 0.1% to 2.0% (w/w) based on total weight of the ZC formulation.
[0086] In an embodiment, the antifreeze agent used in step b) of the disclosed process can be propylene glycol. The antifreeze agent may preferably be used in an amount from 1.0% to 10.0% (w/w) based on total weight of the ZC formulation.
[0087] In some embodiments, the aqueous phase prepared in step b) can further include a biocide such as 1,2-benzisothiazolin-3-one.The biocide may preferably be used in an amount from 0.05% to 1.0% (w/w) based on total weight of the ZC formulation.
[0088] In various embodiments, the oil phase is dispersed in the aqueous phase at an elevated temperature ranging from 40°C to 100°C, preferably from 50°C to 80°C.
[0089] In some embodiments, the emulsion formed in step c) may optionally be treated with aqueous ammonia solution to quench un-reacted isocyanate, if any, present in the emulsion.
[0090] In an embodiment, step f) of the disclosed process includes allowing the emulsion to cool to room temperature, followed by adjusting its pH to 4.5-6.5 using phosphoric acid.
[0091] In an embodiment, the stabilizing agent used in step g) of the disclosed process can bepolymethyl methacrylate-polyethylene glycol graft copolymer. The stabilizing agent may preferably be used in an amount from1.0% to 5.0% (w/w) based on total weight of the ZC formulation.
[0092] In an embodiment, the wetting agent used in step g) of the disclosed process can be polyoxyethylene alkyl ether. The wetting agent may preferably be used in an amount from0.5% to 5.0% (w/w) based on total weight of the ZC formulation.
[0093] In an embodiment, the antifreeze agent used in step g) of the disclosed process can be propylene glycol. The antifreeze agent may preferably be used in an amount from1.0% to 10.0% (w/w) based on total weight of the ZC formulation.

[0094] In an embodiment, the defoamer used in step g) of the disclosed process can be a liquid defoamer, preferably selected from polydimethyl siloxane, polydimethyl silicone oil and the like. The defoamer may preferably be used in an amount from0.05% to 1.0% (w/w) based on total weight of the ZC formulation.
[0095] In some embodiments, the slurry prepared in step g) can further include a biocide such as 1,2-benzisothiazolin-3-one. The biocide may preferably be used in an amount from 0.05% to 1.0% (w/w) based on total weight of the ZC formulation.
[0096] In an embodiment, mixing the microencapsulated Lambda-cyhalothrin and the suspension concentrate of Fipronil in step i) includes mixing the microencapsulated Lambda-cyhalothrin and the Fipronil suspension concentrate under mild agitation at room temperature.
[0097] In an embodiment, the adjuvant used in step j) of the disclosed process can be organosilicone, preferably polyalkyleneoxide modified heptamethyltrisiloxane. The adjuvant may preferably be used in an amount from1.0% to 5.0% (w/w) based on total weight of the ZC formulation.
[0098] In an embodiment, the viscosity modifier used in step j) of the disclosed process can be xanthan gum. The viscosity modifiermay preferably be used in an amount from0.05%to 1.0% (w/w) based on total weight of the ZC formulation.
[0099] According to another embodiment of the present disclosure, the insecticide formulation of the present disclosure can be used to control insects that attack agricultural crops, such as but not limited to chilli, cotton, onion, tomato, brinjal, okra, cabbage, grapes, mango, soybean, ground nut, pigeon pea, maize, tea and the like.
[00100] According to yet another embodiment of the present disclosure, the insecticide formulation shows excellent insecticidal effects against various agricultural insects, such as but not limited to sucking pests like thrips, aphids, jassids, hoppers, leaf miner, mites, tea mosquito bug, pink bollworm, caterpillar pests like bollworms (including pink bollworm), shoot and fruit borer, diamond back moth, fruit borer, semilooper, pod borer, leaf eating caterpillar etc.
[00101] According to another embodiment of the present disclosure, agricultural crops can be protected from attack of insects by spraying ZC formulation comprising microencapsulated Lambda-cyhalothrin and suspension concentrate of Fipronil along with one or more agrochemical excipients.
[00102] In yet another embodiment, the present disclosure is directed to a method of protecting agricultural crops against attack by insects. The method includes applying or spraying an insecticidally effective amountof a ZC formulation comprising microencapsulated Lambda-cyhalothrin and suspension concentrate of Fipronil on crops.
[00103] According to another embodiment of the present disclosure, the application rate of the ZC formulation comprising microencapsulated Lambda-cyhalothrin and suspension concentrate of Fipronil along with one or more agrochemical excipients, is from about 100 g/ml/ha to about 1200 g/ml/ha.
[00104] While the foregoing describes various embodiments of the disclosure, other and further embodiments of the disclosure may be devised without departing from the basic scope thereof. The scope of the invention is determined by the claims that follow. The invention is not limited to the described embodiments, versions or examples, which are included to enable a person having ordinary skill in the art to make and use the invention when combined with information and knowledge available to the person having ordinary skill in the art.
[00105] The present invention is further explained in the form of following examples. However, it is to be understood that the following examples are merely illustrative and are not to be taken as limitations upon the scope of the invention.
[00106] Examples 1-3: Preparation of different ZC formulations having the compositions shown in the Table 1.
Table 1: Different ZC formulations comprising Lambda cyhalothrin and Fipronil
Ingredients Example-1 Example-2 Example-3 Use
% w/w % w/w % w/w
Lambda-cyhalothrin 5.0 10.0 15.0 Active ingredient
Fipronil 12.5 25.0 5.0 Active ingredient
Aromatic hydrocarbon 5.0 8.0 10.0 Solvent
Methylene diisocyanate 0.4 0.8 1.0 Capsule forming agent
Toluene diisocyanate 0.4 0.8 0.5 Capsule forming agent
25% Ammonia solution 0.4 0.8 1.0 Quenching agent
Polyalkyleneoxide modified heptamethyltrisiloxane 2.0 2.0 2.0 Super spreader adjuvant
Cetostearyl alcohol ethoxylates 0.5 0.7 0.8 Emulsifier
Sodium lignosulfonate 0.5 1.0 1.5 Dispersing agent
Polymethyl methacrylate-polyethylene glycol graft copolymer 2.1 2.5 1.7 Stabilizing agent/ Dispersing agent
Polyoxyethylene alkyl ether 1.3 1.5 1.0 Wetting agent
Propylene glycol 5 5 5 Antifreeze agent
1,2-Benzisothiazolin-3-one 0.1 0.1 0.1 Biocide
Polydimethylsiloxane 0.2 0.2 0.2 Defoamer
Phosphoric acid 0.3 0.4 0.3 pH modifier
Xanthan gum 0.3 0.25 0.2 Viscosity modifier
Demineralised water QS* QS* QS* Medium
Total 100 100 100
* QS= Quantity Sufficient to make 100%
[00107] Example 4: Procedure for preparation of ZC formulation comprising Lambda-cyhalothrin and Fipronil
[00108] Step 1: Preparation of Fipronil suspension concentrate (SC): An aqueous Fipronil suspension concentrate was prepared by mixing Fipronil (12.5 gm), polymethyl methacrylate-polyethylene glycol (2.1 gm), polyoxyethylene alkyl ether (1.3 gm), propylene glycol (2.2 gm), 1,2-benzisothiazolin-3-one (0.05 gm) and polydimethylsiloxane (0.1 gm) in demineralised water (23.56 mL), followed by milling (details, machine type, time, milling speed etc) using pressurized bead mill for 30 mins at 10 rpm to reduce particle size of the suspension upto D90 less than 5 micron.
[00109] Step 2: Preparation of microencapsulated Lambda-cyhalothrin (CS): Aromatic hydrocarbon solvent (5 mL) was added to molten Lambda-cyhalothrin technical (5 gm). To this, capsule forming agents, methylene diisocyanate (0.4 gm), and toluene diisocyanate (0.4 gm), were mixed to prepare an oil phase. Aqueous phase was prepared by mixing emulsifier, cetostearyl alcohol ethoxylates (0.5 gm), sodium lignosulfonate (0.5 gm), propylene glycol (2.8 gm), 1,2-benzisothiazolin-3-one (0.05 gm) and demineralised water in a reaction vessel fitted with IKA homoginizer. The temperature of the reaction vessel was then raised to 60°C and oil phase was slowly added to the aqueous phase, and mixed in a high shear to get a median particle size between 5µ and 10µ and to initiate wall formation reaction. The emulsion thus obtained was treated with 25% ammonia solution (0.4 gm) to quench any un-reacted isocyanate present in the emulsion, and then stirred for a period of 2 hrs. Lambda-cyhalothrin CS mixture (52.7 gm), was allowed to cool to room temperature prior to adjusting the pH to 4.5-6.5 using phosphoric acid.
[00110] Step 3: Preparation of ZC formulation: In a clean mixing vessel, added Lambda-cyhalothrin CS (52.7 gm) to Fipronil SC (41.8 gm) under mild agitation at 300 rpm for 3 hrs. Polyalkyleneoxide modified heptamethyltrisiloxane (2 gm), water and 2% xanthan gum gel (1 gm) were added sequentiallyand the stirring was continued until a homogeneous mixture resulted in 100 gm of ZC formulation.
[00111] Example 5: Evaluation of ZC formulation prepared according to example 1
[00112] The Table 2 shows the physical and chemical properties of the ZC formulation prepared according to example 1 before and after the accelerated storage test.
Table 2
SL. NO. TESTS Ambient Sample Accelerated Storage Test @54±2°C for 14 days
1. Description White to off-white colored
suspension free from extraneous matter White to off-white colored
suspension free from extraneous matter without any layer separation
2 Active Ingredient content, % w/w
(i)Lambda Cyhalothrin content 5.1 5.1
(ii)Fipronil content 12.8 12.7
3. Free,non-encapsulated Lambda Cyhalothrin content, % w/w, max 0.05 0.05
4. Suspensibility, %w/w, min
Lambda Cyhalothrin
Fipronil
100
98
99
97
5. Wet sieve passing through 75µ sieve, % w/w, min 99.94 99.92
6. Spontaneity of dispersion, %w/w,min
Lambda Cyhalothrin
Fipronil

98
100

98
99
7. pH (1% aqueous suspension) 6.2 6.2
8. Persistent foam after 1 min, mL, max 10 8
9. Pourability as rinse residue, % w/w 0.2
0.2

[00113] Stability testing of the ZC formulation was carried out using HDPE containers for 14 days @54±2°C and the formulation according to the present invention was found to be stable when compared with the ambient sample.
[00114] Example 6: Field Trials
[00115] Field Trials were conducted to evaluate the effect of pre-mix lambda cyhalothrin 5%+ fipronil 12.5% zc against thrips & fruit borer in chilli and cotton crops.
Field Trial Experiment 1: A study was conducted to evaluate the biological efficacy of the ZC formulation comprising pre-mix lambda cyhalothrin 5%+ fipronil 12.5% (according to the present invention) vs.Fipronil 5% SC alone, Lambda Cyhalothrin 5%EC alone and Thiamethoxam 12.6%+Lambda cyhalothrin 9.5% ZC (standard), against chilli thrips & fruit borer on local variey of chilli crop.
Experiment 1 : Effect of pre-mix Lambda Cyhalothrin 5%+ Fipronil 12.5% ZC against chilli thrips & fruit borer
Crop & Variety : Chilli var., Local
Date of sowing : 05/09/2018
Date of application : 05/12/2018
Dates of observations : Before 1,2,3,6,12 & 16 days after spraying

Treatment Dosage % reduction of thrips over untreated check
(days after spray) % reduction of Fruit borer over of untreated check (12 days after spray)
g a.i./ha Formulation
(g/ml/ha) 1 2 3 6 12 16
Lambda Cyhalothrin 5%+ Fipronil 12.5% ZC 15 + 37.5 300 58.82 76.30 75.18 80.39 60.19 20.74 73.33
Lambda Cyhalothrin 5%+ Fipronil 12.5% ZC 17.5 + 43.5 350 67.06 80.00 79.79 84.31 62.96 34.74 77.78
Lambda Cyhalothrin 5%+ Fipronil 12.5% ZC 20 + 50 400 74.12 82.22 85.11 88.24 67.59 49.47 88.89
Fipronil 5% SC 37.5 750 54.47 70.37 74.12 79.09 58.95 16.53 13.33
Fipronil 5% SC 43.5 875 65.88 76.67 78.72 82.68 60.49 32.95 11.11
Fipronil 5% SC 50 1000 71.76 81.48 83.33 86.93 63.89 41.79 8.89
Lambda Cyhalothrin 5%EC 15 300 51.76 63.33 68.44 73.85 53.08 15.79 53.33
Lambda Cyhalothrin 5%EC 17.5 350 58.82 70.00 72.69 78.43 58.33 27.68 55.56
Lambda Cyhalothrin 5%EC 20 400 66.24 73.70 79.79 83.33 62.96 31.58 60.00
Thiamethoxam 12.6%+Lambda cyhalothrin 9.5% ZC (Standard Check) 25.2 + 19 200 55.29 63.70 68.09 73.53 42.59 20.00 57.78
Untreated control (No Treatment) - - 0.00 0.00 0.00 0.00 0.00 0.00 0.00

[00116] Surprisingly, the insecticidal composition of pre-mix Lambda Cyhalothrin 5%+ Fipronil 12.5% ZC @ 400mL/ha (according to the present invention) presents a higher insect control with better efficacy against thrips & fruit borer of chilli as compared to individual registered formulations Lamda-cyhalothrin 5%EC and Fipronil 5%SC. The ZC formulation of the present invention was found to be superior to use of other insecticides alone as well in comparison to standard check (Thiamethoxam 12.6%+Lambda Cyhalothrin 9.5%, ZC).
[00117] Field Trial Experiment 2: A study was conducted to evaluate the biological efficacy of the ZC formulation comprising pre-mix lambda cyhalothrin 5%+ Fipronil 12.5%; ZC (RIL-237 (17.5%ZC) (according to the present invention) vs. Fipronil 5% SC alone, Lambda Cyhalothrin 5% EC alone and Thiamethoxam 12.6%+Lambda cyhalothrin 9.5% ZC (standard), against cotton thrips & pink bollworm on cotton jay.
Experiment 2 : Effect of pre-mix Lambda Cyhalothrin 5%+ Fipronil 12.5% ZC(RIL-237(17.5%ZC) against cotton thrips & pink bollworm
Crop & Variety : Cotton Jay
Date of sowing : 25/06/2019
Date of application : 21/08/2019
Dates of observations : Before,1,2,5 & 10 days after spraying

Treatment Dosage % reduction of thrips over untreated check
(days after spray) % reduction of pink bollworm over untreated check(10 days after spray)

g a.i./ha Formulation
(g/ml/ha) 1 2 5 10
Lambda Cyhalothrin 5%+ Fipronil 12.5% ZC 15 + 37.5 300 44.37 70.63 70.89 44.88 72.22
Lambda Cyhalothrin 5%+ Fipronil 12.5% ZC 17.5+ 43.5 350 56.47 77.75 80.39 49.91 77.78
Lambda Cyhalothrin 5%+ Fipronil 12.5% ZC 20 + 50 400 61.84 85.00 84.97 55.87 88.89
Fipronil 5% SC 37.5 750 43.08 66.25 67.91 43.39 11.11
Fipronil 5% SC 43.5 875 51.94 74.81 78.43 49.16 8.33
Fipronil 5% SC 50 1000 57.96 83.75 83.96 54.01 5.56
Lambda Cyhalothrin 5%EC 15 300 41.14 64.19 66.13 42.46 69.44
Lambda Cyhalothrin 5%EC 17.5 350 48.25 73.56 73.86 47.49 75.00
Lambda Cyhalothrin 5%EC 20 400 53.88 77.50 81.40 52.51 83.33
Thiamethoxam 12.6%+Lambda cyhalothrin 9.5% ZC (Standard Check) 25.2 + 19 200 56.02 77.31 79.44 47.49 47.22
Untreated control (No Treatment) - - 0.00 0.00 0.00 0.00 0.00

[00118] Surprisingly, the insecticidal composition of pre-mix Lambda Cyhalothrin 5%+ Fipronil 12.5% ZC @ 400ml/ha(according to the present invention) presents a higher insect controlwith better efficacy against against thrips & pink bollworm of cotton as compared to individual registered formulations Lamda-cyhalothrin 5%EC and Fipronil 5%SC. The ZC formulation of the present invention was found to be superior to use of other insecticides alone as well in comparison to standard check (Thiamethoxam 12.6%+Lambda Cyhalothrin 9.5%, ZC).
[00119] The foregoing examples are merely illustrative and are not to be taken as limitations upon the scope of the invention. Various changes and modifications to the disclosed embodiments will be apparent to those skilled in the art. Such changes and modifications may be made without departing from the scope of the invention.

ADVANTAGES OF THE PRESENT INVENTION
[00120] The present invention provides a new and improved agrochemical formulation for protecting agricultural crops such as to chilli, cotton, onion and tomato, from attack by insects.
[00121] The present invention provides an insecticide formulation that exhibits excellent insecticidal activities against various agricultural insects such as thrips, sucking pests and pink bollworm.
[00122] The present invention provides an agricultural insecticide formulation that demonstrates improved safety while maintaining insecticidal efficacy.
[00123] The present invention provides an agricultural insecticide formulation that controls environmental damage and imparts protection against a wider variety of insect pests.
[00124] The present invention provides a new and improved agricultural insecticide formulation which is more affordable by general public.
[00125] The present invention provides a new and improved agricultural insecticide formulation comprising encapsulated of Lambda-cyhalothrin, making it safe for application.
,CLAIMS:1. An agrochemical ZC formulation comprising Lambda-cyhalothrin in combination with Fipronil, along with one or more agrochemical excipients.
2. The agrochemical ZC formulation as claimed in claim 1, wherein Lambda-cyhalothrin is microencapsulated and Fipronil is suspension concentrate.
3. The agrochemical ZC formulation as claimed in claim 1, whereinthe agrochemical excipient is selected from capsule forming agent, emulsifier, dispersing agent, anti-freeze, biocide, stabilizing agent, wetting agent, defoamer, adjuvant, viscosity modifier or combination thereof.
4. The agrochemical ZC formulation as claimed in claim 1, wherein Lambda-cyhalothrin is present at a concentration in the range of 5% to 15% (w/w), and Fipronil is present at a concentration in the range of 5% to 25%(w/w) based on total weight of the formulation.
5. The agrochemical ZC formulation as claimed in claim 1, wherein the capsule forming agent is isocyanate selected from methylene diisocyanate, toluene diisocyanate or a combination thereof, in an amount from 0.1% to 2.0% (w/w) based on total weight of the ZC formulation.
6. The agrochemical ZC formulation as claimed in claim 1,wherein the emulsifier is ionic emulsifier, non-ionic emulsifier or a combination thereof, preferably non-ionic emulsifier selected from cetostearyl alcohol ethoxylate,lauryl myristyl alcohol ethoxylates orcetyl alcohol ethoxylate, in an amount from 0.1% to 2.0% (w/w) based on total weight of the ZC formulation.
7. The agrochemical ZC formulation as claimed in claim 1, wherein the dispersing agent isselected from sodium lignosulfonate, polymethylacrylate polyethylene glycol graft copolymer or a combination thereof, in an amount from 0.1% to 2.0% (w/w) based on total weight of the ZC formulation.
8. The agrochemical ZC formulation as claimed in claim 1, wherein the antifreeze is propylene glycol, in an amount from 1.0% to 10.0% (w/w) based on total weight of the ZC formulation.
9. The agrochemical ZC formulation as claimed in claim 1, wherein the biocide is 1,2-benzisothiazolin-3-one, in an amount from 0.05% to 1.0% (w/w) based on total weight of the ZC formulation.
10. The agrochemical ZC formulation as claimed in claim 1, wherein the stabilizing agent ispolymethyl methacrylate-polyethylene glycol graft copolymer, in an amount from 1.0% to 5.0% (w/w) based on total weight of the ZC formulation.
11. The agrochemical ZC formulation as claimed in claim 1, wherein the wetting agent is polyoxyethylene alkyl ether, in an amount from 0.5% to 5.0% (w/w) based on total weight of the ZC formulation.
12. The agrochemical ZC formulation as claimed in claim 1, wherein the defoamer is a liquid defoamer, selected from polydimethyl siloxane or polydimethyl silicone oil, in an amount of from 0.05% to 1.0% (w/w) based on total weight of the ZC formulation.
13. The agrochemical ZC formulation as claimed in claim 1, wherein the adjuvant is organosilicone, preferably polyalkyleneoxide modified heptamethyltrisiloxan,in an amount of from 1.0 to 5.0% (w/w) based on total weight of the ZC formulation.
14. The agrochemical ZC formulation as claimed in claim 1, wherein the viscosity modifierisxanthan gum, in an amount of from 0.05 to 1.0% (w/w) based on total weight of the ZC formulation.
15. The agrochemical ZC formulation as claimed in claim 1, wherein the application rate of the ZC formulation is from about 100 g/ml/ha to about 1200 g/ml/ha.
16. A method of preparing the agrochemical ZC formulation as claimed in claim 1, comprising the steps of:
a) preparing an oil phase by mixing molten Lambda-cyhalothrin with aromatic hydrocarbon solvent followed by addition of one or more capsule forming agents;
b) preparing an aqueous phase by combining water, an emulsifier, a dispersing agent, biocide and an antifreeze agent;
c) dispersing the oil phase into the aqueous phaseat an elevated temperature using a high shear mixer to form an emulsion;
d) optionally quenching the emulsion with an aqueous ammonia solution;
e) maintaining the emulsion under stirring for a time period ranging from 30 minutes to 5 hours;
f) adjusting the pH in the range of 4.5 to 6.5 and cooling the emulsion to room temperature to obtain microencapsulated Lambda-cyhalothrin;
g) preparing a slurry by combining Fipronil, water, a stabilizing agent, a wetting agent, an antifreeze agent, biocide and a defoamer;
h) wet milling the slurry in a bead mill to form a suspension concentrate of Fipronil;
i) mixing the microencapsulated Lambda-cyhalothrin and the suspension concentrate of Fipronil to form a mix; and
j) adding an adjuvant, water and a viscosity modifier to the mix to obtain the ZC formulation.
17. A method of preparing the agrochemical ZC formulation as claimed in claim 17, wherein the oil phase is dispersed in the aqueous phase at an elevated temperature ranging from 40°C to 100°C, preferably from 50°C to 80°C.
18. A method of preparing the agrochemical ZC formulation as claimed in claim 17, wherein the emulsion formed in step c) may optionally be treated with aqueous ammonia solution to quench un-reacted isocyanate.
19. A method of preparing the agrochemical ZC formulation as claimed in claim 17, wherein step f) of the disclosed process includes allowing the emulsion to cool to room temperature, followed by adjusting its pH to 4.5-6.5 using phosphoric acid.
20. A method of preparing the agrochemical ZC formulation as claimed in claim 17, wherein mixing the microencapsulated Lambda-cyhalothrin and the suspension concentrate of Fipronil in step i) includes mixing the microencapsulated Lambda-cyhalothrin and the Fipronil suspension concentrate under mild agitation at room temperature.