Indian Patents. 271997:NOVEL FORMULATIONS OF BIFENTHRIN AND ENRICHED CYPERMETHRIN

Title of Invention	NOVEL FORMULATIONS OF BIFENTHRIN AND ENRICHED CYPERMETHRIN
Abstract	The present invention is directed to novel insecticidal compositions comprising bifenthrin and enriched cypermethrin, the compositions are physically stable when diluted with water.

Full Text	NOVEL FORMULATIONS OF BIFENTHRIN AND ENRICHED CYPERMETHRIN This application claims the benefit of U.S. Provisional Application No. 60/152,919 filed December 22,2005. FIELD OF THE INVENTION The present invention relates to the field of insecticides and insecticidal compositions. In particular, the invention relates to novel insecticidal compositions comprising bifenthrin and enriched cypermethrin that are physically stable when diluted with water. BACKGROUND OF THE INVENTION To enable the efficient elimination or controlling of imwanted insects in agricultural and other applications, it is desirable to use effective chemical insecticides on these unwanted pests. Formulations containing multiple insecticides are desirable in order to broaden the spectrum of economically important insect, mite, and other pest species killed or controlled and take advantage of the individual pesticidal characteristics of each of the active ingredients. Compositions containing two or more insecticides have been practiced in the art, but problems with the physical stability of such mixtures in water have caused application and efficacy issues. When traditional insecticidal compositions are combined, the combined components (surfactants, viscosity modifiers, wetting agents) of both may cause accelerated physical degradation (phase separation) of the mixture when diluted in low to moderately hard water. This physical degradation can occur in the mix tanks prior to application on plants or another locus where control is desired. Often this problem goes unnoticed and a uniform application of the insecticide .mixture is not achieved, yielding inadequate efficacy. Typically, in commercial applications, the insecticidal formulation comprises less than one percent of the tank mixture to keep the cost of the formulation low, while still yielding spectrum and onset of visual symptomology benefits. The physical stability of the formulation when diluted with water is a key problem in the art. SUMMARY OF THE INVENTION In accordance with the present invention, novel liquid formulations comprising bifenthrin and enriched cypermethrin have been found which have significantly improved the physical stability when diluted in water. DETAILED DESCRTION OF THE INVENTION The present invention is directed to novel insecticidal compositions comprising bifenthrin and enriched cypermethrin in an insecticidal formulation having significantly improved physical stability when the composition is diluted in water. zeto-Cypermethrin is a potent and quick acting insecticide, which controls a broad spectrum of chewing, sucking and flying insects. In addition to controlling chewing, sucking and flying insects, the pyrethroid bifenthrin is also active against a number of key mite pests and exhibits a longer residual activity than zeta-cypermetbrin. •The term "bifenthrin" means 2-methyIbiphenyl-3-ylmethyi (Z)-(lRS)-cis-3-(2-chloro-3,3,3-trifluoroprop-l -enyl)-2,2-dimethyl cyclopropanecarboxylate. The term "cypermethrin" means the synthetic pyrethroid (R,S)-d-cyano-3-phenoxybenzyl-(lRS)-cls-trans-3-(2,2-dichlorovinyl)-2,2- dimethylcyclopropanecarboxylate which consists of a mixture of eight isomers, each of which are present in approximately the same amounts. Since the discovery and commercialization of cypermethrin, products containing increased amounts of certain isomers have been developed. As used herein, thee term "enriched cypennethrin"refers to the following: alpha-cypermetbrin which is a racemate comprising (S)- a-cyano-3-phenoxybenzyl(lR)-cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxyIate and (R)- a-cyano-3-phenoxybenzyl (lS)-cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate; beto-cypermethrin which is a reaction mixture comprising two enantiomeric pairs in a ratio of about 2:3 (S)- a-cyano-3-phenoxybenzyl (lR)-cis-3-(2,2- an acid, severely solveat refined light and heavy paraffinic petroleum oil and a surfactant blend comprising an alkylbenzene sulfonate salt, an eihoxylated castor oil, and an ethoxylated fatty acid or a polyethylene glycol fatty acid ester, wherein said bifenthrin and enriched cypermethrin insecticides are present, collectively, in an insecticidally effective amount. Preferably, the aromatic solvent is selected from alkylated naphthalene aromatic and alkylated naphthalene depleted aromatic fluids, for example Aromatic 200 ND Fluid and Aromatic 200 Fluid (both available from ExxonMobil Chemicals). The aliphatic solvent is selected from de-aromatized hydrocarbon fluids, for example, Exxsol D serious fluids (available from ExxonMobile Chemicals), isoparaffnic fluids, for example Isopar fluids (available from ExxonMobile Chemicals), and hydrocarbon fluids with very high normal paraffin content, for example, Norpar fluids (available from ExxonMobile Chemicals). The aromatic or aliphatic solvent is present in a concentration of from 10% to 90% by weight and preferably, 40% to 55% by weight, based on the total weight of all components in the composition. The most preferred solvent is an alkylated naphthalene depleted aromatic fluid present in a concentration of from 44% to 47% Preferably, the alkylbenzene sulfonate salt is the amine or calcium salt of a branched or linear alkylbenzene sulfonate. More preferred, the alkylbenzene dodecylbenzene sulfonate salt is a branched dodecylbenzene sulfonate aminoethylethanolamine or calcium salt, for example, Agnique ABS 70AE and Agnique ABS 60 BC (available from Cognis Corporation) and Rhodacal 70 (available from Rhodia Corporation). The dodecylbenzene sulfonate, or salt thereof, maybe present in a concentration of from 1.5% to 4.5% by weight, based on the total weight of all components in the composition. The ethoxylated castor oil may be one or more ethoxylated castor oils selected from the group of ethoxylated castor oils having an EO number of 8 to 50. Preferably the ethoxylated castor oil has an EO number of 15 to 40 and most preferred an EO number of 20 to 40, for example, Agnique CSO-25 and Agnique CSO-36 (available from Cognis Corporation). The ethoxylated castor oil may be present in a concentration of from 1.5% to 4.5% by weight, based on the total weight of all the components in the composition. The ethoxylated fatty acid is preferably a C9 to C20 ethoxylated fatty acid, for example, stearic acid monooleate, stearic acid dioleate, and stearic acid monosterate. The polyethylene glycol fatty acid ester is selected from polyethylene glycol monooleates having an average M„ of 100 to 800, preferably an average M„ of 300 to 500, and most preferred, an average M„ of 400, for example, Agnique PEG 400MO (available from Cognis Corporation). The ethoxylated fatty acid or the polyethylene glycol fatty acid ester may be present in a concentration of from 0.10% to 0.60% by weight, based on the total weight of all the components in the composition. The severely solvent refined light and heavy paraffinic petroleum oil is a mixture of from 80% to 100% by volume light paraffinic petroleum oil and from 0% to 20% by volume of heavy paraffinic petroleum oil, for example, Sunpray 6N (available from Sunoco, Inc.), Orchex 796 (available from ExxonMobile US A) and BVA Spray 10 (available from BVA Oils). The severely solvent refined light and heavy paraffinic petroleum oil mixture may be present in a concentration of from 20% to 30% by weight of all the components in the total formulation, preferably in a concentration of from 24% to 26% by weight, based on the total weight of all the components in the composition. An acid is used to buffer the formulation in order to stabilize the zeta-cypermethnn from epimerizing to less active isomers. The acid is preferably acetic acid or glacial acetic acid and is present in a concentration of from 0.01% to 0.15% by weight, based on the total weight of all the components in the composition. The insecticidal formulation may further comprise additional components such as an anti-freeze agent, an anti-foam agent and/or a biocide. A preferred embodiment of this aspect of tiie invention is an insecticidal emulsifiable concentrate formulation wherein said bifenthrin and enriched cypermethrin insecticides are present in a ratio of 1/4 to 4/1 and a concentration of from 0.05% to 30%, the aromatic solvent is present in a concentration of from 40% to 55%, the acetic acid is present in a concentration of from 0.01% to 0.15%, the severely solvent refined light and heavy paraffinic petroleum oil is present in a concentration of from 20% to 30%, the branched dodecylbenzene sulfonate salt is present in a concentration of from 1.5% to 4.5%, the ethoxylated castor oil or mixture of castor oils is present in a concentration of from 1.% to 4.5% and the polyethylene glycol fatty acid ester is present in a concentration of from 0.10% to 0.60% wherein all %'s are % by weight based upon the total weight of the formulation. Another aspect of the present invention is directed to an insecticidal composition comprising an aqueous mixture of bifenthrin and enriched cypermethrin, an aromatic solvent, one or more nonionic polymeric surfactants, an antifoam agent, a preservative and glycerine, wherein the bifenthrin and enriched cypermethrin insecticides are present, at least collectively, in an insecticidally effective amount. The aromatic solvent is selected from alkylated naphthalene aromatic and alkylated naphthalene depleted aromatic fluids, for example Aromatic 200 ND Fluid and Aromatic 200 Fluid (both available from ExxonMobil Chemicals). The aromatic solvent is present in a concentration of from 5% to 30% by weight, preferably 12% to 15% by weight, based on the total weight of all components in the composition. Preferably, the nonionic polymeric surfactant is one or more surfactants selected from the group consisting of an alkyd polyethylene glycol, for example, Atlox 4914 (available from Uniqema Corporation) and a polyalkylene glycol ether, for example. Atlas G-5000 (available from Uniqema Corporation). Preferably the nonionic polymeric surfactant is present in a concentration of from 3% to 20% by weight preferably fiom 8% to 12% by weight, based on the total weight of all components in the composition. The antifoam agent is preferably a silicone containing antifoam agent, for example, Rhodorsil emulsion 1824 antifoam (available from Rhodia Corporation) and Dow Coming AF Emulsion (available fiom Dow Coming Corporation). Preferably the antifoam agent is present in a concentration of from 0.001% to 1.5% by weight, based on the total weight of all the components in the composition. The biocide is an isothiazolone mixture, for example, Kathon CG/ICP preservative or Legend MK preservative (available from Rohm and Haas Corporation).' Preferably the biocide is present in a concentration of fiom 0.001% to 1.5% by weight, based on the total weight of all the components in the composition. The glycerine is preferably refined glycerine, for example, Agnique GLY 99-U glycerine (available fiom Cognis Corporation). Glycerine is present in a concentration of from 3% to 15% by weight, preferably from 5% to 10% by weight, based on the total weight of all the components in the composition. Water is used as a diluent and preferably is purified water, for example, deionized or distilled water, and is present in an amount that would dilute the active ingredients to a desired concentration. Preferably water is present in a concentration of from 40% to 60% by weight, based on the total weight of all the components in the composition. A preferred embodiment of this aspect of the invention is an insecticidal Msncentrated aqueous emulsion formulation wherein said bifenthrin and enriched jypermethrin insecticides are present in a ratio of from 1/4 to 4/1 and in a concentration of from 0.05% to 30%, the aromatic solvent is present in a concentration of fiom 12% to 15%, nonionic polymeric surfactant is present in a concentration of from 8% to 12%, the antifoam agent is present in an amount of from 0.001% to 1.5%, the preservative is present in a concentration of from 0.001% to 1.5%, glycerine is present in a concentration of from 5% to 10% and water is present in a concentration of fiom 40% to 60%, wherein all %'s are % by weight based upon the total weight of all the components in the fismiulation. The term "ambient temperature" as utilized herein shall generally mean any suitable temperature found in a laboratory or other working quarter, and is generally not below about 15" C nor above about 30° C. The formulations of the present invention are further illustrated by the examples below. The examples serve only to illustrate the invention and should not be interpreted as limiting since further modifications of the disclosed invention will be apparent to those skilled in the art. All such modifications are deemed to be within the scope of the invention as defined in the claims. Example 1 This example illustrates one protocol for the preparation of a 2/1 ratio of bifenthrin to ze/a-cypermethrin emulsifiable concentrate formulation of the present invention. To 42,32 grams of Aromatic 200 ND was added 8.34 grams of melted bifenthrin (95.9% active ingredient) and 11.11 grams of zeto-cypermethtin (36% active ingredient, prepared by the process disclosed in U. S. Patent 4,997,970). The EXAMPLE 2 Dilution stability studies were conducted using 2.5 mL of the fonnulation of Example 1 added to 47.5 mL of water with 342 ppm hardness in a 50 mL Nessler tube. The Nessler tube was sealed with a rubber stopper and the contents mixed by inverting the tube ten times. The Nessler tube was placed in a tube rack at ambient temperature and the percent separation was recorded at 2.0 hours and 4,0 hours. The percent separation was calculated by first measuring the height of the separation, if any, then the total height of the mixture. Dividing the separation height by the total height and multiplying by 100 provides the percent separation. Table 2 sets forth the dilution stability percent separation of the formulations described in Example I and Table 1. The formulations are identified by the formulation code corresponding to those in Example 1 and in Table 1. As a control experiment, 6.0 grams of a commercially available formulation of bifenthrin (Capture 2EC available from FMC Corporation) and 1.2 grams of a commercially available formulation of zete-cypermethrin (Mustang Max 0.8EC* available from FMC Corporation) were blended together in 1.2 grams of Aromatic 200. The concentration of AI's was similar to the concentration of AI's in fonnulation code F2. A dilution stability test was performed using 2.5 mL of the control blend in 47.5 mL of water containing 342 ppm hardness as described above. The dilution stability percent separation results of the control experiment are presented in Table 2. TABLE 2 Percent Separation of Formulation in Water Containing 342 ppm Hardness (Agnique CSO-36), 2.12 grams ethoxylatcd castor oil (Agnique CSO-25), 25.00 grama of severely solvent refined light and heavy paraffinic petroleum oil (Sunspray 6N) and 0.1 gram of glacial acetic acid was added. Upon completion of the addition, the agitation was continued until a yellowish homogeneous solution was obtained. Example 4 A dilution stability study was conducted using 2.5 mL of the formulation prepared in Example 3 added to 47.5 mL of water with 342 ppm hardness in a 50 mL Nessler tube. The Nessler tube was sealed with a rubber stopper and the contents mixed by inverting the tube ten times. A total of three Nessler tubes were prepared in this manner. One Nessler tube was placed in a tube rack maintained at 0°C, one in a tube rack maintained at ambient temperature and one in a tube rack maintained at 30 "C, all were maintained for 24 hours. The percent separation after 24 hours was 0% for each temperature. Example S This example illustrates one protocol for the preparation of a 3/1 ratio of bifenthrin to zeto-cypermethrin concentrated aqueous emulsion formulation of the present invraition To a vessel equipped with a mechanical stirrer and a homogenizer was added 0.10 gram of a silicone containing antifoam agent (Rhodorsil emulsion 1824 antifoam), 6.0 grams of a polyalkylene glycol ether nonionic polymeric surfactant (Atlas G5000) and 49.15 grams of deionized water. The mixture was stirred and heated at 50°C to 50^C. While maintaining this temperature, the homogenizar was turned on and a warm (50C to 55'C) mixture of 13.63 grams of alkylated naphthalene depleted aromatic solvent (Aromatic 200 ND), 8.42 grams of zeta-cypemiethriii (36% active ingredient, prepared by the ptxjcess disclosed in U. S. Patent 4,997,970), 10.10 grams of bif«axthrin (95.9% active ingredient) and 4.00 grams of alkyd polyettiylene glycol nonionic surfactant (Atlox 4914) was added slowly. The mixture was homogenized until a particle size of less than three microns at 90% tile was obtained. The homogenizer was turned off and the stirred mixture was allowed to cool to less than 40°C at which time 8.S grams of refined glycerine (Agnique QLY99-U) and 010 grams of preservative (Legend MK) were added. The resulting mixture was stirred until a homogenous solution was obtained while cooling to ambient temperature. Example 6 A dilution stability study was conducted using 2.5 mL of the formulation prepared in Example 5 added to 47.5 mL of water with 342 ppm hardness in a 50 mL Nessler tube. The Nessler tube was sealed with a rubber stopper and the contents mixed by inverting the tube ten times. A total of three Nessler tubes were prepared in this manner. One Nessler tube was placed in a tube rack maintained at 0C, one in a tube rack maintained at ambient temperature and one in a tube rack maintained at 30 °C, all were maintained for 24 hours. The percent separation after 24 hours was 0% for each temperature. While this invention has been described with an emphasis upon preferred embodiments, it will be understood by those of ordinary skill in the art that variations of the preferred embodiments may be used and that it is intended that the invention may be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications encompassed within the spirit and scope of the invention as defined by the following claims. WHAT IS CLAIMED IS; 1 An insecficidal composition comprising: a) bifenthrin; b) enriched cypennethrin; c) one or more aromatic or diphatic solvents; d) an acid; e) a severely solvent refined light and heavy paraffinic petroleum oil; f) a surfactant blend comprising: i) an alkylbenzene sulfonate salt; ii) an ethoxylated castor oil; and iii) a polyethylene glycol fatty acid ester or ethoxylated fatty acid. 2 An insecticidal composition of claim 1 wherein the enriched cypermethrin is selected from the group consisting of ai\|pAo-cypennethrin,/>eto-cypennethrin, theta-cypermethrin and zeto-cypennethrin. 3 An insecticidal composition of claim 2 wherein the enriched cypermethrin is zeto-cypermethrin. 4 An insecticidal composition of claim 3 wherein bifenthrin and zeta-cypennethrin are present in a combined amount of from 0.05% to 30 % by weight based on the total weight of the formulation. 5 An insecticidal composition of claim 4 wherein the ratio of bifenthrin to zeta-cypermethrin is from 1/4 to 4/1. 6 An insecticidal composition of claim 1 wherein the aromatic solvent is selected from 'alkylated naphthalene aromatic solvent and alkylated naphthalene depleted aromatic solvent. 7 An insecticidal composition of claim 6 wherein the aromatic solvent is present in a concentration of from 40% to 55 % by weight based on the total weight of the formulating. 8 An insecticidal composition of claim 1 wherein the alkyl benzene sulfonate salt is selected from branched dodecylbenzene sulfonate, calcium salt and branched dodecylbenzene sulfonate, aminoethylethanolamine salt. 9 An insecticidal composition of claim 8 wherein the alkylbenzene sulfonate salt is present in a concentration of from 1.5% to 4.5% by weight based upon the total weight of the formulation 10 An insecticidal composition of claim 1 wherein the ethoxylated castor oil is selected from ethoxylated castor oils having an EO number of from 20 to 40. 11 An insecticidal composition of claim 10 wherein the ethoxylated castor oil is present in a concentration of from 1.5% to 4.5% by weight based on the total weight of the formulation. 12 An insecticidal composition of claim 1 wherein the polyethylene glycol fatty acid ester is selected from polyethylene glycol monooleate glycols having an average M„ of from 300 to 500. 13 An insecticidal composition of claim 12 wherein the polyethylene glycol fatty acid ester is present in a concentration of from 0.10% to 0.60% by weight based on the total weight of the formulation. 14 An insecticidal composition of claim 1 wherein the severely solvent refined light and heavy parafrinic petroleum oil is present in a concentration of from 20% to30% by weight based on the total weight of the formulation. 15 An insecticidal composition of claim 1 wherein the acid is selected from the group consisting of acetic acid and glacial acetic acid. 16 An insecticidal composition of claim 15 wherein the acid is present ia. a concentration of from 0,10% to 0.15% by weight based on the total weight of the formulation. 17 A method for controlling insects comprising applying the composition of claim 1 to a locus where insects are present or are expected to be present. 18 A composition of claim 1 further comprising at least one additional components selected from an anti-freeze agent, an anti-foam agent and a biocide. 19 An insecticidal composition comprising: a) bifenthrin and zete-cypermethrin present in a ratio of from 1/4 to 4/1 and in a total concentration of from 0.05% to 30%; b) an aromatic solvent present in a concentration of from 40% to 55%; c) acetic acid present in a concentration of from 0.01 % to 0.15%; d) severely solvent refined light and heavy parafSnic petroleum oil in a concentration of form 20% to 30%; e) a surfactant blend consisting of: a. alkylbenzene sulfonate salt in a concentration of from 1.5% to 4.5%; b. ethoxylated castor oil in a concentration of from 1.5% to 4.5%; and c. polyethylene glycol fetty acid ester present in a concentration of from 0.10% to 0.60%; wherein all % are % by weight based on the total weight. 20 A method for controlling insects comprising applying the composition of claim 19 to a locus where insects are present or are expected to be present. 21 A cqinposltion of claim 19 further comprising at least one additional component selected from an anti>freeze agent, an antifoam agent and a biocide. 22 An insecticidal composition comprising: a) bifenthrin; b) enriched cypramethrin; c) one or more aromatic solvent; d) one or more nonionic polymeric surfactant; e) an antifoam agent; f) abiocide; g) glycerine; and h) water. 23 An insecticidal composition of claim 22 wherein the enriched cypeimethrin is selected firom the group consisting of a(pAa-cypermethrin, 6eto-cypermethrin, theta-cypermethrin and zeto-cypermethrin. 24 An insecticidal composition of claim 23 wherein the enriched cypermethrin is zeto-cypermethrin. 25 An insecticidal composition of claim 24 wherein bifenthrin and zetO' cypermethrin are present in a combined amount of from 0.05% to 30 % by weight based on the total weight of the formulation. 26 An insecticidal composition of claim 25 wherein the ratio of bifenthrin to zeta-cypermethrin is from 1/4 to 4/1. 27 An insecticidal composition of claim 22 wherein the aromatic solvent is selected from alkylated naphthalene aromatic solvent and alkylated naphthalene depleted aromatic solvent. 28 An insecticidal composition of claim 27 wherein the aromatic solvent is present in a concentration of from 12% to 15% by weight based on the total weigfht of the formulation 20 An insecticidal composition of claim 22 wherein the nonionic polymeric surfactant is selected from the group consisting of an alkyd polyethylene glycol and a polyalkylene glycol ether. 30 An insecticidal composition of claim 29 wherein the nonionic polymeric surfactant is present in a concentration of from 8% to 12% by weight based on the total weight of the formulation. 31 An insecticidal composition of claim 22 wherein the antifoam agent is present in a concentration of from 0.001 % to 1.5% by weight based on the total weight of the formulation. 32 An insecticidal composition of claim 22 wherein the biocide is present in a concentration of from 0.001% to 1% by weight based on the total weight of the formulation. 33 An insecticidal composition of claim 22 wherein glycerine is present ia a concentration of from 5% to 10% by weight based on the total weight of the formulatioa 34 An insecticidal composition of claim 22 wherein water is present in a concentration of from 40% to 60% by weight based on the total weight of the fomiulation. 35 A method for controlling insects comprising applying the composition of claim 22 to a locus where insects are present or are expected to be present. 36 An insecticidal composition comprising: a) bifenthrin and zeto-cypermethrin present in a ratio of from 1/4 to 4/1 and in a total concentration of from 0.05% to 30%; b) one or more aromatic solvent present in a concentration of from 12% to 15%; c) one or more nonionic polymeric surfactant present in a concentration of from 8% to 12%; ,d) an antifoam agent in a concentration of from 0.001 % to 1.5%; e) a biocide present in a concentration of from 0.001% to 1.5%; f) glycerine present in a concentration of from 5% to 10%; and g) water present in a concentration of from 40% to 60%i wherein all % are % by weight based on the total weight of all the components in the formulation. 37 A method for controlling insects comprising applying the composition of claim 36 to a locus where insects are present or are expected to be present. 38. An insecticidal composition substantially as herein described with reference to the foregoing description, examples and the accompanying tables, 39. A method substantially as herein described with reference to the foregoing description, examples and the accompanying tables.

Full Text

NOVEL FORMULATIONS OF BIFENTHRIN AND ENRICHED
CYPERMETHRIN
This application claims the benefit of U.S. Provisional Application No. 60/152,919 filed December 22,2005.
FIELD OF THE INVENTION
The present invention relates to the field of insecticides and insecticidal compositions. In particular, the invention relates to novel insecticidal compositions comprising bifenthrin and enriched cypermethrin that are physically stable when diluted with water.
BACKGROUND OF THE INVENTION
To enable the efficient elimination or controlling of imwanted insects in agricultural and other applications, it is desirable to use effective chemical insecticides on these unwanted pests. Formulations containing multiple insecticides are desirable in order to broaden the spectrum of economically important insect, mite, and other pest species killed or controlled and take advantage of the individual pesticidal characteristics of each of the active ingredients.
Compositions containing two or more insecticides have been practiced in the art, but problems with the physical stability of such mixtures in water have caused application and efficacy issues. When traditional insecticidal compositions are combined, the combined components (surfactants, viscosity modifiers, wetting agents) of both may cause accelerated physical degradation (phase separation) of the mixture when diluted in low to moderately hard water. This physical degradation can occur in the mix tanks prior to application on plants or another locus where control is desired. Often this problem goes unnoticed and a uniform application of the insecticide .mixture is not achieved, yielding inadequate efficacy.
Typically, in commercial applications, the insecticidal formulation comprises less than one percent of the tank mixture to keep the cost of the formulation low, while still yielding spectrum and onset of visual symptomology benefits. The

physical stability of the formulation when diluted with water is a key problem in the art.
SUMMARY OF THE INVENTION
In accordance with the present invention, novel liquid formulations comprising bifenthrin and enriched cypermethrin have been found which have significantly improved the physical stability when diluted in water.
DETAILED DESCRTION OF THE INVENTION
The present invention is directed to novel insecticidal compositions comprising bifenthrin and enriched cypermethrin in an insecticidal formulation having significantly improved physical stability when the composition is diluted in water.
zeto-Cypermethrin is a potent and quick acting insecticide, which controls a broad spectrum of chewing, sucking and flying insects. In addition to controlling chewing, sucking and flying insects, the pyrethroid bifenthrin is also active against a number of key mite pests and exhibits a longer residual activity than zeta-cypermetbrin.
•The term "bifenthrin" means 2-methyIbiphenyl-3-ylmethyi (Z)-(lRS)-cis-3-(2-chloro-3,3,3-trifluoroprop-l -enyl)-2,2-dimethyl cyclopropanecarboxylate.
The term "cypermethrin" means the synthetic pyrethroid (R,S)-d-cyano-3-phenoxybenzyl-(lRS)-cls-trans-3-(2,2-dichlorovinyl)-2,2-
dimethylcyclopropanecarboxylate which consists of a mixture of eight isomers, each of which are present in approximately the same amounts. Since the discovery and commercialization of cypermethrin, products containing increased amounts of certain isomers have been developed. As used herein, thee term "enriched cypennethrin"refers to the following:
alpha-cypermetbrin which is a racemate comprising (S)- a-cyano-3-phenoxybenzyl(lR)-cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxyIate and (R)- a-cyano-3-phenoxybenzyl (lS)-cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate;
beto-cypermethrin which is a reaction mixture comprising two enantiomeric pairs in a ratio of about 2:3 (S)- a-cyano-3-phenoxybenzyl (lR)-cis-3-(2,2-

an acid, severely solveat refined light and heavy paraffinic petroleum oil and a surfactant blend comprising an alkylbenzene sulfonate salt, an eihoxylated castor oil, and an ethoxylated fatty acid or a polyethylene glycol fatty acid ester, wherein said bifenthrin and enriched cypermethrin insecticides are present, collectively, in an insecticidally effective amount.
Preferably, the aromatic solvent is selected from alkylated naphthalene aromatic and alkylated naphthalene depleted aromatic fluids, for example Aromatic 200 ND Fluid and Aromatic 200 Fluid (both available from ExxonMobil Chemicals). The aliphatic solvent is selected from de-aromatized hydrocarbon fluids, for example, Exxsol D serious fluids (available from ExxonMobile Chemicals), isoparaffnic fluids, for example Isopar fluids (available from ExxonMobile Chemicals), and hydrocarbon fluids with very high normal paraffin content, for example, Norpar fluids (available from ExxonMobile Chemicals). The aromatic or aliphatic solvent is present in a concentration of from 10% to 90% by weight and preferably, 40% to 55% by weight, based on the total weight of all components in the composition. The most preferred solvent is an alkylated naphthalene depleted aromatic fluid present in a concentration of from 44% to 47%
Preferably, the alkylbenzene sulfonate salt is the amine or calcium salt of a branched or linear alkylbenzene sulfonate. More preferred, the alkylbenzene dodecylbenzene sulfonate salt is a branched dodecylbenzene sulfonate aminoethylethanolamine or calcium salt, for example, Agnique ABS 70AE and Agnique ABS 60 BC (available from Cognis Corporation) and Rhodacal 70 (available from Rhodia Corporation). The dodecylbenzene sulfonate, or salt thereof, maybe present in a concentration of from 1.5% to 4.5% by weight, based on the total weight of all components in the composition.
The ethoxylated castor oil may be one or more ethoxylated castor oils selected from the group of ethoxylated castor oils having an EO number of 8 to 50. Preferably the ethoxylated castor oil has an EO number of 15 to 40 and most preferred an EO number of 20 to 40, for example, Agnique CSO-25 and Agnique CSO-36 (available from Cognis Corporation). The ethoxylated castor oil may be present in a concentration of from 1.5% to 4.5% by weight, based on the total weight of all the components in the composition.

The ethoxylated fatty acid is preferably a C9 to C20 ethoxylated fatty acid, for example, stearic acid monooleate, stearic acid dioleate, and stearic acid monosterate. The polyethylene glycol fatty acid ester is selected from polyethylene glycol monooleates having an average M„ of 100 to 800, preferably an average M„ of 300 to 500, and most preferred, an average M„ of 400, for example, Agnique PEG 400MO (available from Cognis Corporation). The ethoxylated fatty acid or the polyethylene glycol fatty acid ester may be present in a concentration of from 0.10% to 0.60% by weight, based on the total weight of all the components in the composition.
The severely solvent refined light and heavy paraffinic petroleum oil is a mixture of from 80% to 100% by volume light paraffinic petroleum oil and from 0% to 20% by volume of heavy paraffinic petroleum oil, for example, Sunpray 6N (available from Sunoco, Inc.), Orchex 796 (available from ExxonMobile US A) and BVA Spray 10 (available from BVA Oils). The severely solvent refined light and heavy paraffinic petroleum oil mixture may be present in a concentration of from 20% to 30% by weight of all the components in the total formulation, preferably in a concentration of from 24% to 26% by weight, based on the total weight of all the components in the composition.
An acid is used to buffer the formulation in order to stabilize the zeta-cypermethnn from epimerizing to less active isomers. The acid is preferably acetic acid or glacial acetic acid and is present in a concentration of from 0.01% to 0.15% by weight, based on the total weight of all the components in the composition.
The insecticidal formulation may further comprise additional components such as an anti-freeze agent, an anti-foam agent and/or a biocide.
A preferred embodiment of this aspect of tiie invention is an insecticidal emulsifiable concentrate formulation wherein said bifenthrin and enriched cypermethrin insecticides are present in a ratio of 1/4 to 4/1 and a concentration of from 0.05% to 30%, the aromatic solvent is present in a concentration of from 40% to 55%, the acetic acid is present in a concentration of from 0.01% to 0.15%, the severely solvent refined light and heavy paraffinic petroleum oil is present in a concentration of from 20% to 30%, the branched dodecylbenzene sulfonate salt is present in a concentration of from 1.5% to 4.5%, the ethoxylated castor oil or mixture of castor oils is present in a concentration of from 1.% to 4.5% and the

polyethylene glycol fatty acid ester is present in a concentration of from 0.10% to 0.60% wherein all %'s are % by weight based upon the total weight of the formulation.
Another aspect of the present invention is directed to an insecticidal composition comprising an aqueous mixture of bifenthrin and enriched cypermethrin, an aromatic solvent, one or more nonionic polymeric surfactants, an antifoam agent, a preservative and glycerine, wherein the bifenthrin and enriched cypermethrin insecticides are present, at least collectively, in an insecticidally effective amount.
The aromatic solvent is selected from alkylated naphthalene aromatic and alkylated naphthalene depleted aromatic fluids, for example Aromatic 200 ND Fluid and Aromatic 200 Fluid (both available from ExxonMobil Chemicals). The aromatic solvent is present in a concentration of from 5% to 30% by weight, preferably 12% to 15% by weight, based on the total weight of all components in the composition.
Preferably, the nonionic polymeric surfactant is one or more surfactants selected from the group consisting of an alkyd polyethylene glycol, for example, Atlox 4914 (available from Uniqema Corporation) and a polyalkylene glycol ether, for example. Atlas G-5000 (available from Uniqema Corporation). Preferably the nonionic polymeric surfactant is present in a concentration of from 3% to 20% by weight preferably fiom 8% to 12% by weight, based on the total weight of all components in the composition.
The antifoam agent is preferably a silicone containing antifoam agent, for example, Rhodorsil emulsion 1824 antifoam (available from Rhodia Corporation) and Dow Coming AF Emulsion (available fiom Dow Coming Corporation). Preferably the antifoam agent is present in a concentration of from 0.001% to 1.5% by weight, based on the total weight of all the components in the composition.
The biocide is an isothiazolone mixture, for example, Kathon CG/ICP preservative or Legend MK preservative (available from Rohm and Haas Corporation).' Preferably the biocide is present in a concentration of fiom 0.001% to 1.5% by weight, based on the total weight of all the components in the composition.
The glycerine is preferably refined glycerine, for example, Agnique GLY 99-U glycerine (available fiom Cognis Corporation). Glycerine is present in a

concentration of from 3% to 15% by weight, preferably from 5% to 10% by weight, based on the total weight of all the components in the composition.
Water is used as a diluent and preferably is purified water, for example, deionized or distilled water, and is present in an amount that would dilute the active ingredients to a desired concentration. Preferably water is present in a concentration of from 40% to 60% by weight, based on the total weight of all the components in the composition.
A preferred embodiment of this aspect of the invention is an insecticidal Msncentrated aqueous emulsion formulation wherein said bifenthrin and enriched jypermethrin insecticides are present in a ratio of from 1/4 to 4/1 and in a concentration of from 0.05% to 30%, the aromatic solvent is present in a concentration of fiom 12% to 15%, nonionic polymeric surfactant is present in a concentration of from 8% to 12%, the antifoam agent is present in an amount of from 0.001% to 1.5%, the preservative is present in a concentration of from 0.001% to 1.5%, glycerine is present in a concentration of from 5% to 10% and water is present in a concentration of fiom 40% to 60%, wherein all %'s are % by weight based upon the total weight of all the components in the fismiulation.
The term "ambient temperature" as utilized herein shall generally mean any suitable temperature found in a laboratory or other working quarter, and is generally not below about 15" C nor above about 30° C.
The formulations of the present invention are further illustrated by the examples below. The examples serve only to illustrate the invention and should not be interpreted as limiting since further modifications of the disclosed invention will be apparent to those skilled in the art. All such modifications are deemed to be within the scope of the invention as defined in the claims.
Example 1 This example illustrates one protocol for the preparation of a 2/1 ratio of bifenthrin to ze/a-cypermethrin emulsifiable concentrate formulation of the present invention.
To 42,32 grams of Aromatic 200 ND was added 8.34 grams of melted bifenthrin (95.9% active ingredient) and 11.11 grams of zeto-cypermethtin (36% active ingredient, prepared by the process disclosed in U. S. Patent 4,997,970). The

EXAMPLE 2
Dilution stability studies were conducted using 2.5 mL of the fonnulation of Example 1 added to 47.5 mL of water with 342 ppm hardness in a 50 mL Nessler tube. The Nessler tube was sealed with a rubber stopper and the contents mixed by inverting the tube ten times. The Nessler tube was placed in a tube rack at ambient temperature and the percent separation was recorded at 2.0 hours and 4,0 hours. The percent separation was calculated by first measuring the height of the separation, if any, then the total height of the mixture. Dividing the separation height by the total height and multiplying by 100 provides the percent separation. Table 2 sets forth the dilution stability percent separation of the formulations described in Example I and Table 1. The formulations are identified by the formulation code corresponding to those in Example 1 and in Table 1.
As a control experiment, 6.0 grams of a commercially available formulation of bifenthrin (Capture 2EC available from FMC Corporation) and 1.2 grams of a commercially available formulation of zete-cypermethrin (Mustang Max 0.8EC* available from FMC Corporation) were blended together in 1.2 grams of Aromatic 200. The concentration of AI's was similar to the concentration of AI's in fonnulation code F2. A dilution stability test was performed using 2.5 mL of the control blend in 47.5 mL of water containing 342 ppm hardness as described above. The dilution stability percent separation results of the control experiment are presented in Table 2.
TABLE 2 Percent Separation of Formulation in Water Containing 342 ppm Hardness

(Agnique CSO-36), 2.12 grams ethoxylatcd castor oil (Agnique CSO-25), 25.00 grama of severely solvent refined light and heavy paraffinic petroleum oil (Sunspray 6N) and 0.1 gram of glacial acetic acid was added. Upon completion of the addition, the agitation was continued until a yellowish homogeneous solution was obtained.
Example 4 A dilution stability study was conducted using 2.5 mL of the formulation prepared in Example 3 added to 47.5 mL of water with 342 ppm hardness in a 50 mL Nessler tube. The Nessler tube was sealed with a rubber stopper and the contents mixed by inverting the tube ten times. A total of three Nessler tubes were prepared in this manner. One Nessler tube was placed in a tube rack maintained at 0°C, one in a tube rack maintained at ambient temperature and one in a tube rack maintained at 30 "C, all were maintained for 24 hours. The percent separation after 24 hours was 0% for each temperature.
Example S
This example illustrates one protocol for the preparation of a 3/1 ratio of bifenthrin to zeto-cypermethrin concentrated aqueous emulsion formulation of the present
invraition
To a vessel equipped with a mechanical stirrer and a homogenizer was added 0.10 gram of a silicone containing antifoam agent (Rhodorsil emulsion 1824 antifoam), 6.0 grams of a polyalkylene glycol ether nonionic polymeric surfactant (Atlas G5000) and 49.15 grams of deionized water. The mixture was stirred and heated at 50°C to 50^C. While maintaining this temperature, the homogenizar was turned on and a warm (50C to 55'C) mixture of 13.63 grams of alkylated naphthalene depleted aromatic solvent (Aromatic 200 ND), 8.42 grams of zeta-cypemiethriii (36% active ingredient, prepared by the ptxjcess disclosed in U. S. Patent 4,997,970), 10.10 grams of bif«axthrin (95.9% active ingredient) and 4.00 grams of alkyd polyettiylene glycol nonionic surfactant (Atlox 4914) was added slowly. The mixture was homogenized until a particle size of less than three microns at 90% tile was obtained. The homogenizer was turned off and the stirred

mixture was allowed to cool to less than 40°C at which time 8.S grams of refined glycerine (Agnique QLY99-U) and 010 grams of preservative (Legend MK) were added. The resulting mixture was stirred until a homogenous solution was obtained while cooling to ambient temperature.
Example 6
A dilution stability study was conducted using 2.5 mL of the formulation prepared in Example 5 added to 47.5 mL of water with 342 ppm hardness in a 50 mL Nessler tube. The Nessler tube was sealed with a rubber stopper and the contents mixed by inverting the tube ten times. A total of three Nessler tubes were prepared in this manner. One Nessler tube was placed in a tube rack maintained at 0C, one in a tube rack maintained at ambient temperature and one in a tube rack maintained at 30 °C, all were maintained for 24 hours. The percent separation after 24 hours was 0% for each temperature.
While this invention has been described with an emphasis upon preferred embodiments, it will be understood by those of ordinary skill in the art that variations of the preferred embodiments may be used and that it is intended that the invention may be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications encompassed within the spirit and scope of the invention as defined by the following claims.

WHAT IS CLAIMED IS;
1 An insecficidal composition comprising:
a) bifenthrin;
b) enriched cypennethrin;
c) one or more aromatic or diphatic solvents;
d) an acid;
e) a severely solvent refined light and heavy paraffinic petroleum oil;
f) a surfactant blend comprising:
i) an alkylbenzene sulfonate salt;
ii) an ethoxylated castor oil; and
iii) a polyethylene glycol fatty acid ester or ethoxylated fatty acid.
2 An insecticidal composition of claim 1 wherein the enriched cypermethrin is selected from the group consisting of ai|pAo-cypennethrin,/>eto-cypennethrin, theta-cypermethrin and zeto-cypennethrin.
3 An insecticidal composition of claim 2 wherein the enriched cypermethrin is zeto-cypermethrin.
4 An insecticidal composition of claim 3 wherein bifenthrin and zeta-cypennethrin are present in a combined amount of from 0.05% to 30 % by weight based on the total weight of the formulation.
5 An insecticidal composition of claim 4 wherein the ratio of bifenthrin to zeta-cypermethrin is from 1/4 to 4/1.
6 An insecticidal composition of claim 1 wherein the aromatic solvent is
selected from 'alkylated naphthalene aromatic solvent and alkylated naphthalene
depleted aromatic solvent.

7 An insecticidal composition of claim 6 wherein the aromatic solvent is present in a concentration of from 40% to 55 % by weight based on the total weight of the formulating.
8 An insecticidal composition of claim 1 wherein the alkyl benzene sulfonate salt is selected from branched dodecylbenzene sulfonate, calcium salt and branched dodecylbenzene sulfonate, aminoethylethanolamine salt.
9 An insecticidal composition of claim 8 wherein the alkylbenzene sulfonate salt is present in a concentration of from 1.5% to 4.5% by weight based upon the total weight of the formulation
10 An insecticidal composition of claim 1 wherein the ethoxylated castor oil is selected from ethoxylated castor oils having an EO number of from 20 to 40.
11 An insecticidal composition of claim 10 wherein the ethoxylated castor oil is present in a concentration of from 1.5% to 4.5% by weight based on the total weight of the formulation.
12 An insecticidal composition of claim 1 wherein the polyethylene glycol fatty acid ester is selected from polyethylene glycol monooleate glycols having an average M„ of from 300 to 500.
13 An insecticidal composition of claim 12 wherein the polyethylene glycol fatty acid ester is present in a concentration of from 0.10% to 0.60% by weight based on the total weight of the formulation.
14 An insecticidal composition of claim 1 wherein the severely solvent refined light and heavy parafrinic petroleum oil is present in a concentration of from 20% to30% by weight based on the total weight of the formulation.
15 An insecticidal composition of claim 1 wherein the acid is selected from the group consisting of acetic acid and glacial acetic acid.

16 An insecticidal composition of claim 15 wherein the acid is present ia. a concentration of from 0,10% to 0.15% by weight based on the total weight of the formulation.
17 A method for controlling insects comprising applying the composition of claim 1 to a locus where insects are present or are expected to be present.
18 A composition of claim 1 further comprising at least one additional components selected from an anti-freeze agent, an anti-foam agent and a biocide.
19 An insecticidal composition comprising:
a) bifenthrin and zete-cypermethrin present in a ratio of from 1/4 to 4/1 and in a total concentration of from 0.05% to 30%;
b) an aromatic solvent present in a concentration of from 40% to 55%;
c) acetic acid present in a concentration of from 0.01 % to 0.15%;
d) severely solvent refined light and heavy parafSnic petroleum oil in a concentration of form 20% to 30%;
e) a surfactant blend consisting of:
a. alkylbenzene sulfonate salt in a concentration of from 1.5% to 4.5%;
b. ethoxylated castor oil in a concentration of from 1.5% to 4.5%; and
c. polyethylene glycol fetty acid ester present in a concentration of from
0.10% to 0.60%;
wherein all % are % by weight based on the total weight.
20 A method for controlling insects comprising applying the composition of claim 19 to a locus where insects are present or are expected to be present.
21 A cqinposltion of claim 19 further comprising at least one additional component selected from an anti>freeze agent, an antifoam agent and a biocide.
22 An insecticidal composition comprising:
a) bifenthrin;

b) enriched cypramethrin;
c) one or more aromatic solvent;
d) one or more nonionic polymeric surfactant;
e) an antifoam agent;
f) abiocide;
g) glycerine; and
h) water.
23 An insecticidal composition of claim 22 wherein the enriched cypeimethrin is selected firom the group consisting of a(pAa-cypermethrin, 6eto-cypermethrin, theta-cypermethrin and zeto-cypermethrin.
24 An insecticidal composition of claim 23 wherein the enriched cypermethrin is zeto-cypermethrin.
25 An insecticidal composition of claim 24 wherein bifenthrin and zetO' cypermethrin are present in a combined amount of from 0.05% to 30 % by weight based on the total weight of the formulation.
26 An insecticidal composition of claim 25 wherein the ratio of bifenthrin to zeta-cypermethrin is from 1/4 to 4/1.
27 An insecticidal composition of claim 22 wherein the aromatic solvent is
selected from alkylated naphthalene aromatic solvent and alkylated naphthalene
depleted aromatic solvent.
28 An insecticidal composition of claim 27 wherein the aromatic solvent is
present in a concentration of from 12% to 15% by weight based on the total weigfht
of the formulation
20 An insecticidal composition of claim 22 wherein the nonionic polymeric surfactant is selected from the group consisting of an alkyd polyethylene glycol and a polyalkylene glycol ether.

30 An insecticidal composition of claim 29 wherein the nonionic polymeric surfactant is present in a concentration of from 8% to 12% by weight based on the total weight of the formulation.
31 An insecticidal composition of claim 22 wherein the antifoam agent is present in a concentration of from 0.001 % to 1.5% by weight based on the total weight of the formulation.
32 An insecticidal composition of claim 22 wherein the biocide is present in a concentration of from 0.001% to 1% by weight based on the total weight of the formulation.
33 An insecticidal composition of claim 22 wherein glycerine is present ia a concentration of from 5% to 10% by weight based on the total weight of the formulatioa
34 An insecticidal composition of claim 22 wherein water is present in a concentration of from 40% to 60% by weight based on the total weight of the fomiulation.
35 A method for controlling insects comprising applying the composition of claim 22 to a locus where insects are present or are expected to be present.
36 An insecticidal composition comprising:
a) bifenthrin and zeto-cypermethrin present in a ratio of from 1/4 to 4/1 and in a total concentration of from 0.05% to 30%;
b) one or more aromatic solvent present in a concentration of from 12% to 15%;
c) one or more nonionic polymeric surfactant present in a concentration of from 8% to 12%;
,d) an antifoam agent in a concentration of from 0.001 % to 1.5%;
e) a biocide present in a concentration of from 0.001% to 1.5%;
f) glycerine present in a concentration of from 5% to 10%; and

g) water present in a concentration of from 40% to 60%i wherein all % are % by weight based on the total weight of all the components in the formulation.
37 A method for controlling insects comprising applying the composition of claim 36 to a locus where insects are present or are expected to be present.

38. An insecticidal composition substantially as herein described with
reference to the foregoing description, examples and the
accompanying tables,
39. A method substantially as herein described with reference to the
foregoing description, examples and the accompanying tables.

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Patent Number

271997

Indian Patent Application Number

3236/CHENP/2008

PG Journal Number

12/2016

Publication Date

18-Mar-2016

Grant Date

14-Mar-2016

Date of Filing

24-Jun-2008

Name of Patentee

FMC CORPORATION

Applicant Address

1735 MARKET STREET, PHILADELPHIA, USA

Inventors:

#	Inventor's Name	Inventor's Address
1	STAETZ, CHARLES A	85 HICKORY LANE , NEWTOWN, PENNSYLVANIA 18940, USA
2	YANG HUI S.	6 DAISY COURT, PLAINSBORO, NEW JERSEY 08536, USA
3	GARCIA HYLSA	918 MCLAIN STREET, ELIZABETH

PCT International Classification Number

A01N35/04

PCT International Application Number

PCT/US2006/049061

PCT International Filing date

2006-12-21

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	60/752,979	2005-12-22	U.S.A.