AU2019236750B2 - Chlorpyrifos formulation - Google Patents

Abstract

The present invention relates to an emulsifiable concentrate formulation of chlorpyrifos. The emulsifiable concentrate formulation comprises chlorpyrifos at a concentration of greater than about 500 g/L; at least one surfactant; and a 5 solvent. The emulsifable concentrate formulation assists in overcoming one or more of the inherent limitations of commercially available chlorpyrifos formulations. Furthermore, the emulsifiable concentrate formulation provides an alternative to the presently available commercial products.

Description

TITLE CHLORPYRIFOS FORMULATION FIELD OF THE INVENTION

[0001] The present invention relates to a chlorpyrifos formulation. More particularly, the invention relates to an emulsifiable concentrate formulation of chlorpyrifos. More particularly, the invention relates to an emulsifiable concentrate of chlorpyrifos that contains a high level of chlorpyrifos as the active agent and to methods of preparing and using said formulation.

BACKGROUND TO THE INVENTION

[0002] Any reference to background art herein is not to be construed as an admission that such art constitutes common general knowledge in Australia or elsewhere.

[0003] Chlorpyrifos belongs to the organothiophosphate pesticide family. Chlorpyrifos is the common name for O,O-diethyl O-3,5,6-trichloro-2-pyridyl phosphorothioate (CAS# 2921-88-2). The organothiophosphate pesticides act by cholinesterase inhibition with acaricide (mite and tic control), nematicide (nematode control) and general insecticide applications via contact, stomach and respiratory routes of exposure on target organisms.

[0004] There is a need for an emusifiable concentrate of chlorpyrifos that overcomes one or more of the inherent limitations of commercially available chlorpyrifos formulations. Furthermore, there is a need for alternatives to the presently available commercial products.

SUMMARY OF THE INVENTION

[0005] In a first aspect, although it need not be the only or indeed the broadest form, the invention resides in an emulsifiable concentrate formulation comprising:

chlorpyrifos at a concentration of greater than about 500 g/L;

at least one surfactant; and

a solvent.

[0005a] In a related aspect of the present invention, there is provided an emulsifiable

concentrate formulation comprising:

chlorpyrifos at a concentration of greater than 550 g/L;

at least one surfactant selected from the group consisting of an alkoxylated

alkylphenol, an alkylbenzenesulphonate, a castor oil ethoxylate an ethoxylated

tristyrylphenol and any combination thereof; and

an organic solvent, wherein the organic solvent is selected from the group

consisting of an alkyl benzoate, an alkyl ketone, an aryl ketone, and any combination

thereof.

[0006] Suitably, chlorpyrifos is present at a concentration of greater than about 525 g/L, greater than about 550 g/l, greater than about 575 g/L, greater than about 600 g/L, greater than about 625 g/L, greater than about 650 g/L, greater than about 675 g/L, greater than about 700 g/L, greater than about 725 g/L, greater than about 750 g/L, greater than about 775 g/L, or greater than about 800g/L of the formulation.

[0007] Suitably, the solvent is present in an amount of at least about 300 g/L or at least about 400 g/L of the formulation. Preferably, the solvent is present in an amount ranging between about 400 g/L to about 700 g/L of the formulation. More preferably, the solvent is present in an amount ranging between about 400 g/L to about 600 g/L of the formulation.

[0008] In one embodiment, the solvent is selected from the group consisting of an aromatic hydrocarbon, a lactam, a ketone, an alkyl benzoate, a carboxamide, a lactone and any combination thereof.

[0009] Suitably, the solvent is selected from aromatic solvents and esters. Suitably, the solvent is selected from the group consisting of ketones, alkyl benzoates, and any combination thereof. More suitably, the solvent is selected from the group consisting of aromatic ketones, unsaturated cyclic ketones, alkyl benzoates and any combination thereof. Preferably, the solvent is selected from the group consisting of aromatic ketones, a,p-unsaturated cyclic ketones, alkyl benzoates and any combination thereof. Most preferably, the solvent is selected from the group consisting of acetophenone, methyl benzoate, ethyl benzoate, isophorone and combinations thereof.

[0010] In one embodiment, the emulsifiable concentrate formulation comprises two or more surfactants. In a particular embodiment, the emulsifiable concentrate formulation comprises two surfactants.

[0011] The surfactant is suitably present in an amount of at least about 20 g/L, at least about 30 g/L, at least about 40 g/L, at least about 50 g/L, at least about 60 g/L, at least about 70 g/L, at least about 80 g/L, or at least about 90 g/L of the formulation. Preferably, the surfactant is present in an amount ranging between about 20 g/L to about 150 g/L, or between about 30 g/L to about 100 g/L of the formulation.

[0012] In one embodiment, the surfactant is selected from the group consisting of an alkoxylated oil, an alkylphenol alkoxylate, an alkoxylated alcohol, an alkyl ether, a polypropylene glycol alkoxylate, an alkoxylated polyaryl phenol, an alkoxylated block co-polymer, an alkylbenzenesulphonate, such as calcium alkylbenzenesulphonate, an alcohol ether sulphate, an alkylamine ethoxylate and any combination thereof. More preferably, the surfactant is selected from the group consisting of an ethoxylated castor oil, an ethoxylated nonylphenol, an ethoxylated alcohol, an ethoxylated tristyrylphenol, an ethoxylate-propoxylate copolymer, a C10-16 alkylbenzenesulphonate (branched or linear in solvent), a branched alcohol ether sulphate, a tallow amine alkoxylated salt, an alkyl polyoxyalkylene ether and any combination thereof.

[0013] In one embodiment, the surfactant comprises a non-ionic surfactant and/or an anionic surfactant.

[0014] In a second aspect, the invention provides a method of preparing an emulsifiable concentrate formulation including the steps of:

(a) combining chlorpyrifos, at least one surfactant and a solvent, wherein chlorpyrifos is present at a concentration of greater than about 500 g/L; and

(b) mixing the mixture of step (a) to thereby prepare the emulsifiable concentrate formulation.

3a

[0014a] In a related aspect, the present invention provides a method of preparing an

emulsifiable concentrate formulation including the steps of:

a) combining chlorpyrifos, at least one surfactant and an organic solvent,

wherein chlorpyrifos is present at a concentration of greater than about 550 g/L and

wherein the organic solvent is selected from the group consisting of an alkyl benzoate,

an alkyl ketone, an aryl ketone, and any combination thereof and wherein the

surfactant is selected from the group consisting of an alkoxylated alkylphenol, an

alkylbenzenesulphonate, a castor oil ethoxylate, an ethoxylated tristyrylphenol and any

combination thereof; and (b) mixing the mixture of step (a) to thereby prepare the emulsifiable concentrate formulation.

[0015] For the present aspect, the emulsifiable concentrate formulation is suitably that of the first aspect.

[0016] In a third aspect, the invention provides an emulsifiable concentrate formulation prepared by the method of the second aspect.

[0017] In a fourth aspect, the invention provides a method of controlling a pest in a target area, including the step of applying a pestidically effective amount of the emulsifiable concentrate formulation of the first and or third aspects mixed with water or a water-containing liquid to the target area to thereby control said pest.

[0018] In one embodiment, the method of the present aspect further includes the initial step of mixing the emulsifiable concentrate formulation with water or water-containing liquid.

[0019] As used herein, except where the context requires otherwise, the term "comprise" and variations of the term, such as "comprising", "comprises" and "comprised", are not intended to exclude further elements, components, integers or steps but may include one or more unstated further elements, components, integers or steps.

[0020] As used herein, the term 'about' means the amount is nominally the number following the term 'about' but the actual amount may vary from this precise number to an unimportant degree.

[0021] It will be appreciated that the indefinite articles "a" and "an" are not to be read as singular indefinite articles or as otherwise excluding more than one or more than a single subject to which the indefinite article refers. For example, "a" surfactant includes one surfactant, one or more surfactants and a plurality of surfactants.

DETAILED DESCRIPTION OF THE INVENTION

[0022] There is an advantage in providing pesticide products in a condensed or highly loaded form having a high concentration of active ingredient(s). By way of example, the treatment of a given volume of produce or target area (e.g., crop, land, commercial or residential premises etc) can be achieved with a reduced amount of pesticide product being used. As such, these highly loaded pesticide products afford a broadly better economic outcome together with reduced costs (e.g., non-active ingredient, packaging, handling, storage, freight, labour, regulatory licensing and disposal costs) and less environmental impact (e.g., reduced non-active ingredients, such as solvents, surfactants, preservatives, anti-oxidants, dyes and consumption deterrents, and packaging, such as containers, closures, labels/booklets, pallets and pallet liners/boxes/wrapping).

[0023] In addition to the above, providing an emulsifiable concentrate form of a pesticide product rather than as a suspension concentrate form, further alleviates some or all of the deficiencies of the latter. To this end, the active ingredient in emulsifiable concentrate formulations is not in the solid phase as it is in suspension concentrate form, and thereby is not subject to settling or physical phase separation of solid from liquid. Furthermore, the selection of appropriate solvents and other excipients typically requires careful consideration so as to achieve a passable emulsifiable concentrate formulation.

[0024] In view of the foregoing, the invention advantageously provides a highly loaded emulsifiable concentrate composition or formulation suitable for the control of a range of pests in an agricultural or horticultural setting.

[0025] As generally used herein, the term "highly loaded" is to be taken to refer to the concentration level of chlorpyrifos in an emulsifiable concentrate formulation on a weight by volume basis (g/L) in the amount of greater than about 500 g/L.

[0026] In a first aspect, although it need not be the only or indeed the broadest form, the invention resides in an emulsifiable concentrate formulation comprising:

chlorpyrifos at a concentration of greater than about 500 g/L;

at least one surfactant; and

a solvent.

[0027] In a related aspect, the invention provides a method of preparing an emulsifiable concentrate formulation including the steps of:

(a) combining chlorpyrifos, at least one surfactant and a solvent, wherein chlorpyrifos is present at a concentration of greater than about 500 g/L; and

(b) mixing the mixture of step (a) to thereby prepare the emulsifiable concentrate formulation.

[0028] The statements which follow apply equally to the aforementioned aspects of the invention.

[0029] It will be well understood that the term "emulsifiable concentrate formulation" or "emulsifiable concentrate" (EC) refers to a liquid formulation or concentrate of an active agent, such as a pesticide, which, on dilution in water or a water-containing liquid, form an emulsion such as a spontaneous milky white emulsion comprising a dispersed water insoluble phase. The term "emulsion", as used herein, refers to a fine dispersion of minute droplets of one liquid in another in which it is not soluble or miscible and includes microemulsions and macroemulsions.

[0030] The term "chlorpyrifos" refers to 0,0-diethyl0-3,5,6-trichloro-2-pyridyl phosphorothioate (CAS# 2921-88-2) in free form or in agrochemically acceptable salt form such as alkali metal salts and amine salts. The term 'chlorpyrifos' also includes similar compounds such as 'chlorpyrifos-methyl'. The term 'chlorpyrifos methyl' refers to 0,0-dimethyl0-3,5,6-trichloro-2-pyridyl phosphorothioate in free form or in agrochemically acceptable salt form such as alkali metal salts and amine salts. With respect to the chlorpyrifos concentration recited herein, it will be appreciated that this refers to the content of chlorpyrifos per se within the formulation rather than, for example, a salt form thereof. The term "chlorpyrifos" as used herein may be interchangeable with the term 'chlorpyrifos-methyl'. The emulsifiable concentrate formulation may comprise both chlorpyrifos and chlorpyrifos-methyl.

[0031] The term 'pest' and the like includes insects and the like. As such, the term 'pests' may be used interchangeably with 'insect'. Similarly, the term 'pesticides' and the like may be used interchangeably with the term 'insecticide' and the like.

[0032] For the present invention, chlorpyrifos is suitably present in a highly loaded concentration (i.e., greater than about 500 g/L) that provides an emulsifiable concentrate formulation suitable for use in the effective prevention, control and/or treatment of a pest. To this end, chlorpyrifos may be present in an amount from about 500 g/L to about 900 g/L or any range therein such as, but not limited to, about 500 to about 850 g/L, or about 500 g/L to about 800 g/L, or about 500 g/L to about 750 g/L, or about 525 g/L to about 725 g/L, or 525 g/L to about 720 g/L, or about 600 g/L to about 700 g/L of the emulsifiable concentrate formulation. In particular embodiments of the present invention, chlorpyrifos is present in an amount of about 500, 505, 510, 515, 520, 525,530, 535,540,545, 550,555,560,565,570,575,580,585,590,595,600,605,610,615,620,625, 630,635,640,645,650,655,660,665,670,675,680,685,690,695,700,705, 710,715,720,725,730,735,740,745,750,755,760,765,770,775,780,785, 790,795,800,805,810,815,820,825,830,835,840,845,850,855,860,865, 870, 875, 880, 885, 890, 895, 900, g/L, or any range therein, of the emulsifiable concentrate formulation.

[0033] The emulsifiable concentrate formulation may further comprise one or more pesticidal agents or ingredients. It will be apparent to the skilled artisan that the one or more pesticidal agents may include any appropriate pesticidal agent known in the art that is compatible with chlorpyrifos. The pesticide agents includes, but at not limited to, insecticidal agents or ingredients, and/or fungicidal agents or ingredients. The insecticidal agent includes, but are not limited to, organophosphates, carbamates, diamides, neonicotinoids, macrocyclic lactones, oxadiazines, pyrazoles, sulfoximines, tetramic acids, tetronic acids and thiazoles By way of example, the pesticidal agent may be bifenthrin and/or alpha cypermethrin. In one embodiment, the emulsifiable concentrate formulation further comprises bifenthrin. In another embodiment, the emulsifiable concentrate formulation further comprises alpha-cypermethrin. The pesticidal agent may be present in an amount of from about 0.1 g/L to about 250 g/L, about 10 g/L to about 150g/L, about 20 g/L to about 100 g/L, about 20 g/L to about 50 g/L, or about 25 g/L to about 35 g/L of the formulation.

[0034] In certain embodiments, the chlorpyrifos and one or more pesticidal agent(s) together may be present in an amount from about 500 g/L to about 900 g/L or any range therein such as, but not limited to, about 500 to about 850 g/L, or about 500 g/L to about 800 g/L, or about 500 g/L to about 750 g/L, or about

525 g/L to about 725 g/L, or 525 g/L to about 720 g/L, or about 600 g/L to about 700 g/L of the emulsifiable concentrate formulation. In particular embodiments of the present invention, chlorpyrifos is present in an amount of about 500, 505, 510, 515, 520, 525, 530, 535, 540, 545, 550, 555, 560, 565, 570,575,580,585, 590,595,600,605,610,615,620,625,630,635,640,645,650,655,660,665, 670,675,680,685,690,695,700,705,710,715,720,725,730,735,740,745, 750,755,760,765,770,775,780,785,790,795,800,805,810,815,820,825, 830,835,840,845,850,855,860,865,870,875,880,885,890, 895, 900, g/L, or any range therein, of the emulsifiable concentrate formulation.

[0035] The term "solvent" refers to any liquid capable of maintaining another substance in solution. Examples of solvents include, but are not limited to, organic solvents. It will be apparent to the skilled artisan that the solvent may include any appropriate solvent as are known in the art. By way of example, the solvent may comprise at least one of an alkyl benzoate (such as methyl benzoate and ethyl benzoate), a solvent naphtha (petroleum), a heavy aromatic petroleum derivative or hydrocarbon, pyrrolidones including N-alkylated pryrrolidones such as N-methyl pyrrolidone and 1-butylpyrrolidone, ketones including alkylketones (such as isophorone) and arylketones (such as acetophenone), and carboxyamides (such as N,N-dimethylformamide, N,N dimethylacetylamide and the pryrrolidones of N-methyl pyrrolidone, N octylpyrrolidoneand1-butylpyrrolidone).

[0036] In one embodiment, the solvent is suitably selected from the group consisting of an aromatic hydrocarbon, a lactam, a ketone, an alkyl benzoate, a carboxamide, a lactone and any combination thereof.

[0037] In one embodiment, the solvent is selected from aromatic solvents and esters. Suitably, the solvent is selected from the group consisting of ketones, alkyl benzoates, and a combination thereof. More suitably, the solvent is selected from the group consisting of aromatic ketones, unsaturated cyclic ketones, alkyl benzoates and a combination thereof. Preferably, the solvent is selected from the group consisting of aromatic ketones, a,p-unsaturated cyclic ketones, alkyl benzoates and a combination thereof. Most preferably, the solvent is selected from the group consisting of acetophenone, methyl benzoate, ethyl benzoate, isophorone and combinations thereof.

[0038] It will also be appreciated that the solvent may be used in combination as a mixture of two, three, four, five or more solvents.

[0039] For the above aspects, the solvent may be present in an amount from about 300 g/L to about 900 g/L or any range therein such as, but not limited to, about 400 g/L to about 700 g/L, or about 400 g/L to about 600 g/L, or about 400 g/L to about 500 g/L of the emulsifiable concentrate formulation. In particular embodiments of the present invention, the solvent is present in an amount of about 300, 305, 310, 315, 320, 325, 330, 335, 340, 345, 350, 355, 360, 365, 370,375,380,385,390,395,400,405,410,415,420,425,430,435,440,445, 450,455,460,465,470,475,480,485,490,495,500,505,510,515,520,525, 530,535,540,545,550,555,560,565,570,575,580,585,590,595,600,605, 610,615,620,625,630,635,640,645,650,655,660,665,670,675,680,685, 690,695,700,705,710,715,720,725,730,735,740,745,750,755,760,765, 770,775,780,785,790,795,800,805,810,815,820,825,830,835,840,845, 850, 855, 860, 865, 870, 875, 880, 885, 890, 895, 900 g/L, or any range therein, of the emulsifiable concentrate formulation.

[0040] The solvent provided herein is preferably an agriculturally acceptable solvent. The term "agriculturally acceptable solvent" as used herein refers to a solvent that is not unacceptably damaging to a plant and/or its environment, and/or not unsafe to the user or others that may be exposed to the solvent when used as described herein.

[0041] As used herein, the term "surfactant" or surface-active agent refers to an agent, usually an organic chemical compound that is at least partially amphiphilic (i.e., typically containing a hydrophobic tail group and hydrophilic polar head group). Given their structure, surfactants are generally capable of lowering the surface tension (or interfacial tension) between two liquids or between a liquid and a solid. Further to this, these properties typically allow solubility of the surfactant in organic solvents as well as in water, and allow the surfactant to promote solubilization or at least dispersal of fatty/waxy materials in water and water-containing solutions. In this regard, a surfactant may act as a detergent, a wetting agent, an emulsifying agent, a foaming agent and/or a dispersing agent.

[0042] Accordingly, in particular embodiments, the surfactant is or comprises an emulsifying agent. As generally used herein, the term "emulsifying agent" or "emulsifier" refers to a chemical agent, compound, or substance capable of producing an emulsion by reducing the interfacial tension between the two insoluble liquids.

[0043] Similar to that for the solvents provided above, the surfactant provided herein is preferably an agriculturally acceptable surfactant. The term "agriculturally acceptable surfactant" as used herein refers to a surfactant that is generally not unacceptably damaging to a plant and/or its environment, and/or generally not unsafe to the user or others that may be exposed to the surfactant when used as described herein.

[0044] The surfactant, including one or a plurality of surfactants (e.g., 1, 2, 3, 4, 5 etc surfactants), are suitably present in a high enough concentration that allows for the production of a highly loaded emulsifiable concentrate chlorpyrifos formulation. Preferably, the emulsifiable concentrate formulation comprises two surfactants. In this regard, it will be apparent that an amount of the surfactant of the emulsifiable concentrate formulation can vary, for example, depending on the particular chlorpyrifos concentration and the particular surfactant and solvents to be included therein.

[0045] To this end, the surfactant may be present in an amount from about 20 g/L to about 300 g/L or any range therein such as, but not limited to, about 20 g/L to about 150 g/L, or about30gLtoabout 100 g/L of the emulsifiable concentrate formulation. In particular embodiments of the present invention, the surfactant is present in an amount of about 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200, 205, 210, 215, 220, 225, 230, 235, 240, 245, 250, 255, 260, 265, 270, 275, 280, 285, 290, 295, 300 g/L, or any range therein, of the emulsifiable concentrate formulation. In certain embodiments of the present invention, the surfactant is present in an amount of at least about 30 g/L of the emulsifiable concentrate formulation. More preferably, the surfactant is present in an amount ranging between about 30 g/L to about 150 g/L of the emulsifiable concentrate formulation.

[0046] For the present invention, the surfactant is suitably selected from the group consisting of non-ionic surfactants, anionic surfactants, cationic surfactants, zwitterionic surfactants, cation-anion composite surfactants and any combination thereof. Preferably, the surfactants are non-ionic surfactants and/or anionic surfactants. Suitable surfactants include, but are not limited to, alkyl ethers, alkoxylated oils, alkylphenol alkoxylates, alkoxylated alcohols, polypropylene glycol alkoxylates, alkylpolyoxyalkylene ether, alkoxylated polyaryl phenols, alkoxylated block co-polymers, alkylbenzenesulphonates, alcohol ether sulphates, alkylamine ethoxylates and any combination thereof.

[0047] In certain preferred embodiments, the one or more surfactants to be included in the emulsifiable concentrate formulation are or comprise an anionic surfactant. As generally used herein, the term "anionic surfactant" refers to a surfactant comprising, as ionic or ionizable groups, only anionic groups. Such anionic groups may include, for example, -CO2H, -C2-, -S03H, -SO3- _ OS03H, -OSO3-, -H2PO3, -HP03-, -P032-, -H2PO2, =HPO2, -HP02-, =p2-, =POH, and =PO- groups. Suitable anionic surfactants may include those hereinbefore described. Such anionic surfactants may be used alone or in combination as a mixture of two, three, four, five or more anionic surfactants.

[0048] Preferably, the surfactant is selected from the group consisting of an ethoxylated castor oil or vegetable oil, an ethoxylated nonylphenol, an ethoxylated alcohol, an ethoxylated tristyrylphenol, an ethoxylate-propoxylate copolymer, a C10-16 alkylbenzenesulphonate (branched or linear in solvent, optionally in a solvent, such as 2-ethylhexanol, solvent naphtha and/or 1 hexanol), a branched alcohol ether sulphate, a tallow amine alkoxylated salt, an alkoxylated polypropylene glycol and any combination thereof.

[0049] The surfactant is suitably selected from the group consisting of alkoxylated alkylphenol (e.g., Termul 200 and Antarox 724/P); alkylbenzenesulfonic acid, calcium salt in 2-ethylhexanol (e.g., Ninate 60E); castor oil ethoxylate (e.g., Termul 1285); and ethoxylated tristyrylphenol (e.g., Termul 3150).

[0050] It will be apparent in light of the foregoing that the at least one surfactant may be introduced into the formulation of the invention as a soluble concentration in a further solvent (e.g., calcium dodecylbenzene sulfonate in 2 ethylhexanol, solvent naphtha and/or 1-hexanol). It will be appreciated that such amounts of the further solvent may make little or no contribution to the solvency of chlorpyrifos within the formulation of the invention.

[0051] In certain embodiments, the surfactant comprises at least calcium alkylbenzenesulfonate optionally in a further solvent. In embodiments, the surfactant comprises alkylbenzenesulfonic acid, calcium salt in 2-ethylhexanol and one or more of alkoxylated alkylphenol, castor oil ethoxylate, and ethoxylatedtristyrylphenol.

[0052] In certain embodiments, the solvent is not N-methyl pyrrolidone, dimethyl sulfoxide, N,N-dimethylacetamide and/or N-N-dimethylformamide.

[0053] One or more additional auxiliary agents, such as adjuvants, synergists, preservatives, colouring agents (e.g., dyes), odourants, embittering agents and other deterrents and the like, as are known in the art, can also be added where desired to modify the properties of the emulsifiable concentrate formulation as required.

[0054] It will be understood that it is desirable for the emulsifiable concentrate provided herein to be readily or easily pumped or poured from a storage vessel. Preferably, the emulsifiable concentrate formulation has a viscosity at room temperature (i.e., 20 0C) of no more than 2000 cPs (e.g., 1, 5, 10, 20, 30, 40, 50, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000 cPs and any range therein), as viscosities above this typically make it difficult or impractical to pump or pour the formulation. Preferably, the emulsifiable concentrate formulation of the invention has a viscosity at room temperature of about or less than about 1000 cPs or less than about 400 cPs. Preferably, the emsulsifiable concentrate formulation of the invention has a viscosity at room temperature of between about1cPsand about100cPs,orabout45cPs.

[0055] In an embodiment, the emulsifiable concentrate formulation has a viscosity at 5 0C of no more than 2000 cPs (e.g., 1, 5, 10, 20, 30, 40, 50, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000 cPs and any range therein). Preferably, the emsulsifiable concentrate formulation of the invention has a viscosity at 50 C of between about 1 cPs and about 100 cPs, or about 55 cPs.

[0056] In one embodiment, the pH of the emulsifiable concentrate formulation according to CIPAC MT 75.3 is suitably between about 4 and about 11, more suitably between about 5 and about 10, preferably between about 5.5 and about 9.5, more preferably between about 6.0 and about 8.5, even more preferably between about 6 and about 8, and most preferably between about 6.3 and about 7.7.

[0057] In certain embodiments, the emulsion characteristics of the emulsifiable concentrate formulation according to CIPAC MT36.1 is suitably 2mL cream after 30 min, trace of oil after 30 min, and complete re-emulsion after 24h; preferably 2mL cream after 30 mins, and ! trace of oil after 30 min; more preferably trace of cream/oil after 1 hour; and most preferably nil cream/oil after 4 hours.

[0058] In embodiments, the persistent foam of the emulsifiable concentrate formulation according to CIPAC MT47.2 is suitably <60mL after 1 min, preferably <30mL after 1 min, and most preferably <25mL after 1 min.

[0059] In some embodiments, the specific gravity of the emulsifiable concentrate formulation according to CIPAC MT3.1 is suitably between about 1.1 and about 1.4, more suitably between about 1.1 and about 1.3, preferably between about 1.17 and about 1.27, more preferably between about 1.21 and about 1.24, and most preferably about 1.222.

[0060] The emulsifiable concentrate formulation described herein preferably maintains the above properties after accelerated aging equivalent to about 2 years or more of usual storage.

[0061] With respect to the aforementioned aspect of preparing an emulsifiable concentrate formulation of chlorpyrifos, it will be appreciated that this method may be performed using commercially available equipment, such as formulation vessels and the like, known in the art.

[0062] In another aspect, the invention provides an emulsifiable concentrate formulation prepared by the method of the aforementioned aspect.

[0063] In a further aspect, the invention resides in a method of controlling a pest in a target area, including the step of applying a pesticidally effective amount of the emulsifiable concentrate formulation of first and or third mentioned aspects mixed with water or a water-containing liquid to the target area to thereby control said pest.

[0064] Suitably, the method of this aspect further includes the initial step of mixing the emulsifiable concentrate formulation with water or the water containing liquid.

[0065] The terms "treat", "treating" and "treatment" are broadly intended to include preventing or controlling a pest. Treating the pest preferably results in at least maintaining, more preferably maintaining or reducing, and even more preferably reducing the degree or severity of the pest in a target area. In one embodiment, treatment with the emulsifiable concentrate formulation provided herein is able to substantially eradicate a pest from the target area.

[0066] As used herein, "preventing" (or "prevent" or "prevention") refers to a course of action (such as administering an effective amount of the emulsifiable concentrate formulation described herein) initiated prior to the onset of a pest. It is to be understood that such preventing need not be absolute to be beneficial to a plant, crop or the like.

[0067] As generally used herein, "control" (or "controlled" or "controlling") refers to an intervention with the emulsifiable concentrate formulation that reduces the amount of the pest. The term "ameliorating", with reference to a pest, refers to any observable beneficial effect thereto as a result of the administration of the emulsifiable concentrate formulation. The beneficial effect can be determined using any methods or standards known to the ordinarily skilled artisan. Accordingly, these terms are meant to include any lethal (i.e., pesticidal) or inhibitory (i.e., pestistatic) activities of the emulsifiable concentrate formulation against a given pest, including those hereinafter described.

[0068] Herein, the terms "target area", "locus" or "space" refer to any area, location or habitat where the prevention, control and/or eradication of a pest is needed or expected to be needed.

[0069] As used herein, the terms "effective amount" or "pestidically effective amount" refer to an amount of the emulsifiable concentrate formulation that is effective to cause such prevention, control, and/or eradication of the pest. By way of example, an effective amount means an amount necessary to produce an observable pesticidal and/or pestistatic effect on pests, including the effects of death, growth inhibition, inhibition of proliferation, and removal, destruction, or otherwise diminishing the occurrence and activity of these unwanted pests. An effective amount of the emulsifiable concentrate formulation of the invention may vary according to the prevailing conditions such as desired pesticidal and/or pestistatic effect and duration, weather, target species, mode of application, and the like.

[0070] In particular embodiments, an effective amount is the amount of the emulsifiable concentrate formulation of the invention that has an adverse effect on at least 25% (e.g., 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 100% or any range therein) of the pests treated or contacted therewith, more preferably at least 50% of the pests treated or contacted therewith, and even more preferably at least 70% or greater of the pests treated or contacted therewith.

[0071] The efficacy of the emulsifiable concentrate formulation of the present invention may be monitored by determining the mortality of or adverse effect upon treated pests. This includes inhibition or modulation of pests growth, inhibition of pest proliferation, or complete destruction/death of the pest, at any stage of the pest's lifecycle. The actual value of an effective amount for the emulsifiable concentrate formulation is preferably determined by routine screening procedures employed to evaluate pesticidal activity and efficacy, such as those methods well known in the art.

[0072] With respect to the above, an effective amount of the emulsifiable concentrate formulation described herein is preferably administered to the target area or locus of the pest. By way of example, to prevent or control pests in a target area, an effective amount of an emulsifiable concentrate formulation comprising chlorpyrifos is administered to an area adjacent and/or including the plant or crop. As such, a pest can be readily contacted with an effective amount of the emulsifiable concentrate formulation of the invention.

[0073] The pest infestation to be prevented and/or controlled by the method of the present aspect may be in respect of any pest, and more particularly any insect or insects, as are well known in the art. Nonlimiting examples of pests, and in particular insects, that may be treated by application of the emulsifiable concentrate formulation of the invention include grasshoppers, locusts, earwigs, crickets, millipedes, slaters, ants, aphids, flies, mites, beetles, bugs, moths, springtails, caterpillars, loopers, bruchids, fleas, mealybugs, midges, thrips, scale, borers, worms, springtails, weevils, butterflies and cockroaches, which can cause significant damage to, for example, a wide range of agricultural and horticultural crops and plants. Non-limiting examples of the crop being treated include pome fruit, bananas, cassava, citrus fruit, brassica vegetables, grapes, ginger, pineapples, potatoes, strawberries, tomatoes, cereals, pastures, forage crop, oilseeds, cotton, hops, Lucerne, medics, maize, soybeans, sunflowers, rice, sorghum, sugarcane, tobacco and vegetable seedlings generally.

[0074] The emulsifiable concentrate formulation of the invention may be applied to the target crop or plant of interest, to a part thereof (such as the leaf or seed), or to surroundings thereof. Methods and techniques for applying the emulsifiable concentrate formulation are known in the art and may include, for example, ground or aerial spraying.

[0075] In a preferred embodiment, the emulsifiable concentrate formulation is applied at a rate of about 5 to about 3000mL per hectare (e.g., about 5mL, 10mL, 15mL, 20mL, 25mL, 30mL, 35mL, 40mL, 45mL, 50mL, 55mL, 60mL, 65mL, 70mL, 75mL, 80mL, 85mL, 90mL, 95mL, 100mL, 105mL, 110mL, 115mL, 120mL, 125mL, 130mL, 135mL, 140mL, 145mL, 150mL, 155mL, 160mL, 165mL, 170mL, 175mL, 180mL, 185mL, 190mL, 195mL, 200mL, 205mL, 210mL, 215mL, 220mL, 225mL, 230mL, 235mL, 240mL, 245mL, 250mL, 255mL, 260mL, 265mL, 270mL, 275mL, 280mL, 285mL, 290mL, 295mL, 300mL, 305mL, 310mL, 315mL, 320mL, 325mL, 330mL, 335mL, 340mL,

345mL, 350mL, 355mL, 360mL, 365mL, 370mL, 375mL, 380mL, 385mL, 390mL, 395mL, 400mL, 405mL, 410mL, 415mL, 420mL, 425mL, 430mL, 435mL, 440mL, 445mL, 450mL, 455mL, 460mL, 465mL, 470mL, 475mL, 480mL, 485mL, 490mL, 495mL, 500mL, 505mL, 510mL, 515mL, 520mL, 525mL, 530mL, 535mL, 540mL, 545mL, 550mL, 555mL, 560mL, 565mL, 570mL, 575mL, 580mL, 585mL, 590mL, 595mL, 600mL, 605mL, 610mL, 615mL, 620mL, 625mL, 630mL, 635mL, 640mL, 645mL, 650mL, 655mL, 660mL, 665mL, 670mL, 675mL, 680mL, 685mL, 690mL, 695mL, 700mL, 705mL, 710mL, 715mL, 720mL, 725mL, 730mL, 735mL, 740mL, 745mL, 750mL, 755mL, 760mL, 765mL, 770mL, 775mL, 780mL, 785mL, 790mL, 795mL, 800mL, 805mL, 810mL, 815mL, 820mL, 825mL, 830mL, 835mL, 840mL, 845mL, 850mL, 855mL, 860mL, 865mL, 870mL, 875mL, 880mL, 885mL, 890mL, 895mL, 900mL, 905mL, 910mL, 915mL, 920mL, 925mL, 930mL, 935mL, 940mL, 945mL, 950mL, 955mL, 960mL, 965mL, 970mL, 975mL, 980mL, 985mL, 990mL, 995mL, 10OOmL 1005mL, 1010mL, 1015mL, 1020mL, 1025mL, 1030mL, 1035mL, 1040mL, 1045mL, 1050mL, 1055mL, 1060mL, 1065mL, 1070mL, 1075mL, 1080mL, 1085mL, 1090mL, 1095mL, 11OOmL, 1105mL, 1110mL, 1115mL, 1120mL, 1125mL, 1130mL, 1135mL, 1140mL, 1145mL, 1150mL, 1155mL, 1160mL, 1165mL, 1170mL, 1175mL, 1180mL, 1185mL, 1190mL, 1195mL, 1200mL, 1205mL, 1210mL, 1215mL, 1220mL, 1225mL, 1230mL, 1235mL, 1240mL, 1245mL, 1250mL, 1255mL, 1260mL, 1265mL, 1270mL, 1275mL, 1280mL, 1285mL, 1290mL, 1295mL, 1300mL, 1305mL, 1310mL, 1315mL, 1320mL, 1325mL, 1330mL, 1335mL, 1340mL, 1345mL, 1350mL, 1355mL, 1360mL, 1365mL, 1370mL, 1375mL, 1380mL, 1385mL, 1390mL, 1395mL, 1400mL, 1405mL, 1410mL, 1415mL, 1420mL, 1425mL, 1430mL, 1435mL, 1440mL, 1445mL, 1450mL, 1455mL, 1460mL, 1465mL, 1470mL, 1475mL, 1480mL, 1485mL, 1490mL, 1495mL, 1500mL, 1505mL, 1510mL, 1515mL, 1520mL, 1525mL, 1530mL, 1535mL, 1540mL, 1545mL, 1550mL, 1555mL, 1560mL, 1565mL, 1570mL, 1575mL, 1580mL, 1585mL, 1590mL, 1595mL, 1600mL, 1605mL, 1610mL, 1615mL, 1620mL, 1625mL, 1630mL, 1635mL, 1640mL, 1645mL, 1650mL, 1655mL, 1660mL, 1665mL, 1670mL, 1675mL, 1680mL, 1685mL, 1690mL, 1695mL, 1700mL, 1705mL, 1710mL, 1715mL, 1720mL, 1725mL, 1730mL, 1735mL,

1740mL, 1745mL, 1750mL, 1755mL, 1760mL, 1765mL, 1770mL, 1775mL, 1780mL, 1785mL, 1790mL, 1795mL, 1800mL, 1805mL, 1810mL, 1815mL, 1820mL, 1825mL, 1830mL, 1835mL, 1840mL, 1845mL, 1850mL, 1855mL, 1860mL, 1865mL, 1870mL, 1875mL, 1880mL, 1885mL, 1890mL, 1895mL, 1900mL, 1905mL, 1910mL, 1915mL, 1920mL, 1925mL, 1930mL, 1935mL, 1940mL, 1945mL, 1950mL, 1955mL, 1960mL, 1965mL, 1970mL, 1975mL, 1980mL, 1985mL, 1990mL, 1995mL, 2000mL, 2050 mL, 2010mL, 2015mL, 2020mL, 2025mL, 2030mL, 2035mL, 2040mL, 2045mL, 2050mL, 2055mL, 2060mL, 2065mL, 2070mL, 2075mL, 2080mL, 2085mL, 2090mL, 2095mL, 2100mL, 2105mL, 211OmL, 2115mL, 2120mL, 2125mL, 2130mL, 2135mL, 2140mL, 2145mL, 2150mL, 2155mL, 2160mL, 2165mL, 170mL, 2175mL, 2180mL, 2185mL, 2190mL, 2195mL, 2200mL, 2205mL, 2210mL, 2215mL, 2220mL, 2225mL, 2230mL, 2235mL, 2240mL, 2245mL, 2250mL, 2255mL, 2260mL, 2265mL, 2270mL, 2275mL, 2280mL, 2285mL, 2290mL, 2295mL, 2300mL, 2305mL, 2310mL, 2315mL, 2320mL, 2325mL, 2330mL, 2335mL, 2340mL, 2345mL, 2350mL, 2355mL, 2360mL, 2365mL, 2370mL, 2375mL, 2380mL, 2385mL, 2390mL, 2395mL, 2400mL, 2405mL, 2410mL, 2415mL, 2420mL, 2425mL, 2430mL, 2435mL, 2440mL, 2445mL, 2450mL, 2455mL, 2460mL, 2465mL, 2470mL, 2475mL, 2480mL, 2485mL, 2490mL, 2495mL, 2500mL, 2505mL, 2510mL, 2515mL, 2520mL, 2525mL, 2530mL, 2535mL, 2540mL, 2545mL, 2550mL, 2555mL, 2560mL, 2565mL, 2570mL, 2575mL, 2580mL, 2585mL, 2590mL, 2595mL, 2600mL, 2605mL, 2610mL, 2615mL, 2620mL, 2625mL, 2630mL, 2635mL, 2640mL, 2645mL, 2650mL, 2655mL, 2660mL, 2665mL, 2670mL, 2675mL, 2680mL, 2685mL, 2690mL, 2695mL, 2700mL, 2705mL, 2710mL, 2715mL, 2720mL, 2725mL, 2730mL, 2735mL, 2740mL, 2745mL, 2750mL, 2755mL, 2760mL, 2765mL, 2770mL, 2775mL, 2780mL, 2785mL, 2790mL, 2795mL, 2800mL, 2805mL, 2810mL, 2815mL, 2820mL, 2825mL, 2830mL, 2835mL, 2840mL, 2845mL, 2850mL, 2855mL, 2860mL, 2865mL, 2870mL, 2875mL, 2880mL, 2885mL, 2890mL, 2895mL, 2900mL, 2905mL, 2910mL, 2915mL, 2920mL, 2925mL, 2930mL, 2935mL, 2940mL, 2945mL, 2950mL, 2955mL, 2960mL, 2965mL, 2970mL, 2975mL, 2980mL, 2985mL, 2990mL, 2995mL, 3000mL,per hectare and any range therein) and more preferably at a rate of about 30mL to about 2000mL, or about

500mL to about 1500mL per hectare subsequent to dilution thereof in a suitable spray liquid. Obviously, the amount of the emulsifiable concentrate to be applied per hectare will depend, at least in part, upon the concentration of chlorpyrifos therein, the particular pest to be targeted and the type of target crop to which the formulation is to be applied.

[0076] Throughout the specification the aim has been to describe the preferred embodiments of the invention without limiting the invention to any one embodiment or specific collection of features. It will therefore be appreciated by those of skill in the art that, in light of the instant disclosure, various modifications and changes can be made in the particular embodiments exemplified without departing from the scope of the present invention.

[0077] All computer programs, algorithms, patent and scientific literature referred to herein is incorporated herein by reference.

[0078] In order that the invention may be more readily understood and put into practice, one or more preferred embodiments thereof will now be described, by way of example only.

Examples: Embodiments of an emulsifiable concentrate formulation

[0079] The present example provides a number of embodiments of an emulsificable concentrate formulation of the invention including a highly loaded concentration of chlorpyrifos.

Embodiment 1 - 720g/L chlorpyrifos emulsifiable concentrate Composition as follows: Ingredient CAS# Concentration Chlorpyrifos 2921-88-2 734.8g/L (Technical material, 98.1%) (yields 720.8g/L chlorpyrifos) Alkoxylated alkylphenol 37251-69-7 12.1g/L Proprietary (Termul 200, Antarox 724/P) Alkylbenzenesulfonic acid, calcium salt in 2- 68584-23-6, 104- 19.4g/L ethylhexanol 76-7, (Proprietary: Ninate 60E) Acetophenone 98-86-2 463.1g/L (to 1229g/L total)

Chemical and physical parameters as follows: Test As- Accelerated Aged Result manufactured Presentation: Clear, brown Clear, brown liquid liquid Assay: 718.7g/L 724.8g/L Require 695g/L5 schlorpyrifos5 s745g/L pH1% 7.4 7.4 Nominally: 5.5 to 9.5 Persistent foaming 30mL 35mL Require: <60mL foam after 1 min Emulsion characteristics 0.1mL of cream; 0.2mL of cream; Require: <2mL cream after 30 min, <trace of No oil; No oil; oil after 30 min and complete re-emulsion Re-emulsifies/24h Re-emulsifies/24h after 24h

Embodiment 2 - 700g/L chlorpyrifos emulsifiable concentrate

Composition as follows: Ingredient CAS# Concentration Chlorpyrifos 2921-88-2 714.1g/L (Technical material, 98.1%) (yields 700.5g/L chlorpyrifos) Alkoxylated alkylphenol 37251-69-7 11.7g/L Proprietary (Termul 200, Antarox 724/P) Alkylbenzenesulfonic acid, calcium salt in 2- 68584-23-6, 104- 19.4g/L ethylhexanol 76-7, (Proprietary: Ninate 60E) Methyl benzoate 93-58-3 506.6g/L

(to 1252g/L total)

Chemical and physical parameters as follows: Test As- Accelerated Aged Result manufactured Presentation: Clear, brown Clear, brown liquid liquid Assay: 700.9g/L 704.7g/L Require 675g/L5 chlorpyrifos 725g/L pH1% 7.5 7.4 Nominally: 5.5 to 9.5 Persistent foaming 30mL 20mL Require: <60mL foam after 1 min Emulsion characteristics 0.2mL of cream; 0.2mL of cream; Require: <2mL cream after 30 min, <trace of No oil; No oil; oil after 30 min and complete re-emulsion Re-emulsifies/24h Re-emulsifies/24h after 24h

Embodiment 3 - 700g/L chlorpyrifos emulsifiable concentrate Composition as follows: Ingredient CAS# Concentration Chlorpyrifos 2921-88-2 714.1g/L (Technical material, 98.1%) (yields 700.5g/L chlorpyrifos) Alkoxylated alkylphenol 37251-69-7 12.2g/L Proprietary (Termul 200, Antarox 724/P) Alkylbenzenesulfonic acid, calcium salt in 2- 68584-23-6, 104- 19.0g/L ethylhexanol 76-7, (Proprietary: Ninate 60E) Acetophenone 98-86-2 477.1g/L (to 1222g/L total)

Chemical and physical parameters as follows: Test As- Accelerated Aged Result manufactured Presentation: Clear, brown Clear, brown liquid liquid Assay: 698.1g/L 698.8g/L Require 675g/L5 schlorpyrifos5 s725g/L pH1% 7.5 7.5 Nominally: 5.5 to 9.5 Persistent foaming 25mL 20mL Require: <60mL foam after 1 min Emulsion characteristics Traces of cream; 0.2mL of cream; Require: <2mL cream after 30 min, <trace of No oil; No oil; oil after 30 min and complete re-emulsion Re-emulsifies/24h Re-emulsifies/24h after 24h

Embodiment 4 - 650g/L chlorpyrifos emulsifiable concentrate Composition as follows: Ingredient CAS# Concentration

Chlorpyrifos 2921-88-2 663.2g/L (Technical material, 98.1%) (yields 650.6g/L chlorpyrifos) Alkoxylated alkylphenol 37251-69-7 38.1g/L Proprietary (Termul 200, Antarox 724/P) Alkylbenzenesulfonic acid, calcium salt in 2- 68584-23-6, 104- 52.2g/L ethylhexanol 76-7, (Proprietary: Ninate 60E) Methyl benzoate 93-58-3 460.2g/L (to 1214g/L total)

Chemical and physical parameters as follows: Test As- Accelerated Aged Result manufactured Presentation: Clear, brown Clear, brown liquid liquid Assay: 650.5g/L 649.8g/L Require 625g/L5 chlorpyrifos5 675g/L Assay: 650.5g/L 649.8g/L Require 625g/L 5 chlorpyrifos5 675g/L pH1% 6.5 6.6 Nominally: 5.5 to 9.5 Persistent foaming 30mL 30mL Require: <60mL foam after 1 min Emulsion characteristics Traces of cream; Traces of cream; Require: <2mL cream after 30 min, <trace of No oil; No oil; oil after 30 min and complete re-emulsion Re-emulsifies/24h Re-emulsifies/24h after 24h I II

Embodiment 5 - 650g/L chlorpyrifos emulsifiable concentrate Composition as follows: Ingredient CAS# Concentration Chlorpyrifos 2921-88-2 663.2g/L (Technical material, 98.1%) (yields 650.6g/L chlorpyrifos) Alkoxylated alkylphenol 37251-69-7 38.1g/L Proprietary (Termul 200, Antarox 724/P) Alkylbenzenesulfonic acid, calcium salt in 2- 68584-23-6, 104- 52.2g/L ethylhexanol 76-7, (Proprietary: Ninate 60E) Acetophenone 98-86-2 481.9g/L (to 1235g/L total)

Chemical and physical parameters as follows: Test As- Accelerated Aged Result manufactured Presentation: Clear, brown Clear, brown liquid liquid Assay: 644.3g/L 647.2g/L Require 625g/L5 chlorpyrifos5 675g/L pH1% 6.3 6.3 Nominally: 5.5 to 9.5

Persistent foaming 25mL 25mL Require: <60mL foam after 1 min Emulsion characteristics Traces of cream; No cream; Require: <2mL cream after 30 min, <trace of No oil; No oil; oil after 30 min and complete re-emulsion Re-emulsifies/24h Re-emulsifies/24h after 24h I II

Embodiment 6 - 650q/L chlorpyrifos emulsifiable concentrate Composition as follows: Ingredient CAS# Concentration Chlorpyrifos 2921-88-2 664.1g/L (Technical material, 98.1%) (yields 651.5g/L chlorpyrifos) Castor oil ethoxylate 61791-12-6, 49.6g/L Proprietary (Termul 1285) Alkylbenzenesulfonic acid, calcium salt in 2- 68584-23-6, 104- 40.9g/L ethylhexanol 76-7, (Proprietary: Ninate 60E) Acetophenone 98-86-2 481.1g/L (to 1236g/L total)

Chemical and physical parameters as follows: Test As- Accelerated Aged Result manufactured Presentation: Clear, brown Clear, brown liquid liquid Assay: 644.9g/L 654.4g/L Require 625g/L5 chlorpyrifos5 675g/L pH1% 6.3 6.7 Nominally: 5.5 to 9.5 Persistent foaming 40mL 25mL Require: <60mL foam after 1 min Emulsion characteristics 0.2mL cream; 0.2mL cream; Require: <2mL cream after 30 min, <trace of No oil; No oil; oil after 30 min and complete re-emulsion Re-emulsifies/24h Re-emulsifies/24h after 24h

Embodiment 7 - 650g/L chlorpyrifos emulsifiable concentrate Composition as follows: Ingredient CAS# Concentration Chlorpyrifos 2921-88-2 663.6g/L (Technical material, 98.1%) (yields 651.0g/L chlorpyrifos) Ethoxylated tristyrylphenol 99734-09-5, 72.2g/L Proprietary (Termul 3150) Alkylbenzenesulfonic acid, calcium salt in 2- 68584-23-6, 104- 18.0g/L ethylhexanol 76-7, Proprietary (Ninate 60E) Acetophenone 98-86-2 488.4g/L (to 1242g/L total)

Chemical and physical parameters as follows: Test |As- Accelerated Aged Result manufactured Presentation: Clear, brown Clear, brown liquid liquid Assay: 649.2g/L 649.7g/L Require 625g/L5 chlorpyrifos5 675g/L pH1% 7.7 7.5 Nominally: 5.5 to 9.5 Persistent foaming 30mL 35mL Require: <60mL foam after 1 min Emulsion characteristics 1.0mL cream; 1.5mL cream; Require: <2mL cream after 30 min, <trace of No oil; No oil; oil after 30 min and complete re-emulsion Re-emulsifies/24h Re-emulsifies/24h after 24h I II

Embodiment 8 - 600g/L chlorpyrifos emulsifiable concentrate Composition as follows: Ingredient CAS# Concentration Chlorpyrifos 2921-88-2 612.3g/L (Technical material, 98.1%) (yields 600.7g/L chlorpyrifos) Alkoxylated alkylphenol 37251-69-7 21.2g/L Proprietary (Termul 200, Antarox 724/P) Alkylbenzenesulfonic acid, calcium salt in 2- 68584-23-6, 104- 29.3g/L ethylhexanol 76-7, (Proprietary: Ninate 60E) Ethyl benzoate 93-89-0 542.8g/L (to 1206g/L total)

Chemical and physical parameters as follows: Test As- Accelerated Aged Result manufactured Presentation: Clear, brown Clear, brown liquid liquid Assay: 596.2g/L 606.8g/L Require 575g/L 5 chlorpyrifos5 625g/L pH1% 7.0 7.0 Nominally: 5.5 to 9.5 Persistent foaming 20mL 25mL Require: <60mL foam after 1 min Emulsion characteristics 0.2mL cream; Traces of cream; Require: <2mL cream after 30 min, <trace of No oil; No oil; oil after 30 min and complete re-emulsion Re-emulsifies/24h Re-emulsifies/24h after 24h

Embodiment 9 - 550g/L chlorpyrifos emulsifiable concentrate Composition as follows: Ingredient CAS# Concentration Chlorpyrifos 2921-88-2 562.0g/L (Technical material, 98.1%) (yields 551.3g/L chlorpyrifos)

Alkoxylated alkylphenol 37251-69-7 38.4g/L Proprietary (Termul 200, Antarox 724/P) Alkylbenzenesulfonic acid, calcium salt in 2- 68584-23-6, 104- 52.2g/L ethylhexanol 76-7, (Proprietary: Ninate 60E) Isophorone 78-59-1 475.0g/L (to 1128g/L total)

Chemical and physical parameters as follows: Test As- Accelerated Aged Result manufactured Presentation: Clear, brown Clear, brown liquid liquid Assay: 550.9g/L 564.5g/L Require 525g/L5 schlorpyrifos 5 575g/L pH1% 6.7 6.7 Nominally: 5.5 to 9.5 Persistent foaming 30mL 30mL Require: <60mL foam after 1 min Emulsion characteristics Traces of cream; Traces of cream; Require: <2mL cream after 30 min, <trace of No oil; No oil; oil after 30 min and complete re-emulsion Re-emulsifies/24h Re-emulsifies/24h after 24h

Embodiments further comprising a further insecticidal agent

Embodiment 10 - 600g/L chlorpyrifos + 30q/L bifenthrin emulsifiable concentrate Composition as follows: Ingredient CAS# Concentration Chlorpyrifos 2921-88-2 612.7g/L (Technical material, 98.1%) (yields 601.1g/L chlorpyrifos) Bifenthrin 82657-04-3 32.1g/L (Technical material, 98.0%) (yields 31.5g/L bifenthrin) Alkoxylated alkylphenol (e.g. Termul 200, 37251-69-7 34.1g/L Antarox 724/P) Proprietary (Termul 200, Antarox 724/P) Alkylbenzenesulfonic acid, calcium salt in 2- 68584-23-6, 104- 46.2g/L ethylhexanol 76-7, (Proprietary: Ninate 60E) Methyl benzoate 93-58-3 503.0g/L (to 1228g/L total)

Chemical and physical parameters as follows: Test As- Accelerated Aged Result manufactured Presentation: Clear, brown Clear, brown liquid liquid Assay: 598.8g/L 601.0g/L Require 575g/L 5 chlorpyrifos 5 625g/L I II

Assay: 30.4g/L 31.3g/L Require 27g/L 5 bifenthrin 33g/L pH1% 6.4 6.5 Nominally: 5.5 to 9.5 Persistent foaming 35mL 40mL Require: <60mL foam after 1 min Emulsion characteristics Traces of cream; Traces of cream; Require: <2mL cream after 30 min, <trace of No oil; No oil; oil after 30 min and complete re-emulsion Re-emulsifies/24h Re-emulsifies/24h after 24h

Embodiment 11 - 600g/L chlorpyrifos + 30q/L bifenthrin emulsifiable concentrate Composition as follows: Ingredient CAS# Concentration Chlorpyrifos 2921-88-2 613.0g/L (Technical material, 98.1%) (yields 601.4g/L chlorpyrifos) Bifenthrin 82657-04-3 32.9g/L (Technical material, 98.0%) (yields 32.2g/L bifenthrin) Alkoxylated alkylphenol 37251-69-7 34.2g/L Proprietary (Termul 200, Antarox 724/P) Alkylbenzenesulfonic acid, calcium salt in 2- 68584-23-6, 104- 46.2g/L ethylhexanol 76-7, (Proprietary: Ninate 60E) Acetophenone 98-86-2 475.6g/L (to 1202g/L total)

Chemical and physical parameters as follows: Test As- Accelerated Aged Result manufactured Presentation: Clear, brown Clear, brown liquid liquid Assay: 596.9g/L 596.4g/L Require 575g/L : chlorpyrifos 5 625g/L Assay: 30.9g/L 29.9g/L Require 27g/L 5 bifenthrin5 33g/L pH1% 6.9 6.9 Nominally: 5.5 to 9.5 Persistent foaming 40mL 20mL Require: <60mL foam after 1 min Emulsion characteristics Traces of cream; Traces of cream; Require: <2mL cream after 30 min, <trace of No oil; No oil; oil after 30 min and complete re-emulsion Re-emulsifies/24h Re-emulsifies/24h after 24h

Embodiment 12 - 500g/L chlorpyrifos + 25g/ alpha-cypermethrin emulsifiable concentrate Composition as follows:

Ingredient Role Concentration Chlorpyrifos 2921-88-2 510.5g/L (Technical material, 98.1%) (yields 500.1g/L chlorpyrifos) Alpha-Cypermethrin 67375-30-8 25.7g/L (Technical material, 98.0%) (yields 25.2 alpha cypermethrin) Alkoxylated alkylphenol 37251-69-7 21.4g/L Proprietary (Termul 200, Antarox 724/P) Alkylbenzenesulfonic acid, calcium salt in 2- 68584-23-6, 104- 29.5g/L ethylhexanol 76-7, (Proprietary: Ninate 60E) Isophorone 78-59-1 526.8g/L (to 1114g/L total)

Chemical and physical parameters as follows: Test As- Accelerated Aged Result manufactured Presentation: Clear, brown Clear, brown liquid liquid Assay: 502.5g/L 497.7g/L Require 475g/L s chlorpyrifos 5 525g/L Assay: 25.5g/L 23.9g/L Require 21.3g/15 alpha-cypermethrin s 28.7g/L pH1% 6.8 6.6 Nominally: 5.5 to 9.5 Persistent foaming 35mL 30mL Require: <60mL foam after 1 min Emulsion characteristics Traces of cream; 0.1mL cream; Require: <2mL cream after 30 min, <trace of No oil; No oil; oil after 30 min and complete re-emulsion Re-emulsifies/24h Re-emulsifies/24h after 24h

Example Manufacturing Process

[0080] The following working steps were taken to produce the emulsifiable concentrate formulation:

a. add solvent and active agent(s) (chlorpyrifos and optional pesticidal agent(s)) to a suitably sized vessel;

b. add surfactant(s); and

c. mix for 30 minutes;

[0081] The above description of various embodiments of the present invention is provided for purposes of description to one of ordinary skill in the related art. It is not intended to be exhaustive or to limit the invention to a single disclosed embodiment. As mentioned above, numerous alternatives and variations to the present invention will be apparent to those skilled in the art of the above teaching. Accordingly, while some alternative embodiments have been discussed specifically, other embodiments will be apparent or relatively easily developed by those of ordinary skill in the art. Accordingly, this invention is intended to embrace all alternatives, modifications and variations of the present invention that have been discussed herein, and other embodiments that fall within the spirit and scope of the above described invention.

Claims (16)

1. An emulsifiable concentrate formulation comprising:

chlorpyrifos at a concentration of greater than 550 g/L;

at least one surfactant selected from the group consisting of an alkoxylated alkylphenol, an alkylbenzenesulphonate, a castor oil ethoxylate, an ethoxylated tristyrylphenol and any combination thereof; and

an organic solvent, wherein the organic solvent is selected from the group consisting of an alkyl benzoate, an alkyl ketone, an aryl ketone, and any combination thereof.

2. A method of preparing an emulsifiable concentrate formulation including the steps of:

(a) combining chlorpyrifos, at least one surfactant and an organic solvent, wherein chlorpyrifos is present at a concentration of greater than 550 g/L, wherein the organic solvent is selected from the group consisting of an alkyl benzoate, an alkyl ketone, an aryl ketone, and any combination thereof and wherein the surfactant is selected from the group consisting of an alkoxylated alkylphenol, an alkylbenzenesulphonate, a castor oil ethoxylate, an ethoxylated tristyrylphenol and any combination thereof; and

(b) mixing the mixture of step (a) to thereby prepare the emulsifiable concentrate formulation.

3. The emulsifiable concentrate formulation of claim 1 or the method of claim 2, wherein chlorpyrifos is present at a concentration of greater than about 575 g/L, greater than about 600 g/L, greater than about 625 g/L, greater than about 650 g/L, greater than about 675 g/L, greater than about 700 g/L, greater than about 725 g/L, greater than about 750 g/L, greater than about 775 g/L, or greater than about 800g/L of the formulation.

4. The emulsifiable concentrate formulation or the method of any one of the preceding claims, wherein the organic solvent is present in an amount of at least 300 g/L of the formulation.

5. The emulsifiable concentrate formulation or the method of claim 4, wherein the organic solvent is present in an amount of between about 400 g/L and about 700 g/L of the formulation.

6. The emulsifiable concentrate formulation or the method of any one of the preceding claims, wherein the organic solvent is or comprises acetophenone, methyl benzoate, ethyl benzoate and/or isophorone.

7. The emulsifiable concentrate formulation or the method of any one of the preceding claims, wherein the surfactant is present in an amount of at least about g/L.

8. The emulsifiable concentrate formulation or the method of claim 7, wherein the surfactant is present in an amount of between 20 g/L to about 150 g/L.

9. The emulsifiable concentrate formulation or the method of any one of the preceding claims, wherein the formulation comprises two surfactants.

10. The emulsifiable concentrate formulation or the method of claim 9, wherein one of the two surfactants is calcium alkylbenzenesulphonate.

11. The emulsifiable concentrate formulation of method of claim 9, wherein a second of the two surfactants is selected from group consisting of alkoxylated alkylphenol, castor oil ethoxylate, and ethoxylated tristyrylphenol.

12. The emulsifiable concentrate formulation or the method of any one of the preceding claims, the formulation further comprising a pesticidal agent.

13. The emulsifiable concentrate formulation or the method of claim 12, wherein the pesticidal agent is bifenthrin and/or alpha-cypermethrin.

14. The emulsifiable concentrate formulation or the method of claim 12 or 13, wherein the pesticidal agent is present in an amount from about 0.1 g/L to 250 g/L.

15. A method of controlling a pest in a target area, including the step of applying a pesticidally effective amount of the emulsifiable concentrate formulation of any one of claims 1 and 3-13 mixed with water or a water-containing liquid to the target area to thereby control said pest.

16. The method of claim 15, further including the initial step of mixing the emulsifiable concentrate formulation with water or the water-containing liquid.

Imtrade Australia Pty Ltd Patent Attorneys for the Applicant/Nominated Person SPRUSON & FERGUSON