AU2018229453A1 - Pyrethroid formulation - Google Patents

Abstract

Provided is an emulsifiable and/or dispersible concentrate formulation that includes alpha-cypermethrin at a concentration of at least 5 about 125 g/L, a surfactant and two or more solvents and methods of making same. Methods of preventing and/or controlling pest infestations by applying a pesticidally effective amount of the emulsifiable and/or dispersible concentrate formulation of alpha-cypermethrin to a target area are also provided.

Description

FIELD OF THE INVENTION

This invention relates to a pyrethroid formulation. In particular, the present invention relates to an emulsifiable and/or dispersible concentrate formulation of alpha-cypermethrin that contains a high level of alphacypermethrin as active agent and to methods of preparing and using said formulation.

BACKGROUND TO THE INVENTION

Cypermethrin is a highly active synthetic pyrethroid insecticide, effective against a wide range of pests in agriculture, public health and animal husbandry. Alpha-cypermethrin is an isomeric subset of cypermethrin and a well-established insecticidal agent in its own right.

Alpha-cypermethrin is a contact insecticide that controls a broad range of insects through contact and stomach action following ingestion of treated material. To this end, the insecticide function as a neuropoison acting on axons in the peripheral and central nervous systems by interacting with sodium channels in insects.

Alpha-cypermethrin can be applied in diverse settings, including broad acre cropping (cereals, oilseeds, legumes, cotton, etc.), horticulture (vegetables, stone-fruit, pome-fruit, etc.), viticulture and forestry uses. In this respect, alpha-cypermethrin is typically applied to a target area in the

2018229453 12 Sep 2018 form of a diluted concentrate.

Notwithstanding the commercial availability of a range of alphacypermethrin formulations, there remains a need for an emulsifiable and/or dispersible concentrate formulation thereof that overcomes one or more of 5 the inherent limitations of commercially available alpha-cypermethrin formulations.

SUMMARY OF THE INVENTION

In a first aspect, the invention provides an emulsifiable and/or dispersible concentrate formulation comprising:

alpha-cypermethrin at a concentration of at least about 125 g/L;

a surfactant; and two or more solvents.

In certain embodiments, alpha-cypermethrin is present at a concentration of at least about 200 g/L of the total weight of the formulation.

Suitably, the two or more solvents are present in an amount of at least about 500 g/L. Preferably, the two or more solvents are present in an amount ranging between about 500 g/L to about 800 g/L.

At least one of the two or more solvents is suitably selected from the group consisting of an aromatic hydrocarbon, a lactam, an alkyl benzoate, a lactone and any combination thereof. Preferably, at least one of the two or more solvents are selected from the group consisting of a

2018229453 12 Sep 2018 heavy aromatic solvent naphtha (petroleum), a pyrrolidone, methyl benzoate, ethyl benzoate, caprolactone and any combination thereof. In particular preferred embodiments, the pyrrolidone is N-methyl pyrrolidone and/or octyl-pyrrolidone.

Suitably, the two or more solvents comprise first and second solvents. Preferably, the first solvent is selected from the group consisting of a lactam, a lactone, and any combination thereof and/or the second solvent is selected from the group consisting of an aromatic hydrocarbon, an alkyl benzoate and any combination thereof. In particular embodiments, 10 the ratio of the first solvent to the second solvent is in the range of about 3:1 to about 1:3.

The surfactant is suitably present in an amount of at least about 40 g/L. Preferably, the surfactant is present in an amount ranging between about 50 g/L to about 150 g/L.

In one embodiment, the surfactant is selected from the group consisting of an alkoxylated oil, an alkylphenol alkoxylate, an alkoxylated alcohol, 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 20 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 ethoxylatepropoxylate copolymer, a C10-16 alkylbenzenesulphonate (branched or

2018229453 12 Sep 2018 linear in solvent), a branched alcohol ether sulphate, a tallow amine alkoxylated salt and any combination thereof.

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

In a second aspect, the invention provides a method of preparing an emulsifiable and/or dispersible concentrate alpha-cypermethrin formulation including the steps of:

(a) combining alpha-cypermethrin, a surfactant and two or more solvents, wherein alpha-cypermethrin is present at a concentration of at least about 125 g/L; and (b) mixing the mixture of step (a) to thereby prepare the emulsifiable and/or dispersible concentrate alpha-cypermethrin formulation.

For the present aspect, the emulsifiable and/or dispersible concentrate alpha-cypermethrin formulation is suitably that of the first 15 aspect.

In a third aspect, the invention provides an emulsifiable and/or dispersible concentrate alpha-cypermethrin formulation prepared by the method of the second aspect.

In a fourth aspect, the invention provides a method of preventing and/or controlling a pest infestation in a target area, including the step of applying a pesticidally effective amount of the emulsifiable and/or dispersible concentrate formulation of the first or third aspects mixed with water or a water-containing liquid to the target area to thereby prevent

2018229453 12 Sep 2018 and/or control the pest infestation.

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

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.

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

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 20 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., non5

2018229453 12 Sep 2018 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, antioxidants, dyes and consumption deterrents, and packaging, such as 5 containers, closures, labels/booklets, pallets and pallet liners/boxes/wrapping).

In addition to the above, providing an emulsifiable and/or dispersible concentrate form of a pesticide product rather than as a suspension concentrate form, further alleviates some or all of the 10 deficiencies of the latter. To this end, the active ingredient in emulsifiable and/or dispersible concentrate formulations is not in the solid phase as it is in suspension concentrates, and thereby is not subject to settling or physical phase separation of solid from liquid. Furthermore, the development of appropriate solvents and other excipients typically requires 15 careful consideration so as to achieve a passable emulsifiable and/or dispersible concentrate formulation.

In view of the foregoing, the invention advantageously provides a highly loaded emulsifiable and/or dispersible concentrate alphacypermethrin composition or formulation suitable for the prevention, 20 control or treatment of a range of pest infestations in an agricultural or horticultural setting.

As generally used herein, the term “highly loaded” is to be taken to refer to the concentration level of alpha-cypermethrin pesticide in an

2018229453 12 Sep 2018 emulsifiable and/or dispersible concentrate formulation on a weight by volume basis (g/L) in the amount from at least about 125 g/L.

In one aspect, the invention provides an emulsifiable and/or dispersible concentrate formulation comprising:

alpha-cypermethrin at a concentration of at least about 125 g/L;

a surfactant; and two or more solvents.

In a related aspect, the invention provides a method of preparing an emulsifiable and/or dispersible concentrate alpha-cypermethrin formulation including the steps of:

(a) combining alpha-cypermethrin, a surfactant and two or more solvents, wherein alpha-cypermethrin is present at a concentration of at least about 125 g/L; and (b) mixing the mixture of step (a) to thereby prepare the emulsifiable and/or dispersible concentrate alpha-cypermethrin formulation.

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

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 immiscible phase. By way of example, a water insoluble active ingredient

2018229453 12 Sep 2018 is typically dissolved in a largely water insoluble solvent that upon combination with water or the like and agitation forms an emulsion being a distribution of droplets of the water insoluble solvent and active ingredient amongst a water matrix stabilised by surfactants. The term emulsion, as 5 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.

Similarly, it will be appreciated that the term “dispersible concentrate formulation” or “dispersible concentrate” (DC) refers to a liquid 10 formulation or concentrate of an active agent, such as a pesticide, which, on dilution in water or a water-containing liquid, form a dispersion therein. By way of example, a water insoluble active ingredient is typically dissolved in a largely water-soluble solvent that upon combination with water forms a single mixed liquid phase with the water insoluble active 15 ingredient coming out of solution and the resulting combination being a dispersion as stabilised by surfactants. The term dispersion, as used herein, refers to a liquid medium containing a suspension of minute solids, such as minute colloid particles.

In particular embodiments, the present formulation is or comprises 20 an emulsion concentrate. In alternative embodiments, the present formulation is or comprises a dispersible concentrate. It will be appreciated, however, that in further embodiments, the formulation type can have characteristics or features that are intermediate an emulsifiable

2018229453 12 Sep 2018 concentrate and a dispersion concentrate. This may be achieved, for example, by the two or more solvents including a water-soluble (miscible) solvent (e.g., NMP) and a water-insoluble (immiscible) solvent (e.g., solvent naphtha). Accordingly, in particular embodiments, the two or more 5 solvents of the present formulation comprise a water soluble solvent and/or a water insoluble solvent.

The term “cypermethrin” refers to the synthetic pyrethroid (R,S)-acyano-3-phenoxybenzyl-(1RS)-cis-trans-3-(2,2-dichlorovinyl)-2,2dimethylcyclopropanecarboxylate. It is generally appreciated that 10 cypermethrin can comprise eight isomers (i.e., four cis isomers and four trans isomers), with the cis isomers typically being the more biologically active. Depending upon the manufacturing source of cypermethrin, the cis:trans isomer ratio can vary from 40:60 to 80:20. Since the discovery and commercialization of cypermethrin, products containing increased or 15 enriched amounts of certain isomers have been developed.

It will be appreciated that use of the term “cypermethrin” herein can refer to one or more of these eight isomers, including specific mixtures and/or ratios thereof as are known in the art, such as the enriched cypermethrins of alpha-cypermethrin, beta-cypermethrin, theta20 cypermethrin and zeta-cypermethrin.

With respect to alpha-cypermethrin, it will be understood that alphacypermethrin contains more than 90% of the insecticidally most active enantiomer pair of the four cis isomers of cypermethrin as a racemic

2018229453 12 Sep 2018 mixture (i.e., (S)-a-cyano-3-phenoxybenzyl (1R)-cis-3-(2,2-dichlorovinyl)2,2-dimethylcyclopropanecarboxylate and (R)-a-cyano-3-phenoxybenzyl (1S)-cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate).

Cypermethrin demonstrates markedly higher solubility than alpha5 cypermethrin when dissolved in a number benchmark solvents. For example, in ethyl acetate at 20°C, cypermethrin has been shown to be in of the order of 4 times more soluble than alpha-cypermethrin (200 v 58.4g/L). Furthermore, in methanol at 20°C, it has been previously demonstrated cypermethrin is of the order of 20 times more soluble than alpha-cypermethrin (450 v 21.3g/L) (International Union of Pure and Applied Chemistry (IUPAC). 2017. Cypermethrin (Ref: OMS 2002). University of Hertfordshire; International Union of Pure and Applied Chemistry (IUPAC). 2017. Alpha-cypermethrin (Ref: OMS 3004).

University of Hertfordshire). Additionally, in hexane at 20°C, cypermethrin has been shown to be in the order of 15 times more soluble than alphacypermethrin (103 v 7g/L) (British Crop Protection Council (BCPC). 2002.

The e-Pesticide Manual, edn. 2.2. Wise and Loveys Information Services Ltd). Accordingly, there are significant differences between cypermethrin and alpha-cypermethrin in terms of their ability to be formulated as an 20 emulsifiable and/or dispersible concentrate.

For the present invention, alpha-cypermethrin, is suitably present in a highly loaded concentration (i.e., at least about 125 g/L) that provides an emulsifiable and/or dispersible concentrate formulation suitable for use in

2018229453 12 Sep 2018 the effective prevention, control and/or treatment of a pest infestation. To this end, alpha-cypermethrin, may be present in an amount from about

125 g/L to about 500 g/L or any range therein such as, but not limited to, about 150 g/L to about 450 g/L, or about 200 g/L to about 300 g/L of the emulsifiable and/or dispersible concentrate formulation. In particular embodiments of the present invention, alpha-cypermethrin is present in an amount of about 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, 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 g/L, or any range therein, of the emulsifiable and/or dispersible concentrate formulation. In certain embodiments of the present invention, alpha-cypermethrin is present in an amount of about 150 g/L to about 450 g/L, more preferably about 200 g/L to about 400 g/L and even more preferably about 250 g/L to about 350 g/L of the emulsifiable and/or dispersible concentrate formulation.

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 two or more solvents may include any appropriate solvent as are known in the art. By way of example, the two or more solvents may comprise at least one of solvent naphtha (petroleum), heavy aromatic fraction, xylene,

2018229453 12 Sep 2018 toluene, pyrrolidones including N-alkylated pryrrolidones such as n-methyl pyrrolidone, cyclohexanone, acetone, glycol ethers such as diethylene glycol monomethyl ether (including the material sold under the trade name Carbitol), ethylene glycol monobutyl ethers (including the material sold under the trade name Butyl Glysolv), propylene glycol monomethyl ether (including the material sold under the trade name Glysolv PM), methanol, ethanol, isopropanol, decanol, paraffins, hexane, acetic acid C6-C8 branched alkyl ester (including the material sold under the trade name Exxate 700).

In one preferred embodiment, at least one of the two or more solvents is suitably selected from the group consisting of an aromatic hydrocarbon, a lactam, an alkyl benzoate, a lactone and any combination thereof. More preferably, at least one of the two or more solvents are selected from the group consisting of a heavy aromatic solvent naphtha 15 (petroleum), a pyrrolidone, methyl benzoate, ethyl benzoate, caprolactone and any combination thereof.

Such solvents may be used in combination as a mixture of two, three, four, five or more solvents. In one particular embodiment, the two or more solvents comprise first and second solvents. It will be appreciated 20 that the first and second solvents may be or comprise any solvent known in the art. Preferably, the first solvent is selected from the group consisting of a lactam, a lactone, and any combination thereof and/or the second solvent is selected from the group consisting of an aromatic hydrocarbon,

2018229453 12 Sep 2018 an alkyl benzoate and any combination thereof.

For the present aspect, the ratio of the first solvent to the second solvent is suitably about 3:1, 2.9:1, 2.8:1, 2.7:1, 2.6:1, 2.5:1, 2.4:1, 2.3:1, 2.2:1, 2.1:1, 2:1, 1.9:1, 1.8:1, 1.7:1, 1.6:1, 1.5:1, 1.4:1, 1.3:1, 1.2:1, 1.1:1,

1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4:, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2, 1:2.1,

1:2.2, 1:2.3, 1:2.4, 1:2.5, 1:2.6, 1:2.7, 1:2.8, 1:2.9, 1:3 and any range therein. In one preferred embodiment, the ratio of the first solvent to the second solvent is in the range of about 3:1 to about 1:3.

For the above aspects, the two or more solvents may be present in an amount from about 500 g/L to about 800 g/L or any range therein such as, but not limited to, about 600 g/L to about 700 g/L, or about 650 g/L to about 750 g/L of the emulsifiable and/or dispersible concentrate formulation. In particular embodiments of the present invention, the two or more solvents are present in an amount of about 500, 510, 520, 530, 540,

550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680,

690, 700, 710, 720, 730, 740, 750, 760, 770, 780, 790, 800 g/L, or any range therein, of the emulsifiable and/or dispersible concentrate formulation. In certain embodiments of the present invention, the two or more solvents are present in an amount of at least about 500 g/L of the 20 emulsifiable and/or dispersible concentrate formulation. More preferably, the two or more solvents are present in an amount ranging between about

500 g/L to about 800 g/L of the emulsifiable and/or dispersible concentrate formulation.

2018229453 12 Sep 2018

Further to the above, the solvents provided herein are preferably two or more agriculturally acceptable solvents. The term agriculturally acceptable solvent as used herein refers to a solvent is not unacceptably damaging to a plant and/or its environment, and/or not unsafe to the user 5 or others that may be exposed to the solvent when used as described herein.

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 10 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 15 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.

Accordingly, in particular embodiments, the surfactant is or comprises an emulsifying agent. As generally used herein, the term 20 “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.

2018229453 12 Sep 2018

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 is not unacceptably damaging to a plant and/or its environment, 5 and/or not unsafe to the user or others that may be exposed to the surfactant when used as described herein.

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 10 and/or dispersible concentrate alpha-cypermethrin formulation. In this regard, it will be apparent that an amount of the surfactant of the emulsifiable and/or dispersible concentrate formulation can vary, for example, depending on the particular alpha-cypermethrin concentration and the particular surfactant to be included therein.

To this end, the surfactant may be present in an amount from about g/L to about 300 g/L or any range therein such as, but not limited to, about 30 g/L to about 200 g/L, or about 50 g/L to about 100 g/L of the emulsifiable and/or dispersible concentrate formulation. In particular embodiments of the present invention, the surfactant is present in an 20 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

2018229453 12 Sep 2018 any range therein, of the emulsifiable and/or dispersible concentrate formulation. In certain embodiments of the present invention, the surfactant is present in an amount of at least about 40 g/L of the emulsifiable and/or dispersible concentrate formulation. More preferably, 5 the surfactant is present in an amount ranging between about 50 g/L to about 150 g/L of the emulsifiable and/or dispersible concentrate formulation.

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. Suitable non-ionic surfactants are may include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polyoxypropylene ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, polyoxyethylene polyoxypropylene block copolymers, sorbitan alkyl esters, higher fatty acid alkanolamides and any combination thereof. Suitable cationic surfactants may include alkylamine salts, quaternary ammonium salts and combinations thereof. Further, suitable anionic surfactants may include naphthalenesulfonic acid polycondensate, alkenylsulfonate, naphthalenesulfonate, formalin condensate of a naphthalenesulfonate, formadehyde condensate of an alkylnaphthalenesulfonate, lignin sulfonate, alkylarylsulfonate, alkylaryl sulfonate sulfate, polystyrene sulfonate, polycarboxylate, polyoxyethylenealkyl ether sulfate, polyoxyethylenealkylaryl ether sulfate,

2018229453 12 Sep 2018 alkylsulfosuccinate, alkyl sulfate, alkyl ether sulfonate, a higher fatty acid alkali salt and any combination thereof.

In certain preferred embodiments, the one or more surfactants to be included in the emulsifiable and/or dispersible 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, -CO2^-, -SO3H, -SO3^-, -OSO3H, -OSO3^-, -H2PO3, -HPO3^-, -PO3², -H2PO2, =HPO₂, -HPO2-, =PO₂-, =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.

In particular embodiments, the surfactant is selected from the group consisting of an alkoxylated oil (e.g., ~54 x ethoxylated (e.g., T1285)), an alkylphenol alkoxylate (e.g., ~10 x ethoxylated (e.g., TericNIO)), an alkoxylated alcohol (Alcohol C12 - C15, ~23 x ethoxylated (e.g. Teric 12A23); Alcohol C12, ~3 x ethoxylated (e.g. Surfactant 12A3)), an alkoxylated polyaryl phenol (e.g., Tristyryl Phenol, ~16 x ethoxylated (e.g.

TSP15)), an alkoxylated block co-polymer (Ethoxylate-Propoxylate copolymer (e.g. Teric PE64)), an alkylbenzenesulphonate (e.g., Calcium

C10-16 alkylbenzyl sulphonate, branched or linear chain in solvent (e.g. Ninate 60E, NANSA EVM70/2E, Kemmat HF60)), an alcohol ether sulphate (e.g. Toximul TANS-5), an alkylamine ethoxylate (e.g. Toximul

2018229453 12 Sep 2018

TAABS-5) 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 5 alkylbenzenesulphonate (branched or linear in solvent), a branched alcohol ether sulphate, a tallowamine alkoxylated salt and any combination thereof.

Preferably, the castor oil alkoxylate has a degree of alkoxylation of about 36 or greater. Preferably, the alkylphenol alkoxylate has a degree of 10 alkoxylation greater than 2, more preferably greater than 6 and even more preferably greater than 8. Preferably, the alkoxylated alcohol has a degree of alkoxylation greater than 2. Preferably, the alkoxylated polyaryl phenol has a degree of alkoxylation greater than 8.

It will be apparent in light of the foregoing that one or more surfactants may be introduced into the formulation of the invention as a soluble concentration in a further solvent (e.g., calcium dodecylbenzene sulfonate in ethyl hexanol) and the latter may equate, for example, to amounts up to about 10 g/L to about 25 g/L or more of the formulation. Given the above, it will be appreciated that such amounts of the further solvent may make little or no contribution to the solvency of alphacypermethrin within the formulation of the invention.

Accordingly, in particular embodiments, at least two of the two or more solvents are each present in an amount of at least about 30 g/L

2018229453 12 Sep 2018 (e.g., 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250 g/L and any range therein). More preferably, at least two of the two or more solvents are each present in an amount of at least about 100 g/L and even more preferably at least about 5 200 g/L.

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 10 emulsifiable and/or dispersible concentrate formulation as required.

It will be understood that it is desirable for the emulsifiable and/or dispersible concentrate provided herein to be readily or easily pumped or poured from a storage vessel. Preferably, the emulsifiable and/or dispersible concentrate formulation has a viscosity at room temperature 15 (i.e., 20°C) 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 and/or dispersible 20 concentrate formulation of the invention has a viscosity at room temperature of about or less than 400 cPs.

With respect to the aforementioned aspect of preparing an emulsifiable and/or dispersible concentrate formulation of alpha19

2018229453 12 Sep 2018 cypermethrin, 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.

In another aspect, the invention provides an emulsifiable and/or dispersible concentrate formulation prepared by the method of the aforementioned aspect.

In a further aspect, the invention resides in a method of preventing and/or controlling a pest infestation in a target area, including the step of applying a pesticidally effective amount of the emulsifiable and/or 10 dispersible concentrate formulation of first or third mentioned aspects mixed with water or a water-containing liquid to the target area to thereby prevent and/or control the pest infestation.

Suitably, the method of this aspect further includes the initial step of mixing the emulsifiable and/or dispersible concentrate alpha-cypermethrin 15 formulation with water or the water-containing liquid.

The terms “treat”, “treat” and “treatment” are broadly intended to include preventing or controlling a pest infestation. Treating the pest infestation preferably results in at least maintaining, more preferably maintaining or reducing, and even more preferably reducing the degree or 20 severity of the pest infestation in a target area. In one embodiment, treatment with the emulsifiable and/or dispersible concentrate formulation provided herein is able to substantially eradicate an existing pest infestation.

2018229453 12 Sep 2018

As used herein, “preventing” (or “prevent” or “prevention”) refers to a course of action (such as administering an effective amount of the emulsifiable and/or dispersible concentrate formulation described herein) initiated prior to the onset of a symptom, aspect, or characteristic of the 5 pest infestation (e.g., plant or crop damage) so as to prevent, reduce or delay the symptom, aspect, or characteristic thereof. It is to be understood that such preventing need not be absolute to be beneficial to a plant, crop or the like.

As generally used herein, “control” (or “controlled” or “controlling”) 10 refers to an intervention with the emulsifiable and/or dispersible concentrate formulation that reduces or ameliorates a symptom, aspect, or characteristic of the pest infestation after it has begun to develop. The term “ameliorating”, with reference to a pest infestation, refers to any observable beneficial effect thereto as a result of the administration of the 15 emulsifiable and/or dispersible 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 and/or dispersible concentrate formulation against a given 20 pest, including those hereinafter described.

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 infestation is needed or expected to be needed.

2018229453 12 Sep 2018

As used herein, the terms “effective amount” or “pesticidally effective amount” refer to an amount of the emulsifiable and/or dispersible concentrate formulation that is effective to cause such prevention, control, and/or eradication of the pest infestation. By way of example, an effective 5 amount means an amount necessary to produce an observable pesticidal and/or pestistatic effect on unwanted pests (e.g., insects), including the effects of death, growth inhibition, reproduction inhibition, inhibition of proliferation, and removal, destruction, or otherwise diminishing the occurrence and activity of these unwanted pests. An effective amount of 10 the emulsifiable and/or dispersible 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, habitat, mode of application, and the like.

In particular embodiments, an effective amount is the amount of the emulsifiable and/or dispersible concentrate formulation of the invention that has an adverse effect (e.g., reproduction inhibition, knockdown and/or death) 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 20 pests treated or contacted therewith, and even more preferably at least 70% or greater of the pests treated or contacted therewith.

The efficacy of the emulsifiable and/or dispersible concentrate formulation of the present invention may be monitored by determining the

2018229453 12 Sep 2018 mortality of or adverse effect upon treated pests (e.g., insects). This includes inhibition or modulation of pest growth, inhibition of pest reproduction by slowing or arresting its proliferation, or complete destruction/death of the pest. The actual value of an effective amount for 5 the emulsifiable and/or dispersible 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.

With respect to the above, an effective amount of the emulsifiable and/or dispersible concentrate formulation described herein is preferably administered to the target area or locus of the pest infestation. By way of example, to prevent or control pest-related damage to a plant or crop, an effective amount of an emulsifiable and/or dispersible concentrate formulation comprising alpha-cypermethrin is administered to an area adjacent and/or including the plant or crop. As such, a pest, and in particular insects, can be readily contacted with an effective amount of the emulsifiable and/or dispersible concentrate formulation of the invention.

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 20 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 and/or dispersible concentrate formulation of the invention include grasshoppers, locusts, earwigs, crickets,

2018229453 12 Sep 2018 millipedes, slaters, ants, aphids, flies, mites, beetles, bugs, moths, springtails, caterpillars, loopers, bruchids, fleas, mealybugs, midges, thrips, weevils, butterflies and cockroaches, which can cause significant damage to, for example, a wide range of agricultural and horticultural crops and plants.

The emulsifiable and/or dispersible 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 and/or dispersible concentrate 10 formulation are known in the art and may include, for example, ground or aerial spraying.

In a preferred embodiment, the emulsifiable and/or dispersible concentrate formulation is applied at a rate of about 5 to 500mL per hectare (e.g., about 5mL, 10mL, 15mL, 20mL, 25mL, 30mL, 35mL, 40mL, 15 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, 20 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,

2018229453 12 Sep 2018

455mL, 460mL, 465mL, 470mL, 475mL, 480mL, 485mL, 490mL, 495mL,

500mL per hectare and any range therein) and more preferably at a rate of about 15mL to about 300mL per hectare subsequent to dilution thereof in a suitable spray liquid. Obviously, the amount of the emulsifiable and/or dispersible concentrate to be applied per hectare will depend, at least in part, upon the concentration of alpha-cypermethrin therein, the particular pest infestation to be targeted and the type of target crop to which the formulation is to be applied.

Throughout the specification the aim has been to describe the 10 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 15 invention.

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

Any reference to publications cited in this specification is not an admission that the disclosures constitute common general knowledge in 20 Australia.

2018229453 12 Sep 2018

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.

2018229453 12 Sep 2018

Example 1: Embodiments of a Highly Loaded Alpha-Cypermethrin Emulsifiable Concentrate Formulation

There are currently a number of existing 100g/L alpha-cypermethrin emulsifiable concentrate products that are commercially available in

Australia, such as Imtrade’s Dictate Duo 100 Insecticide, Relyon’s

Alphanex 100Ec Insecticide (APVMA Product No. 81781), NovaGuard’s

Alpha-Cypermethrin Duo 100 Insecticide (APVMA Product No. 80899),

Chieftain Duo 100EC Insecticide (APVMA Product No. 69532), Mascot

Duo Insecticide (APVMA Product No. 67541) and Farmalinx’s AlphaCyper

Insecticide (APVMA Product No. 64298). A typical 100g/L emulsifiable concentrate of alpha-cypermethrin combines ingredients as provided in Tables 1 and 2 below.

2018229453 12 Sep 2018

Table 1: Standard formulation of an emulsifiable concentrate of 100 g/L alpha-cypermethrin

Ingredient	Role	Concentration
Alpha-cypermethrin (CAS#	Active	insecticidal	103g/L (to yield
67375-30-8) technical	ingredient		100g/L on 100%
material, typically 97%			basis)
Surfactants (various)	Emulsification		~5 to 15% w/w
	(predominantly);
	Other	surfactant
	properties	such as
	wetting,	spreading,
	sticking
Ancillaries (various)	Various:	dyes,	variable
	odourants,	synergists,
	deterrents, emetics, etc.
Solvent (various)	Solvent		Balance to 100%
			w/w

2018229453 12 Sep 2018

Table 2: An embodiment of a formulation of an emulsifiable concentrate of 100 g/L alpha-cypermethrin

Ingredient	Role	Concentration
Alpha-cypermethrin (CAS# 67375-30-8) technical material, 97%	Active insecticidal ingredient	103g/L (to yield 100g/L on 100% basis)
Vegetable oil alkoxylate (CAS# 61791-12-6)	Emulsifying agent	28g/L
Alkylbenzenesulfonic acid, calcium salt in 2-ethylhexanol (CAS# 26264-06-2 1 104-767)	Emulsifying agent	32g/L
Solvent naphtha (petroleum), heavy aromatic (CAS# 64742-94-5)	Solvent	~755g/L (Balance to 100% w/w)

2018229453 12 Sep 2018

To achieve a pesticide formulation with markedly higher concentration of alpha-cypermethrin than the usual 100g/L therein, and to retain a liquid form, one may pursue a suspension concentrate formulation. This effectively presents the active ingredient as finely divided 5 particles physically suspended in a viscous carrier (water + thickener) with included surfactants assisting in maintaining the product as a uniform formulation. Nevertheless, suspension concentrates are not thermodynamically stable and typically inevitably suffer from some settling of active ingredient and in severe cases resolve into fully settled layers of 10 active ingredient and other solid components beneath an overlying layer of the liquid carrier and other solubilised components, making this type of formulation practically useless.

In the present example, alternatives to suspension concentrates and single solvent emulsifiable concentrates were tested in terms of 15 emulsion and cold temperature stability (i.e., CIPAC MT39.3 testing protocol). In particular, the present Example provides embodiments of emulsifiable concentrates in which the solubility of the alpha-cypermethrin active ingredient is increased by using two or more solvents. Without being bound by any theory, it is believed that the solubility of the alpha20 cypermethrin active ingredient is increased by providing a liquid matrix that is more amenable to dissolving the solid active ingredient in terms of the packing of particles through molecule sizing and the enduring prevailing

2018229453 12 Sep 2018 forces of attraction and repulsion specific to the combination of solvents used.

In choosing solvent options, there are many considerations, including but not limited to the candidates nature/classification with respect 5 to:

- Chemical and physical character - compatibility, stability, solubility of target active, molecule size, viscosity

- Economics - price and availability

- Environment - acidity/alkalinity, persistence, degradation character, partitioning coefficients

- Safety - toxicity, flammability, corrosiveness

- Regulation - status amongst classifications of hazardous substances and/or dangerous goods

Such considerations are complex in themselves, though the level of complexity increases quite significantly when two or more solvents are considered in combination, given that both solvent selection and the relative proportion of the solvent combination must be considered. Further intricacy is added in that one or more surfactants must also be added to impart the ability on the emulsifiable concentrate formulation to adequately disperse the solvent containing dissolved active ingredient when added into a diluent, such as water.

SINGLE SOLVENT EMBODIMENTS

2018229453 12 Sep 2018

In the present Example, the active ingredient content was initially increased by displacing the solvent naphtha (petroleum), heavy aromatic (e.g., Recosol 150) (and adjusting surfactants and other components to suit) so as to achieve a higher concentration variant of the benchmark 5 product. This was attempted for emulsifiable concentrate formulations having 150 g/L, 200 g/L and 300 g/L alpha-cypermethrin in each case delivering an acceptable emulsion character. Unfortunately, as shown in Table 3, at the same time in each case it failed to achieve a marked increase in active ingredient concentration in a stable manner.

It will be appreciated that the solvent of choice for most large volume, well-established, generic-type presentations of the alphacypermethrin active ingredient, including those listed above, is solvent naphtha (petroleum), heavy aromatic. This is particularly owing to this solvent’s wide availability, low relative cost and broadly favourable solubilisation of many non-water soluble pesticide agents. As alluded to earlier, however, simple displacement of some of this solvent with substantially more active ingredient is not a viable option to increase the loading of alpha-cypermethrin in the emulsifiable concentrate formulations, as this results in a final product that is not heterogeneous. That is, the additional active ingredient is not stably solubilised, such that when subject to standard cold temperature stability testing the alphacypermethrin active ingredient will crystallise out of solution, which is unacceptable for commercially passable formulations.

2018229453 12 Sep 2018

Given the above, the present Example then focussed on uncovering a suitable alternative single solvent capable of producing an emulsifiable concentrate having a relatively high concentration of alphacypermethrin therein, the solvent having a flash-point beyond the 5 flammable liquid classification (dangerous goods qualification as a class 3 flammable liquid requires the flash point of the subject liquid to be < 60°C for closed cup testing or < 65.6°C for open cup testing). This was first tested by the way of NMP (N-methyl-2-pyrrolidone). However while this embodiment delivered a stable heterogeneous formulation comprising the 10 alpha-cypermethrin active ingredient and included surfactants, NMP’s high water solubility prohibited the formation of an enduring, high quality emulsion upon product dilution in water (Table 3). To this end, NMP is highly water soluble and upon combination with water the active ingredient seemingly fell out of emulsion as the solvent dissolved in water rather than 15 establishing a stable emulsion of insoluble active ingredient-containing liquid particles dispersed in water as facilitated by the surfactant components.

As shown in Table 3, additional single solvents were tested and found to not be suitable or passable in this respect. Using xylenes (mixed 20 isomers CAS# 1330-20-7) as a single solvent option, both 300g/L and 400g/L emulsifiable concentrate embodiments were tested, but both displayed insufficient cold temp stability, yielding crystals of active ingredient upon cold temperature storage of 7 days at 2C. Using

2018229453 12 Sep 2018 cyclohexanones (CAS# 108-94-1) as a single solvent option, 400g/L, 500g/L and 600g/L emulsifiable concentrate variations were constructed. A stable heterogeneous formulation was not achieved for any of these attempts with cold temperature stability the deficiency. In any event, 5 cyclohexanone is undesirably flammable (with a flash point of < 60°C for closed cup testing or < 65.6°C for open cup testing).

Emulsifiable concentrate formulations based individually on isophorone (CAS# 78-59-1), methyl benzoate (CAS# 93-58-3) and acetophenone (CAS# 98-86-2) were also evaluated. All of these 10 formulations failed to achieve adequate cold temperature stability with crystallisation of alph-cypermethrin content (see Table 3).

2018229453 12 Sep 2018

Table 3 - Embodiments of higher-loading emulsifiable or dispersible concentrate formulations using a single solvent system

Trial	Sample number	Solvent	Loading	Emulsion	CTS	Remarks
Single Solvent
1.1	IAS16213	Solvent naphtha	150g/L	Pass	Fail	Fail
1.2	IAS16212	(petroleum), heavy	200 g/L	Pass	Fail	Fail
1.3	IAS16211	aromatic (Recosol 150)	300 g/L	Pass	Fail	Fail
2.1	IAS16228	N-methyl	150g/L	Failed	Pass	Fail
2.2	IAS16229	Pyrrolidone	200 g/L	Failed	Pass	Fail
2.3	IAS16219		300 g/L	Failed	Pass	Fail
3.1	IAS17009	Xylene	300 g/L	Pass	Fail	Fail
3.2	IAS17010		400 g/L	n/a	Fail	Fail
4.1	IAS17014	Isophorone	300 g/L	Pass	Fail	Fail
4.2	IAS17015		400 g/L	Failed	Fail	Fail
5.1	IAS17029		400 g/L	Pass	Fail	Fail
5.2	IAS17028	Cyclohexanone	500 g/L	n/a	n/a	Fail
5.3	IAS17016		600 g/L	n/a	n/a	Fail
6.1	IAS17030	Methyl	300 g/L	Pass	Fail	Fail
6.2	IAS17031	Benzoate	400 g/L	n/a	n/a	Fail
7.1	IAS 17044	Acetophenone	300 g/L	Pass	Fail	Fail
7.2	IAS17043		400 g/L	Pass	Fail	Fail

2018229453 12 Sep 2018

DUAL SOLVENT EMBODIMENTS

Given the above results in respect of single solvent embodiments, embodiments including two solvents were then tested in terms of emulsion and cold temperature stability. The results of this testing is outlined in 5 Table 4 below, which demonstrates that the dual solvent systems tested were effective in producing passable highly loaded alpha-cypermethrin emulsifiable concentrate formulations.

Table 4 - Embodiments of higher-loading emulsifiable and/or dispersible concentrate formulations using a dual solvent system

Trial	Sample number	Solvent	Loading	Emulsion	CTS	Remarks
A	IAS16075	Recosol 150 + NMP	300g/L	Pass	Pass	Pass
8.1	1AS16164	Methyl Benzoate/ NMP	300 g/L	Pass	Pass	Pass
		Ethyl Benzoate/NMP	300 g/L	Pass	Pass	Pass
12.1	1AS17132	R150/ Octyl pyrrolidone	300 g/L	Pass	Pass	Pass
12.2	1AS17133	R150/ Caprolactone	300 g/L	Pass	Pass	Pass

2018229453 12 Sep 2018

In one embodiment, it was found that by combining solvent naphtha (petroleum), heavy aromatic and N-methyl-pyrrolidone together, the best of both worlds is achieved - i.e. concurrently acceptable cold temperature stability and emulsion quality. A preferred embodiment of such a 5 formulation that attains a 300g/L alpha-cypermethrin emulsifiable concentrate is provided in Table 5 below.

Table 5 - Formulation of Recosol 150 + NMP embodiment

Ingredient	Role	Concentration
Alpha-cypermethrin (CAS# 67375-30-8) technical material, 97%	Active insecticidal ingredient	316g/L (to yield 300g/L on 100% basis)
Vegetable oil alkoxylate (CAS# 61791-12-6)	Surfactant	33g/L
Alkylbenzenesulfonic acid, calcium salt in 2-ethylhexanol (CAS# 26264-06-2 / 104-767)	Surfactant	33g/L
N-methyl pyrrolidone (CAS# 872-50-4)	Solvent	~425g/L
Solvent naphtha (petroleum), heavy aromatic (CAS# 64742-94-5)	Solvent	~244g/L (Balance to 100% w/w)

2018229453 12 Sep 2018

The combination of alpha-cypermethrin with solvent naphtha (petroleum), heavy aromatic and N-methyl-pyrrolidone as an emulsifiable and/or dispersible concentrate was further exemplified with a range of alternative surfactants, as shown in Tables 6 and 7 below. This reinforces 5 that the success of these dual solvent formulations resides largely with the solvent combinations rather than the included surfactant(s).

Table 6 - Variation of surfactant trials at 300g/L

Sample number	Solvent	Surfactant used	Emulsion / Dispersion	CTS	Remarks
Variation of non-ionics with anionic surfactant set as N60E
IAS 17053		Teric N10	Pass	Pass	Pass
IAS 17054	Recosol	Teric 12A3	Pass	Pass	Pass
IAS17055	150/ N- methyl	Surfactant 12A3	Pass	Pass	Pass
IAS17056	Pyrrolidone	TSP16	Pass	Pass	Pass
IAS17057		Teric PE64	Pass	Pass	Pass
Variation ofAnionics with non-ionic surfactant set as T1285
IAS 17058	Recosol	Nansa EVM 70/B	Pass	Pass	Pass
IAS 17060	150/ N- methyl	Kemmat HF60	Pass	Pass	Pass
IAS17061	Pyrrolidone	TANS 5	Pass	Pass	Pass
IAS 17062		TAABS 5	Pass	Pass	Pass

Solvent used is R150/NMP, surfactant loading at 50:50 ratio

2018229453 12 Sep 2018

Table 7 - Formulations of surfactant trials

	Trial 9.1	Trial 9.2	Trial 9.3	Trial 9.4	Trial 9.5	Trial 9.6	Trial 9.7	Trial 9.8	Trial 9.9
Component
Loading, g/L	300	300	300	300	300	300	300	300	300
Alpha cypermethrin tech	316	316	316	316	316	316	316	316	316
Solvent naphtha (petroleum), heavy aromatic (eg. Recosol 150)	244	244	244	244	244	244	244	244	244
N-Methyl Pyrrolidone	425	425	425	425	425	425	425	425	425
Castor oil ethoxylate (eg. T1285)						33	33	33	33
Nonyl phenol ethoxylate (eg. TericNIO)	33
Ethoxylated alcohol C12 -C15 (EO23) (eg. Teric 12A23)		33
Polyoxyethylene Lauryl Ether (eg. Surfactant 12A3)			33
Tristyryl Phenol ethoxylate (eg. TSP16)				33
Block co-polymer (eg. Teric PE64)					33
Calcium dodecyl benzyl sulphonate in 2-EH	33	33	33	33	33

2018229453 12 Sep 2018

(eg. Ninate 60E)
Calcium dodecyl benzyl sulphonate in butanolbranched (eg. NANSAEVM 70/B)						33
Calcium dodecyl benzyl sulphonate in - linear (eg. Kemmat HF60)							33
Alkyl phenol ether sulphate/ tallowamine ethoxylated salt (eg. TANS 5)								33
Branched alcohol ether sulphate/ tallow amine ethoxylated salt (eg. TAABS 5)									33

2018229453 12 Sep 2018

A number of higher-loading alpha-cypermethrin emulsifiable and/or dispersible concentrate formulations using one or more alternative solvents to the previously described solvent naphtha (petroleum), heavy aromatic and N-methyl-pyrrolidone pairing were also developed as 5 provided in Tables 8 to 11 below.

Table 8 - Formulation of methyl benzoate + NMP embodiment

Ingredient	Role	Concentration
Alpha-cypermethrin (CAS# 67375-30-8) technical material, 97%	Active insecticidal ingredient	316g/L (to yield 300g/L on 100% basis)
Vegetable oil alkoxylate (CAS# 61791-12-6)	Surfactant	33g/L
Alkylbenzenesulfonic acid, calcium salt in 2-ethylhexanol (CAS# 26264-06-2 / 104-767)	Surfactant	33g/L
N-methyl pyrrolidone (CAS# 872-50-4)	Solvent	~425g/L
Methyl benzoate (CAS# 93- 58-3)	Solvent	~330g/L (Balance to 100% w/w)

2018229453 12 Sep 2018

Table 9 - Formulation of Recosol 150 + octyl-pyrrolidone embodiment

Ingredient	Role	Concentration
Alpha-cypermethrin (CAS# 67375-30-8) technical material, 97%	Active insecticidal ingredient	316g/L (to yield 300g/L on 100% basis)
Vegetable oil alkoxylate (CAS# 61791-12-6)	Surfactant	33g/L
Alkylbenzenesulfonic acid, calcium salt in 2-ethylhexanol (CAS# 26264-06-2 1 104-767)	Surfactant	33g/L
N-octyl-pyrrolidone (CAS# 2687-94-7)	Solvent	~293g/L
Solvent naphtha (petroleum), heavy aromatic (CAS# 64742-94-5)	Solvent	~324g/L (Balance to 100% w/w)

2018229453 12 Sep 2018

Table 10 - Formulation of Recosol 150 + caprolactone embodiment

Ingredient	Role	Concentration
Alpha-cypermethrin (CAS# 67375-30-8) technical material, 97%	Active insecticidal ingredient	316g/L (to yield 300g/L on 100% basis)
Vegetable oil alkoxylate (CAS# 61791-12-6)	Surfactant	33g/L
Alkylbenzenesulfonic acid, calcium salt in 2-ethylhexanol (CAS# 26264-06-2 1 104-767)	Surfactant	33g/L
Caprolactone (CAS# 502-44- 3)	Solvent	~327g/L
Solvent naphtha (petroleum), heavy aromatic (CAS# 64742-94-5)	Solvent	~338g/L (Balance to 100% w/w)

2018229453 12 Sep 2018

Table 11 - Formulation of N-methyl pyrrolidone + ethyl benzoate embodiment

Ingredient	Role	Concentration
Alpha-cypermethrin (CAS# 67375-30-8) technical material, 97%	Active insecticidal ingredient	316g/L (to yield 300g/L on 100% basis)
Vegetable oil alkoxylate (CAS# 61791-12-6)	Surfactant	35g/L
Alkylbenzenesulfonic acid, calcium salt in 2-ethylhexanol (CAS# 26264-06-2 1 104-767)	Surfactant	33g/L
N-methyl pyrrolidone (CAS# 872-50-4)	Solvent	~504g/L
Ethyl benzoate (CAS# 93-89- 0)	Solvent	~216g/L (Balance to 100% w/w)

2018229453 12 Sep 2018

A further stable embodiment of higher-loading emulsifiable and/or dispersible concentrate formulation using a different solvent naphtha (petroleum), heavy aromatic to N-methyl-pyrrolidone ratio to that provided in Table 5 is provided in Table 12 below.

Table 12 - Formulation of Recosol 150 + NMP embodiment with varied solvent proportions

Ingredient	Role	Concentration
Alpha-cypermethrin (CAS# 67375-30-8) technical material, 97%	Active insecticidal ingredient	316g/L (to yield 300g/L on 100% basis)
Vegetable oil alkoxylate (CAS# 61791-12-6)	Surfactant	33g/L
Alkylbenzenesulfonic acid, calcium salt in 2-ethylhexanol (CAS# 26264-06-2 / 104-767)	Surfactant	33g/L
N-methyl pyrrolidone (CAS# 872-50-4)	Solvent	~325g/L
Solvent naphtha (petroleum), heavy aromatic (CAS# 64742-94-5)	Solvent	~332g/L (Balance to 100% w/w)

2018229453 12 Sep 2018

Further embodiments having higher loadings than the previously exemplified 300g/L alpha-cypermethrin content were developed as outlined in Tables 13 to 15 below. Each embodiment was determined as having adequate emulsion quality and cold temperature stability.

Table 13: 350 g/L alpha-cypermethrin EC formulation

Ingredient	Role	Concentration
Alpha-cypermethrin (CAS# 67375-30-8) technical material, 97%	Active insecticidal ingredient	368g/L (to yield 350g/L on 100% basis)
Vegetable oil alkoxylate (CAS# 61791-12-6)	Surfactant	34g/L
Alkylbenzenesulfonic acid, calcium salt in 2-ethylhexanol (CAS# 26264-06-2 1 104-767)	Surfactant	34g/L
N-methyl pyrrolidone (CAS# 872-50-4)	Solvent	~398g/L
Solvent naphtha (petroleum), heavy aromatic (CAS# 64742-94-5)	Solvent	~229g/L (Balance to 100% w/w)

2018229453 12 Sep 2018

Table 14: 400 g/L alpha-cypermethrin EC and/or DC formulation

Ingredient	Role	Concentration
Alpha-cypermethrin (CAS# 67375-30-8) technical material, 97%	Active insecticidal ingredient	421 g/L (to yield 400g/L on 100% basis)
Vegetable oil alkoxylate (CAS# 61791-12-6)	Surfactant	34g/L
Alkylbenzenesulfonic acid, calcium salt in 2-ethylhexanol (CAS# 26264-06-2 1 104-767)	Surfactant	34g/L
N-methyl pyrrolidone (CAS# 872-50-4)	Solvent	~373g/L
Solvent naphtha (petroleum), heavy aromatic (CAS# 64742-94-5)	Solvent	~215g/L (Balance to 100% w/w)

2018229453 12 Sep 2018

Table 15: 450 g/L alpha-cypermethrin EC and/or DC formulation

Ingredient	Role	Concentration
Alpha-cypermethrin (CAS# 67375-30-8) technical material, 97%	Active insecticidal ingredient	474g/L (to yield 450g/L on 100% basis)
Vegetable oil alkoxylate (CAS# 61791-12-6)	Surfactant	34g/L
Alkylbenzenesulfonic acid, calcium salt in 2-ethylhexanol (CAS# 26264-06-2 / 104-767)	Surfactant	34g/L
N-methyl pyrrolidone (CAS# 872-50-4)	Solvent	~348g/L
Solvent naphtha (petroleum), heavy aromatic (CAS# 64742-94-5)	Solvent	~200g/L (Balance to 100% w/w)

2018229453 12 Sep 2018

Claims (20)

1. An emulsifiable and/or dispersible concentrate formulation comprising:

5 alpha-cypermethrin at a concentration of at least about 125 g/L;

a surfactant; and two or more solvents.

2. The emulsifiable and/or dispersible concentrate formulation of 10 Claim 1, wherein alpha-cypermethrin is present at a concentration of at least about 200 g/L of the total weight of the formulation.

3. The emulsifiable and/or dispersible concentrate formulation of any one of the preceding claims, wherein the two or more solvents are present

15 in an amount of at least about 500 g/L.

4. The emulsifiable and/or dispersible concentrate formulation of

Claim 3, wherein the two or more solvents are present in an amount ranging between about 500 g/L to about 800 g/L.

5. The emulsifiable and/or dispersible concentrate formulation of any one of the preceding claims, wherein at least one of the two or more solvents are selected from the group consisting of an aromatic

2018229453 12 Sep 2018 hydrocarbon, a lactam, an alkyl benzoate, a lactone and any combination thereof.

6. The emulsifiable and/or dispersible concentrate formulation of

5 Claim 5, wherein at least one of the two or more solvents are selected from the group consisting of a heavy aromatic solvent naphtha (petroleum), a pyrrolidone, methyl benzoate, ethyl benzoate, caprolactone and any combination thereof.

10

7. The emulsifiable and/or dispersible concentrate formulation of any one of the preceding claims, comprising first and second solvents.

8. The emulsifiable and/or dispersible concentrate formulation of

Claim 7, wherein the ratio of the first solvent to the second solvent is in the 15 range of about 3:1 to about 1:3.

9. The emulsifiable and/or dispersible concentrate formulation of Claim 7 or Claim 8, wherein the first solvent is selected from the group consisting of a lactam, a lactone, and any combination thereof

10. The emulsifiable and/or dispersible concentrate formulation of any one of Claims 7 to 9, wherein the second solvent is selected from the group consisting of an aromatic hydrocarbon, an alkyl benzoate and any

2018229453 12 Sep 2018 combination thereof.

11. The emulsifiable and/or dispersible concentrate formulation of any one of the preceding claims, wherein the surfactant is present in an

5 amount of at least about 40 g/L.

12. The emulsifiable and/or dispersible concentrate formulation of

Claim 11, wherein the surfactant is present in an amount ranging between about 50 g/L to about 150 g/L.

13. The emulsifiable and/or dispersible concentrate formulation of any one of the preceding claims, wherein the surfactant is selected from the group consisting of an alkoxylated oil, an alkylphenol alkoxylate, an alkoxylated alcohol, an alkoxylated polyaryl phenol, an alkoxylated block

15 co-polymer, an alkylbenzenesulphonate, an alcohol ether sulphate, an alkylamine ethoxylate and any combination thereof.

14. The emulsifiable and/or dispersible concentrate formulation of

Claim 13, wherein the surfactant is selected from the group consisting of 20 an ethoxylated castor oil, an ethoxylated nonylphenol, an ethoxylated alcohol, an ethoxylated tristyrylphenol, an ethoxylate-propoxylate copolymer, a C10-16 alkylbenzenesulphonate, a branched alcohol ether sulphate, a tallowamine alkoxylated salt and any combination thereof.

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15. The emulsifiable and/or dispersible concentrate formulation of any one of the preceding claims, wherein the surfactant comprises a non-ionic surfactant and/or an anionic surfactant.

16. A method of preparing an emulsifiable and/or dispersible concentrate alpha-cypermethrin formulation including the steps of:

(a) combining alpha-cypermethrin, a surfactant and two or more solvents, wherein alpha-cypermethrin is present at a concentration of at

10 least about 125 g/L; and (b) mixing the mixture of step (a) to thereby prepare the emulsifiable and/or dispersible concentrate alpha-cypermethrin formulation.

17. The method of Claim 16, wherein the emulsifiable and/or

15 dispersible concentrate alpha-cypermethrin formulation is that of any one of Claims 1 to 16.

18. An emulsifiable and/or dispersible concentrate alpha-cypermethrin formulation prepared by the method of Claim 16 or Claim 17.

19. A method of preventing and/or controlling a pest infestation in a target area, including the step of applying a pesticidally effective amount of the emulsifiable and/or dispersible concentrate formulation of any one of

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Claims 1 to 15 and 18 mixed with water or a water-containing liquid to the target area to thereby prevent and/or control the pest infestation.

20. The method of Claim 19, further including the initial step of mixing

5 the emulsifiable and/or dispersible concentrate formulation with water or the water-containing liquid.