AU2020204435B2 - Pesticide formulation - Google Patents

Abstract

Provided herein is a pesticide formulation, such as an emulsifiable concentrate formulation, containing a highly loaded concentration of beta cyfluthrin, a synergist, such as piperonyl butoxide, a surfactant and 5 optionally a solvent. Methods of making and using said pesticide formulation are further described herein. 48 2020

Description

Jul 2020

PESTICIDE FORMULATION PESTICIDE FORMULATION

FIELD OF THE INVENTION 2020204435 02

This invention relates to a pesticide formulation. In particular, the 5 5 present invention relates to a pesticide formulation containing high concentrations of beta-cyfluthrin as an active agent and piperonyl butoxide as a synergist and to methods of preparing and using said formulation.

BACKGROUNDTOTOTHE BACKGROUND THEINVENTION INVENTION 10 10 Cyfluthrin is a synthetic pyrethroid insecticide which is effective against a wide range of agricultural and public-health pests. It acts by inhibiting membrane sodium channel systems with resultant interference of nerve signalling in the peripheral and central nervous systems of target organisms. 15 15 Beta-cyfluthrin ((1RS, 3RS; 1RS, 3SR)-3-(2,2-dichloro-vinyl)-2,2 dimethyl-cyclopropane- carboxylic acid (RS)-cyano-(4-fluoro-3-phenoxy phenyl)-methyl ester) is an isomeric subset of cyfluthrin and a well established insecticidal agent in its own right and particularly as a household pesticide. In this regard, beta-cyfluthrin acts as a contact 20 20 insecticide that controls a broad range of insects through contact and stomach action following ingestion of treated material. Notwithstanding the commercial availability of a range of beta cyfluthrin formulations for household use, there remains a need for formulations thereof formulations thereof thatovercomes that overcomes one one or or of more more the of the inherent inherent limitations limitations

25 25 of commercially available beta-cyfluthrin formulations that facilitates their use in an agricultural setting.

SUMMARYOF SUMMARY OFTHE THE INVENTION INVENTION In a first aspect, the invention provides a pesticide formulation 30 30 comprising: a highly loaded concentration of beta-cyfluthrin; a synergist; a surfactant; and optionally a solvent. 2020204435 02

In a second aspect, the invention provides an emulsifiable 5 5 concentrate formulation comprising: beta-cyfluthrin at a concentration of at least about 25 g/L; piperonyl butoxide or an analogue or derivative thereof at a concentration of at least about 50 g/L; a surfactant; and 10 10 optionally a solvent. In various embodiments, beta-cyfluthrin is present at a concentration of at least about 100 g/L of the total weight of the formulation. formulation.

In certain embodiments, piperonyl butoxide is present at a 15 15 concentration of at least about 400 g/L of the total weight of the formulation. formulation.

In some embodiments, the surfactant is present in an amount of at least about 20 g/L. More particularly, the surfactant is suitably present in an amount ranging between about 25 g/L to about 100 g/L. 20 20 Suitably, the surfactant is selected from the group consisting of an alkylphenol, a polyoxyalkylene ether, an alkylbenzenesulphonate, an alkoxylated styryl phenol, an alkoxylated oil and any combination thereof. Preferably, the surfactant is selected from the group consisting of an alkoxylated alkylphenol, an alkyl polyoxyalkalene ether, calcium C10-16 25 25 alkylbenzyl sulphonate, an ethoxylated tristyryl phenol, an ethoxylated castor oil and any combination thereof. In various embodiments, the solvent is present in an amount of at least about 200 g/L. More particularly, the solvent can be present in an amount ranging between about 300 g/L to about 800 g/L. 30 30 Suitably, the solvent is selected from the group consisting of a petroleum derivative, a carboxamide, a benzoate, a ketone and any

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combination thereof. Preferably, the solvent is selected from the group consisting of a heavy aromatic hydrocarbon, a pyrrolidone, an alkyl benzoate, an alkyl ketone, an alkyl ester and any combination thereof. More preferably, the solvent is selected from the group consisting of a 5 heavy aromatic solvent naphtha (petroleum), N-methyl pyrrolidone, methyl benzoate, isophorone, an acetate ester and any combination thereof. 2020204435

In a third aspect, the invention provides a method of preparing a pesticide formulation including the steps of: (a) combining beta-cyfluthrin, a synergist such as piperonyl 10 butoxide, a surfactant and optionally a solvent, wherein beta-cyfluthrin is present at a highly loaded concentration; and (b) mixing the mixture of step (a) to thereby prepare the pesticide formulation. Suitably, the pesticide formulation is that of the first aspect or the 15 emulsifiable concentrate formulation of the second aspect. In a fourth aspect, the invention provides a pesticide formulation prepared by the method of the third aspect. In a fifth aspect, the invention provides a method of preventing and/or controlling a pest infestation in a target area, including the step of 20 applying a pesticidally effective amount of the pesticide formulation of the first or fourth aspects and/or the emulsifiable concentrate formulation of the second aspect mixed with water or a water-containing liquid to the target area to thereby prevent and/or control the pest infestation. In one embodiment, the method of the present aspect further 25 includes the initial step of mixing the pesticide formulation and/or the emulsifiable concentrate formulation with water or the water-containing liquid. In one particular embodiment of the present invention, there is provided an emulsifiable concentrate formulation comprising: 30 beta-cyfluthrin at a concentration of at least about 100 g/L; piperonyl butoxide at a concentration of at least about 50 g/L;

a surfactant; and optionally a solvent.

In another particular embodiment of the present invention, there is 5 provided a method of preparing a pesticide formulation including the steps of: 2020204435

(a) combining beta-cyfluthrin, piperonyl butoxide, a surfactant and optionally a solvent, wherein beta-cyfluthrin is present at a concentration of at least about 100 g/L; and 10 (b) mixing the mixture of step (a) to thereby prepare the pesticide formulation.

As used herein, except where the context requires otherwise, the term “comprise” and variations of the term, such as “comprising”, “comprises” 15 and “comprised”, are not intended to exclude further elements, components, integers or steps but may include one or more

3a unstated further elements, components, integers or steps.

2020204435 02 Jul 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. 5 For example, "a" surfactant includes one surfactant, one or more surfactants and a plurality of surfactants. As used in this specification, the term "about" refers to a variation or tolerance in a stated amount, concentration, ratio or proportion. The extent of such tolerances and variances are well understood by persons skilled in 10 the art. Typically, such tolerances and variances do not compromise the structure, function and/or implementation of the methods described herein. Preferably, "about"is defined as being no more than 10%, 5%, 2% or 1% above or below a stated amount, concentration, ratio or proportion.

15 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 produce or target area (e.g., crop, land, commercial or residential 20 20 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., reduced non-active ingredients, packaging, handling, storage, freight, labour, regulatory licensing and disposal costs) and less environmental 25 25 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). In addition to the above, providing an emulsifiable concentrate form 30 30 of a pesticide product can further alleviate some or all of the deficiencies of other product formulations or preparations of the pesticide in question. To this end, the active ingredient in emulsifiable concentrate formulations is not in the solid phase, 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 careful 5 5 consideration so as to achieve a passable emulsifiable concentrate 2020204435 formulation. formulation.

In view of the foregoing, the invention advantageously provides a highly loaded beta-cyfluthrin composition or formulation suitable for the prevention, control or treatment of a range of pest infestations in an 10 10 agricultural or horticultural setting. Accordingly, in one broad form the invention resides in a pesticide formulation comprising: a highly loaded concentration of beta-cyfluthrin; a synergist; 15 15 a surfactant; and optionally a solvent. The term "cyfluthrin" refers to the synthetic pyrethroid [(R)-cyano-[4 fluoro-3-(phenoxy)phenyl]methyl] (1R,3R)-3-(2,2-dichloroethenyl)-2,2 dimethylcyclopropane-1-carboxylate. It is generally appreciated that 20 20 cyfluthrin can comprise 4 isomers (i.e., 2 cis isomers and 2 trans isomers), with diastereoisomeric enantiomers II and IV typically considered the more biologically active of these. Since the discovery and commercialization of cyfluthrin, products containing increased or enriched amounts of certain isomers have been developed, such as beta-cyfluthrin. It will be 25 25 appreciated that use of the term "cyfluthrin" herein can refer to one or more of these four isomers, including specific mixtures and/or ratios thereof as are known in the art, such as the enriched isomers of beta cyfluthrin. With respect to beta-cyfluthrin, it will be understood that beta 30 30 cyfluthrin is an isomeric mixture enriched for the two biologically active diastereoisomeric pairs of cyfluthrin. A typical composition for beta

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cyfluthrin is outlined in the table below.

Table - Beta-cyfluthrin is a mixture of four diasterioisomeric pairs of enantiomers and their ratio as expressed as a percentage of the sum 5 of the of the four four diasterioisomers diasterioisomers

DiastereoisomericI (R )-alpha, (1R)-cis +(S)- alpha, (1s)-cis 2.0% maximum 2.0% maximum

(S)- alpha, (IR)-cis +(R)- alpha, (IS)-cis 30.0-40.0% 30.0-40.0% Diastereoisomerc II

Diastereoisomeric III (R)- alpha, (1R)-trans +(S)- alpha, (15)-trans 3.0% maximum

Diastereoisomeric IV (S)- alpha, (1R)-trans +(R)- alpha, (1S)-trans 57-67%

As generally used herein, the term "highly loaded" means that beta cyfluthrin occupies a substantial portion of the pesticide formulation on a 10 weight basis. In the context of liquid pesticide formulations, inclusive of emulsifiable concentrate formulations, for example, "highly loaded" refers to a concentration level of beta-cyfluthrin pesticide therein on a weight by volume basis (g/L) in the amount from at least about 25 g/L. In relation to solid pesticide formulations, for example, "highly loaded" refers to a 15 concentration level of beta-cyfluthrin pesticide therein on a weight basis (g/kg) in the amount from at least about 100 g/kg. The term "synergist" as generally used herein refers to an agent that synergizes the activity of a pesticide or an insecticide, such as a pyrethroid like beta-cyfluthrin. Synergists may include any as are known in 20 the art, such as, piperonyl butoxide (PBO), N-octyl bicycloheptene dicarboximide (MGK-264), piprotal, propyl isome, sesamex, sesamolin, sulfoxide and inclusive of any analogues or derivatives thereof. It is well established that the use of synergists such as piperonyl butoxide (PBO) can enhance pesticidal, insecticidal, acaricidal, fungicidal, 25 molluscicidal and vermicidal activity in vitro and/or in vivo, by, for example,

6 inhibiting the activity of certain insect metabolic enzymes involved in detoxification and resistance or by other mechanisms of action (see, e.g., Gunning R.V. et al., "Piperonyl Butoxide", pages 215-225, Academic Press 2020204435 02

(1998); Benchaoui H.A. et al. J. Pharm. Pharmacol. 1996, 48, 753-759; 5 5 Wen Z. et al., Pest. Science 1997, 49, 367-371; Zhao J-Z J. Econ. Entomol. 2000, 93,1508-1514; Nishiwaki H. et al., J. Pest. Science 2004, 29,1 10-1 16 and the patent applications DE 4426942, EP 617890). By way of example, piperonyl butoxide is capable of interacting with and inhibiting phase 1 metabolic enzymes, specifically esterases and 10 10 cytochrome P450s. The addition of a synergist, such as piperonyl butoxide, to the present pesticide formulation thereby facilitates or potentiates the activity of beta-cyfluthrin and thus advantageously increases the biological effectiveness thereof, while achieving substantial savings on the cost of 15 15 the composition formulation. Further to the above, beta-cyfluthrin surprisingly demonstrates at least partial solubility in piperonyl butoxide which allows for combination formulations in a liquid form having a highly loaded concentration of beta-cyfluthrin and optionally together with a highly loaded concentration of piperonyl butoxide (e.g., greater than 100 20 20 g/L). The surfactant and solvent of the pesticide formulation may be any as are known in the art, including those hereinafter described. It is envisaged that the pesticide formulation may take the form of any solid formulation and/or liquid formulation known in the art. Exemplary 25 25 solid formulations include dustable powders, emulsifiable granules, emulsifiable powders, granules, water soluble gel, water soluble granules, water soluble powders, water soluble tablets, water dispersible granules, wettable powders and water dispersible tablets. Exemplary liquid formulations include oil-miscible liquids, soluble concentrates, ultra-low 30 30 volume (ULV) liquids, dispersible concentrates, emulsifiable concentrates,

Jul 2020

emulsions including oil-in-water and micro-emulsions, suspension concentrates and suspoemulsions. In one particular embodiment, the pesticide formulation is or 2020204435 02

comprises an emulsifiable concentrate. 5 5 It will It willbebewell wellunderstood that the understood that term "emulsifiable the term "emulsifiable concentrate 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 10 10 immiscible phase. By way of example, a water insoluble active ingredient 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 15 15 used herein, refers to a fine dispersion of minute droplets of one liquid in anotherininwhich another whichit itisisnot notsoluble soluble or or miscible miscible and and includes includes microemulsions microemulsions

and macroemulsions. In one aspect, the invention provides an emulsifiable concentrate formulation comprising: 20 20 beta-cyfluthrin at a concentration of at least about 25 g/L; piperonyl butoxide or an analogue or derivative thereof at a concentration of at least about 50 g/L; a surfactant; and optionally a solvent. 25 25 In a related aspect, the invention provides a method of preparing a pesticide formulation including the steps of: (a) combining beta-cyfluthrin, a synergist such as piperonyl butoxide or an analogue or derivative thereof, a surfactant and optionally a solvent, wherein beta-cyfluthrin is present at a highly loaded concentration; 30 30 and and (b) mixing the mixture of step (a) to thereby prepare the pesticide

8 formulation. formulation.

The statements which follow apply equally to the aforementioned aspects of the invention. 2020204435 02

For the present invention, beta-cyfluthrin, is suitably present in a 5 5 highly loaded concentration (e.g., at least about 25 g/L) that provides a pesticide formulation, such as an emulsifiable concentrate formulation, suitable for use in the effective prevention, control and/or treatment of a pest infestation. In relation to liquid pesticide formulations, such as emulsifiable 10 10 concentrate formulations, beta-cyfluthrin may be present in an amount from about 25 g/L to about 300 g/L or any range therein such as, but not limited to, about 50 g/L to about 150 g/L, or about 75 g/L to about 125 g/L of the liquid pesticide formulation. In particular embodiments of the present invention, beta-cyfluthrin is present in an amount of about 25, 30, 35, 40, 15 15 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 liquid pesticide formulation. In certain embodiments of the present invention, 20 20 beta-cyfluthrin is present in an amount of about 25 g/L to about 100 g/L of the liquid pesticide formulation. For solid pesticide formulations, beta-cyfluthrin may be present in an amount from about 100 g/kg to about 600 g/kg or any range therein such as, but not limited to, about 150 g/kg to about 450 g/kg, or about 200 25 25 g/kg to about 300 g/kg of the solid pesticide formulation. In particular embodiments of the present invention, beta-cyfluthrin is present in an amount of about 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, 30 30 295, 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,

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Jul 2020

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 g/kg or any range therein, of the solid 2020204435 02

pesticide formulation. 5 5 Piperonyl butoxide (PBO) is a well-known insecticide synergist that can enhance the potency of certain pesticides, such as carbamates, pyrethrins, pyrethroids, and rotenone. An analogue or derivative of piperonyl butoxide may be any as are known in the art and include, for example, a range of additional side chains and moieties (e.g., alkyl side 10 chains, alkynyl side chains). Examples of piperonyl butoxide analogues are described in Panini et al., Pest Management Science, 2017, v73(2); 371-379 and Philippou et al. (2010), Imperial College London, PhD Thesis (Thesis:519289), which are incorporated by reference herein. Suitably, the piperonyl butoxide analogue or derivative retains at least partly the 15 15 synergist activity of PBO. In relation to liquid pesticide formulations, such as emulsifiable concentrate formulations, piperonyl butoxide may be present in an amount from about 50 g/L to about 600 g/L or any range therein such as, but not limited to, about 100 g/L to about 500 g/L, or about 200 g/L to about 400 20 20 g/L of the liquid pesticide formulation. In particular embodiments of the present invention, piperonyl butoxide is present in an amount of about 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, 25 280, 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, 505, 510, 515, 520, 525, 530, 535, 540, 545, 550, 555, 560, 565, 570, 575, 580, 585, 590, 595, 600 g/L, or any range therein, of 30 the liquid pesticide formulation. In certain embodiments of the present invention, piperonyl butoxide is present in an amount of about 100 g/L to

10 about 500 g/L of the liquid pesticide formulation. In other embodiments, piperonyl butoxide is present at a concentration of at least about 100 g/L, preferably at least about 200 g/L, more preferably at least about 300 g/L and even more preferably at least about 400 g/L of the total weight of the formulation. formulation.

For solid pesticide formulations, piperonyl butoxide may be present in an amount from about 10 g/kg to about 250 g/kg or any range therein such as, but not limited to, about 50 g/kg to about 150 g/kg, or about 20 g/kg to about 130 g/kg of the solid pesticide formulation. In particular

embodiments of the present invention, piperonyl butoxide is present in an amount of about 10, 15, 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 g/kg, or any range therein, of the solid pesticide

formulation. As will be appreciated by the skilled artisan, piperonyl butoxide is a liquid at room temperature and will generally need to be at least partly adsorbed and/or absorbed into other components of the solid pesticide formulation so as to maintain a solid consistency of said 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 solvent may include any appropriate solvent as are known in the art. By way of example, the solvent may comprise a petroleum derivative or

hydrocarbon, such as a heavy aromatic solvent naphtha (petroleum) (e.g., Recosol 150), a carboxamide having an amidoalkyl structure (i.e., R-CO NR'R" structure wherein R, R' and R" are independent an organic moiety or hydrogen) inclusive of lactams and pyrrolidones, such as N-substituted pyrrolidones (e.g., N-methyl pyrrolidone, N-butylpyrrolidone and N

octylpyrrolidone), N,N-dimethylformamide and N,N-dimethylacetamide, an alkyl ester, such as acetate esters (e.g., an acetic acid C6-C8 branched

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Jul 2020

alkyl ester including the material sold under the trade name Exxate 700), a ketone inclusive of cyclic ketones, aromatic ketones, alkylketones (e.g., isophorone) and arylketones (e.g., acetophenone), a benzoate, inclusive 2020204435 02

of alkyl benxoates (e.g., methyl benzoate, ethyl benzoate), 5 5 cyclohexanone, acetone, glycols, inclusive of 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 10 Glysolv PM), methanol, ethanol, isopropanol, decanol, paraffins and hexane. In particular embodiments, the solvent is selected from the group consisting of a petroleum derivative, a carboxamide, a benzoate, a ketone, an ester and any combination thereof. More particularly, the solvent is 15 selected from the group consisting of a heavy aromatic hydrocarbon, a pyrrolidone, an alkyl benzoate, an alkyl ketone, an alkyl ester and any combination thereof. Even more particularly, the solvent is selected from the group consisting of a heavy aromatic solvent naphtha (petroleum), N methyl pyrrolidone, methyl benzoate, isophorone, an acetate ester and 20 any combination thereof. Such solvents may be used in isolation or in combination as a mixture of two, three, four, five or more solvents. In one particular embodiment, the solvent comprises first and second solvents. It will be appreciated that the first and second solvents may be or comprise any 25 solvent known in the art. Preferably, the first solvent is a lactam and the second solvent is a petroleum derivative. 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, 30 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 or 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 solvent of a liquid pesticide formulation, 2020204435 02 including an emulsifiable concentrate formulation, of the present invention, 5 5 may be present in an amount from about 10 g/L to about 800 g/L or any range therein such as, but not limited to, about 350 g/L to about 650 g/L, or about 400 g/L to about 550 g/L of the liquid pesticide formulation. In particular embodiments of the present invention, the solvent is present in an amount of about 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 10 10 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 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 15 15 therein, of the liquid pesticide formulation. In certain embodiments of the present invention, the solvent is present in an amount of at least about 300 g/L of the liquid pesticide formulation. More particularly, the solvent is present in an amount ranging between about 300 g/L to about 800 g/L of the liquid pesticide formulation. 20 20 Further to the above, the solvent provided herein is preferably an agriculturally acceptable solvent. 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 or others that may be exposed to the solvent when used as described herein. 25 25 In some embodiments of the aforementioned aspects, the pesticide formulation formulation ororthe theemulsifiable emulsifiable concentrate concentrate formulation formulation contains contains no solvent no solvent or is substantially free of a solvent (e.g., has no more than about 5, 1, 0.5, 0.2, 0.1 or 0.05 g/L or g/kg solvent by volume or weight of the formulation), such as those described herein. 30 30 As used herein, the term "surfactant" or surface-active agent refers to an agent, usually an organic chemical compound that is at least partially

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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) 2020204435 02

between two liquids or between a liquid and a solid. Further to this, these 5 5 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. 10 10 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. 15 15 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 not unacceptably damaging to a plant and/or its environment, and/or not unsafe to the user or others that may be exposed 20 20 to the to surfactant when the surfactant when used used as described as described herein. 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 beta cyfluthrin pesticide formulation, such as an emulsifiable concentrate 25 25 formulation. In this regard, it will be apparent that an amount of the surfactant of the pesticide formulation can vary, for example, depending on the specific form of the pesticide formulation (e.g., liquid or solid formulation), the particular beta-cyfluthrin concentration and the particular surfactant to be included therein. 30 30 With regard to liquid pesticide formulations, such as emulsifiable concentrate formulations, the surfactant may be present in an amount from

14 about 20 g/L to about 300 g/L or any range therein such as, but not limited to, about 25 g/L to about 200 g/L, or about 30 g/L to about 100 g/L thereof. In particular embodiments of the present invention, the surfactant is 2020204435 02 present in an amount of about 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 5 5 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 liquid pesticide formulation. In certain embodiments of the present invention, the surfactant is present in 10 10 an amount of at least about 20 g/L of the liquid pesticide formulation. More preferably, the surfactant is present in an amount ranging between about 25 g/L to about 100 g/L of the liquid pesticide formulation. Referring to solid pesticide formulations of the invention, such as a water dispersible granule formulation, the surfactant may be present in an 15 15 amount from about 20 g/kg to about 300 g/kg or any range therein such as, but not limited to, about 25 g/kg to about 200 g/kg, or about 30 g/kg to about 100 g/kg thereof. 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, 20 20 140, 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/kg, or any range therein, of the solid pesticide formulation. In certain embodiments of the present invention, the surfactant is present in an amount of at least about 20 g/kg of the solid 25 25 pesticide formulation. More preferably, the surfactant is present in an amount ranging between about 25 g/kg to about 100 g/kg of the solid pesticide formulation. For the present invention, the surfactant is suitably selected from the group consisting of non-ionic surfactants, anionic surfactants, cationic 30 30 surfactants, zwitterionic surfactants, cation-anion composite surfactants and any combination thereof. Suitable non-ionic surfactants are may

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Jul 2020

include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polyoxypropylene ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, polyoxyethylene polyoxypropylene 2020204435 02

block copolymers, sorbitan alkyl esters, higher fatty acid alkanolamides 5 5 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 10 10 alkylnaphthalenesulfonate, lignin sulfonate, alkylarylsulfonate, alkylaryl sulfonate sulfate, polystyrene sulfonate, polycarboxylate, polyoxyethylenealkyl ether sulfate, polyoxyethylenealkylaryl ether sulfate, alkylsulfosuccinate, alkyl sulfate, alkyl ether sulfonate, a higher fatty acid alkali salt and any combination thereof. 15 15 In certain preferred embodiments, the one or more surfactants to be included in the pesticide formulation, including the emulsifiable concentrate formulation described herein, 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. 20 20 Such anionic groups may include, for example, -CO2H, -C02-, -S03H, S03-, -OS03H, -OS03-, -H2PO3, -HP03-, -P32 -, -H2PO2, =HPO2, -HP02-, =P02-, =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 25 25 anionic surfactants. anionic surfactants. It will be appreciated that the surfactant may be any suitable surfactant know in the art. Exemplary surfactants include an alkoxylated alkylphenol (e.g., Termul 200), a polyoxyalkylene ether (e.g., Termul 203), an alkoxylated oil (e.g., Vegetable oil, -54 x ethoxylated (e.g., Termul 30 30 1285)), an alkylphenol alkoxylate (e.g., Nonylphenol, -10 x ethoxylated (e.g., Teric N10)), an alkoxylated alcohol (Alcohol C12 - C15, -23 x

16 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. Termul 3150)), an alkoxylated block co-polymer 2020204435 02

(Ethoxylate-Propoxylate copolymer (e.g. Teric PE64)), an 5 5 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 TAABS-5), a silicone polymer, inclusive of polysiloxanes (e.g., Evonik Break-Thru OE 446, Evonik Break 10 10 Thru AF 9903, Jiangxi Tiansheng QS-302) and silicone glycol copolymers (e.g., Xiameter OFX-5211), a block co-polymer (e.g., Teric PE64), an alkoxylated alcohol (e.g., Teric BL8), an alkyl polyglucoside (e.g., Croda AL-2575), an ethoxylate-propoxylate copolymer, a C10-16 alkylbenzenesulphonate (branched or linear in solvent), a branched 15 15 alcohol ether sulphate, a tallowamine alkoxylated salt, and a mineral oil (e.g., Rhodoline DF5888). Preferably, the castor oil alkoxylate has a degree of alkoxylation of about 36 or greater. Preferably, the alkylphenol alkoxylate has a degree of alkoxylation greater than 2, more preferably greater than 6 and even more 20 20 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. In particular embodiments, the surfactant is selected from the group consisting of an alkoxylated alkylphenol (e.g., Termul 200), a 25 25 polyoxyalkylene ether (e.g., Termul 203), an alkylbenzenesulphonate (e.g., Ninate 60E, NANSA EVM70/2E, Kemmat HF60), an alkoxylated styryl phenol (e.g., alkoxylated monostyryl phenols, alkoxylated distyryl phenols, alkoxylated tristyryl phenols, such as Termul 3150), an alkoxylated oil, such as an alkoxylated vegetable oil (e.g., Termul 1284 and Termul 1285) 30 30 and any combination thereof. More particularly, the surfactant can be selected from the group

Jul 2020

consisting of an alkoxylated alkylphenol (e.g., Termul 200), an alkyl polyoxyalkalene ether (e.g., Termul 203), calcium C10-16 alkylbenzyl sulphonate (branched or linear chain in solvent) (e.g., Ninate 60E, NANSA 2020204435 02

EVM70/2E, Kemmat HF60), an ethoxylated tristyryl phenol (e.g., Termul 5 5 3150), an ethoxylated castor oil (e.g., Termul 1284 and Termul 1285) and any combination thereof. 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 10 10 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 beta-cyfluthrin within the formulation of the invention. 15 15 One or more additional auxiliary agents, such as adjuvants, 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 pesticide formulation, including the emulsifiable concentrate formulation, as required. 20 20 Referring to solid forms thereof, the pesticide formulation can further include a filler (e.g., inorganic salts, mineral earths and clays such as bentonite, kaolin, attapulgite, diatomaceous earth, zeolites, calcium carbonate, talc, muscovite mica and manufactured materials such as precipitated silicas and silicates, fused sodium potassium, aluminium 25 25 silicate (heat processed perlite) or organic materials such as coals, lignites and plastics) a binder, and/or one or more additional auxiliary agents, such as adjuvants (e.g., ammonium sulfate, ammonium dihydrogen phosphate), disintegrating agents, lubricants, preservatives, parting agents, and the like, as are known in the art, to modify the properties of the solid pesticide 30 30 formulation as required. It will be understood that it is desirable for liquid forms of the

18 pesticide formulation, including the emulsifiable concentrate formulation, provided herein to be readily or easily pumped or poured from a storage vessel. Preferably, the liquid pesticide formulation has a viscosity at room 2020204435 02 temperature (i.e., 20 0C) of no more than 2000 cPs (e.g., 1, 5, 10, 20, 30, 5 5 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 liquid pesticide formulation of the invention has a viscosity at room temperature of about or less than 400 10 10 cPs. cPs.

With respect to the aforementioned aspect of preparing pesticide formulation of beta-cyfluthrin, it will be appreciated that this method may be performed using methods and commercially available equipment, such as formulation vessels and the like, known in the art. 15 15 In another aspect, the invention provides a pesticide 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 pesticide formulation of the 20 20 first mentioned aspect and/or the emulsifiable concentrate formulation of the second mentioned aspect 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 pesticide formulation and/or the emulsifiable concentrate beta 25 25 cyfluthrin 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 30 30 severity of the pest infestation in a target area. In one embodiment, treatment with the pesticide formulation and/or the emulsifiable

19

concentrate formulation provided herein is able to substantially eradicate an existing pest infestation. As used herein, "preventing" (or "prevent" or "prevention") refers to a course of action (such as administering an effective amount of the 5 5 pesticide formulation and/or the emulsifiable concentrate formulation described herein) initiated prior to the onset of a symptom, aspect, or characteristic of the 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 10 10 beneficial to a plant, crop or the like. As generally used herein, "control" (or "controlled" or "controlling") refers to an intervention with the pesticide formulation and/or the emulsifiable concentrate emulsifiable concentrate formulation formulationthat thatreduces reduces or ameliorates aa or ameliorates symptom, aspect, or characteristic of the pest infestation after it has begun 15 15 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 pesticide formulation and/or the emulsifiable concentrate formulation. The beneficial effect can be determined using any methods or standards known to the ordinarily skilled artisan. 20 20 Accordingly, these terms are meant to include any lethal (i.e., pesticidal) or inhibitory (i.e., pestistatic) activities of the pesticide formulation and/or the emulsifiable concentrate formulation against a given pest, including those hereinafter described. hereinafter described. Herein, the terms "target area", "locus" or "space" refer to any area, 25 25 location or habitat where the prevention, control and/or eradication of a pest infestation is needed or expected to be needed. As used herein, the terms "effective amount", "pesticidally effective amount" and "insecticidally effective amount" refer to an amount of the pesticide formulation and/or the emulsifiable concentrate formulation that 30 30 is effective to cause such prevention, control, and/or eradication of the pest infestation. By way of example, an effective amount means an

20

Jul 2020

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 2020204435 02

removal, destruction, or otherwise diminishing the occurrence and activity 5 5 of these unwanted pests. An effective amount of the pesticide formulation and/or 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, habitat, mode of application, and the like. 10 10 In particular embodiments, an effective amount is the amount of the pesticide formulation and/or the emulsifiable 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 15 15 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. The efficacy of the pesticide formulation and/or the emulsifiable 20 20 concentrate formulation of the present invention may be monitored by determining the 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 25 25 the pesticide formulation and/or the emulsifiable concentrate formulation is preferably determined by routine screening procedures employed to evaluate pesticidal activity and efficacy, such as those methods well knownininthe known theart. art. With respect to the above, an effective amount of the pesticide 30 30 formulation and/or the formulation and/or theemulsifiable emulsifiableconcentrate concentrate formulation formulation described described

herein is preferably administered to the target area or locus of the pest

21 infestation. By way of example, to prevent or control pest-related damage to a plant or crop, an effective amount of a pesticide formulation and/or an emulsifiable concentrate formulation comprising beta-cyfluthrin is 2020204435 02 administered to an area adjacent and/or including the plant or crop. As 5 5 such, a pest, and in particular insects, can be readily contacted with an effective amount of the pesticide formulation and/or the emulsifiable concentrateformulation concentrate formulation of of thethe invention. 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 10 10 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 pesticide formulation of the invention include grasshoppers, locusts, earwigs, crickets, millipedes, slaters, ants, aphids, flies, mites, beetles, bugs, moths, springtails, caterpillars, loopers, 15 15 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. In specific embodiments, the pest or pest infestation to be targeted, prevented and/or controlled by the method for the present aspect is a 20 20 spotting bug, such as the fruitspotting bug (Amblypelta nitida) and the banana-spotting bug (A. lutescens lutescens). Spotting bugs attack a wide variety of horticultural crops, including avocado, custard apples, lychee, mango, passionfruit, macadamia and pecans, as well as many native and ornamentalfruit ornamental fruitand andnuts. nuts. 25 25 In other embodiments, the pest or pest infestation to be targeted, prevented and/or controlled by the method for the present aspect is a nutborer, such as the macadamia nutborer (Cryptophlebia ombrodelta). The pesticide formulation and/or the emulsifiable concentrate formulation of the invention may be applied to the target crop or plant of 30 30 interest, to a part thereof (such as the leaf or seed), or to surroundings thereof. Methods and techniques for applying the pesticide formulation

22

Jul 2020

and/or the and/or the emulsifiable emulsifiable concentrate formulation are concentrate formulation are known knownininthe theart art and and may include, for example, ground or aerial spraying. In one embodiment, liquid forms of the pesticide formulation and/or 2020204435 02

the emulsifiable concentrate formulation are applied at a rate of about 5 to 5 5 500mL 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, 10 10 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, 15 15 445mL, 450mL, 455mL, 460mL, 465mL, 470mL, 475mL, 480mL, 485mL, 490mL, 495mL, 500mL per hectare and any range therein) and more preferably at a rate of about 30mL to about 300mL per hectare subsequent to dilution thereof in a suitable spray liquid. Obviously, the amount of the pesticide formulation and/or the emulsifiable concentrate to 20 20 be applied per hectare will depend, at least in part, upon the concentration of beta-cyfluthrin therein, the particular pest infestation to be targeted and the type of target crop to which the formulation is to be applied. In another embodiment, solid forms of the pesticide formulation are applied at a rate of about 10g to about 10OOg per hectare (e.g., about 10, 25 25 20, 30, 40, 50, 60, 70, 80, 90, 100, 125, 150, 175, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, 500, 525, 550, 575, 600, 625, 650, 675, 700, 725, 750, 775, 800, 825, 850, 875, 900, 925, 950, 975, 1000 g per hectare and any range therein) and more preferably at a rate of about 30g to about 500g per hectare subsequent to dilution thereof in a 30 30 suitable spray liquid.

23

In one embodiment, the pH of the emulsifiable concentrate formulation according to CIPAC MT 75.3 is between about 4.5 and about 9.5 (e.g., about pH 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5 and 2020204435 02

any range therein), more suitably between about 6.0 and about 8.0, 5 5 preferably between about 6.5 and about 7.5 and more preferably about 7.0. Suitably, the emulsion characteristics of the emulsifiable concentrate formulation according to CIPAC MT36.1 are 2mL of cream and little or no trace of oil after 30 min and complete re-emulsion after 24 10 10 hours. hours.

In certain embodiments, the persistent foam of the emulsifiable concentrate formulation according to CIPAC MT47 can be 60mL after 1 min, more suitably 30mL after 1 min, preferably l5mL after 1 min, and most preferably! 10mL after 1 min. 15 15 The specific gravity of the emulsifiable concentrate formulation according to CIPAC MT3.1 is suitably between about 0.980 to about 1.020 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 20 20 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. invention.

All computer programs, algorithms, patent and scientific literature 25 25 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 Australia. Australia.

24

Jul 2020

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. 2020204435 02

25

Example 1: Embodiments of a Highly Loaded Beta-cyfluthrin Emulsifiable Concentrate Formulation

2020204435 02

A numberofofembodiments A number embodiments of emulsifiable of emulsifiable concentrate concentrate formulations formulations

5 5 across a range of beta-cyfluthrin concentrations, a range of overall beta cyfluthrin and piperonyl butoxide concentrations/proportions, and some alternative solvents and surfactants are provided below.

26

Jul 2020

Table 1 - Beta-cyfluthrin 100 + Piperonyl butoxide 400 EC Nominal QC Parameters

Test Test Test Method Test Method Required Observed Observed Required, Required, Required, Parameter (Advised Preferably More Ideally preferred Preferably 2020204435 02

formulation) Appearance Visual Visual Clear, yellow Clear, yellow Clear, yellow to brown liquid liquid Assay Validated 90 to 110g/L chromatographic beta method cyfluthrin (Accuracy: 98 102%) 101g/L beta (Linearity: R > cyfluthrin - - -

0.99) (Precision: s/average << 2%) Assay Validated 380 380 to to chromatographic 420g/L method piperonyl (Accuracy: 98- butoxide 393g/L 102%) piperonyl (Linearity: R > butoxide - - -

0.99) (Precision: s/average << 2%) pH (1%) CIPAC MT 75.3 4.5 to9.5 4.5 to 9.5 7.1 7.1 - - - s2mLcream 2mL cream after 30 min, trace of oil Emulsion Emulsion CIPAC MT36.1 after 30 min, Traces Traces of of :1%w/w characteristics and cream only over 75pm - -

complete re emulsion after 24h Persistent CIPAC MT47 560mL after OmL 530mL (1 515mL (1 foam 1 min minute) minute) -

Specific CIPAC MT3.1 ~0.980 to ~0.980 to 0.998 gravity 1.020 - - -

Long Term Various as per Test Test Complies Performance above parameter maintained within required range after - - -

accelerated aging to approximate 2 years.

5 5

27

Embodiment 1 - Recipe for a nominally 100g/L beta-cyfluthrin emulsifiable concentrate with 400g/L piperonyl butoxide, constructed and determined as having adequate active ingredient concentration, emulsion 2020204435 02

properties upon dilution in water prior to application, and physical and 5 5 chemical stability, at the point of manufacturing and again after accelerated aging to approximate two years of shelf life.

Composition as follows: Ingredient Role Concentration Beta-cyfluthrin Active 103.9g/L (CAS# 68359-37-5, Technical material, insecticidal (yields 100.3g/L beta 96.5%) ingredient cyfluthrin) Piperonyl butoxide Insecticidal 426.0g/L (CAS# 51-03-6, Technical material, synergist (yields 401.3g/L piperonyl 94.2%) butoxide) Alkoxylated alkylphenol Surfactant 8.7g/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Alkyl polyoxyalkylene ether Surfactant Surfactant 5.7g/L (CAS# Proprietary, e.g. Termul 203) Alkylbenzenesulfonic acid, calcium salt in Surfactant 25.2g/L 2-ethylhexanol (CAS# 68584-23-6 in 104-76-7, e.g. Ninate 60E) Solvent naphtha (petroleum), heavy Solvent 423.3g/L aromatic (to 993g/L total) (CAS# 64742-94-5, e.g. Recosol 150)

10 10 Chemical and physical parameters as follows: Test As- Accelerated Aged manufactured Result Assay: 103.2g/L 106.3g/L Require 90g/L 5 beta-cyfluthrin 110g/L Assay: 405.8g/L 403.6g/L Require 380g/L : piperonyl butoxide 420g/L pH1% 8.0 8.0 7.8 7.8 Nominally: 4.5 to 9.5 Persistent foaming OmL 0mL 3mL 3mL Require:560mL foam after 1 min Emulsion characteristics No cream; No cream; Require: 52mL cream after 30 min, No oil; No oil; trace of oil after 30 min and complete Re-emulsifies/24h Re-emulsifies/24h re-emulsion after 24h

28

Jul 2020

Embodiment 2 - Recipe for a nominally 100g/L beta-cyfluthrin emulsifiable concentrate with 400g/L piperonyl butoxide, constructed and determined as having adequate active ingredient concentration, emulsion 2020204435 02

properties upon dilution in water prior to application, and physical and 5 5 chemical stability, at the point of manufacturing and again after accelerated aging to approximate two years of shelf life.

Composition as follows: Ingredient Role Role Concentration Concentration Beta-cyfluthrin Active 103.9g/L (CAS# 68359-37-5, Technical material, insecticidal (yields 100.4g/L beta 96.5%) ingredient cyfluthrin) Piperonyl butoxide Insecticidal 426.1g/L (CAS# 51-03-6, Technical material, synergist (yields 401.3g/L piperonyl 94.2%) butoxide) Tristryrylphenol ethoxylate Surfactant Surfactant 9.9g/L (CAS# 99734-09-5, e.g. Termul 3150) Alkylbenzenesulfonic acid, calcium salt in Surfactant Surfactant 18.2g/L 2-ethylhexanol (CAS# 68584-23-6 in 104-76-7, e.g. Ninate 60E) Solvent naphtha (petroleum), heavy Solvent Solvent 433.4g/L aromatic (to 992g/L total) (CAS# 64742-94-5, e.g. Recosol 150)

10 10 Chemical and physical parameters as follows: Test As- Accelerated Aged manufactured Result Assay: 106.8g/L 107.1g/L Require 90g/L 5 beta-cyfluthrin 5 110g/L Assay: 404.8g/L 397.0g/L Require 380g/L : piperonyl butoxide 420g/L pH1% 7.6 7.6 7.8 7.8 Nominally: 4.5 to 9.5 Persistent foaming 3mL 3mL 3mL 3mL Require: 560mL foam after 1 min Emulsion characteristics No cream; No cream; Require: 52mL cream after 30 min, No oil; No oil; trace of oil after 30 min and complete Re-emulsifies/24h Re-emulsifies/24h re-emulsion after 24h

29

Embodiment 3 - Recipe for a nominally 100g/L beta-cyfluthrin emulsifiable concentrate with 400g/L piperonyl butoxide, constructed and determined as having adequate active ingredient concentration, emulsion properties upon dilution in water prior to application, and physical and 5 5 chemical stability, at the point of manufacturing and again after 2020204435

accelerated aging to approximate two years of shelf life.

Composition as follows: Ingredient Role Concentration Beta-cyfluthrin Active 103.9g/L (CAS# 68359-37-5, Technical material, insecticidal (yields 100.4g/L beta 96.5%) ingredient cyfluthrin) Piperonyl butoxide Insecticidal 425.9g/L (CAS# 51-03-6, Technical material, synergist (yields 401.2g/L piperonyl 94.2%) butoxide) Castor oil ethoxylate Surfactant Surfactant 10.2g/L (CAS# 61791-12-6, e.g. Termul 1285) Alkylbenzenesulfonic acid, calcium salt in Surfactant Surfactant 18.5g/L 2-ethylhexanol (CAS# 68584-23-6 in 104-76-7, e.g. Ninate 60E) Solvent naphtha (petroleum), heavy Solvent 431.8g/L aromatic (to 990g/L total) (CAS# 64742-94-5, e.g. Recosol 150)

10 10 Chemical and physical parameters as follows: Test Test As- Accelerated Aged manufactured Result Assay: 103.4g/L 105.6g/L Require 90g/L 5 beta-cyfluthrin5 110g/L Assay: 403.0g/L 402.3g/L Require 380g/L : piperonyl butoxide 420g/L pH1% 7.5 7.5 7.7 7.7 Nominally: 4.5 to 9.5 Persistent foaming 2mL 2mL 3mL 3mL Require: 560mL foam after 1 min Emulsion characteristics Emulsion characteristics No cream; No cream; Require: 52mL cream after 30 min, No oil; No oil; trace of oil after 30 min and complete Re-emulsifies/24h Re-emulsifies/24h re-emulsion after 24h

30

Jul 2020

Embodiment 4 - Recipe for a nominally 100g/L beta-cyfluthrin emulsifiable concentrate with 400g/L piperonyl butoxide, constructed and determined as having adequate active ingredient concentration, emulsion properties upon dilution in water prior to application, and physical and 5 5 chemical stability, at the point of manufacturing and again after accelerated aging to approximate two years of shelf life.

Composition as follows: Ingredient Role Concentration Concentration Beta-cyfluthrin Active 104.0g/L (CAS# 68359-37-5, Technical material, insecticidal (yields 100.4g/L beta 96.5%) ingredient cyfluthrin) Piperonyl butoxide Insecticidal 426.0g/L (CAS# 51-03-6, Technical material, synergist (yields 401.3g/L piperonyl 94.2%) butoxide) Alkoxylated alkylphenol Surfactant Surfactant 7.7g/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Alkyl polyoxyalkylene ether Surfactant 4.9g/L (CAS# Proprietary, e.g. Termul 203) Alkylbenzenesulfonic acid, calcium salt in Surfactant Surfactant 22.4g/L 2-ethylhexanol (CAS# 68584-23-6 in 104-76-7, e.g. Ninate 60E) Solvent naphtha (petroleum), heavy Solvent Solvent 428.0g/L aromatic (to 993g/L total) (CAS# 64742-94-5, e.g. Recosol 150)

10 10 Chemical and physical parameters as follows: Test As- Accelerated Aged manufactured Result Assay: 101.4g/L 105.4g/L Require 90g/L 5 beta-cyfluthrin 110g/L Assay: 402.3g/L 400.9g/L Require 380g/L : piperonyl butoxide 5 420g/L pH1% 8.0 7.5 Nominally: 4.5 to 9.5 Persistent foaming OmL 1mL Require:560mL foam after 1 min Emulsion characteristics No cream; No cream; Require: 52mL cream after 30 min, No oil; No oil; trace of oil after 30 min and complete Re-emulsifies/24h Re-emulsifies/24h re-emulsion after 24h

31

Embodiment 5 - Recipe for a nominally 100g/L beta-cyfluthrin emulsifiable concentrate with 400g/L piperonyl butoxide, constructed and determined as having adequate active ingredient concentration, emulsion 2020204435 02

properties upon dilution in water prior to application, and physical and 5 5 chemical stability, at the point of manufacturing and again after accelerated aging to approximate two years of shelf life.

Composition as follows: Ingredient Role Role Concentration Concentration Beta-cyfluthrin Active 104.1g/L (CAS# 68359-37-5, Technical material, insecticidal (yields 100.5g/L beta 96.5%) ingredient cyfluthrin) Piperonyl butoxide Insecticidal 426.1g/L (CAS# 51-03-6, Technical material, synergist (yields 401.4g/L piperonyl 94.2%) butoxide) Alkoxylated alkylphenol Surfactant Surfactant 12.5g/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Alkylbenzenesulfonic acid, calcium salt in Surfactant 12.7g/L 2-ethylhexanol (CAS# 68584-23-6 in 104-76-7, e.g. Ninate 60E) Solvent naphtha (petroleum), heavy Solvent 436.0g/L aromatic (to 991g/L total) (CAS# 64742-94-5, e.g. Recosol 150)

10 10 Chemical and physical parameters as follows: Test As- As- Accelerated Aged manufactured Result Assay: 107.9g/L 105.1g/L Require 90g/L 5 beta-cyfluthrin 110g/L Assay: 401.6g/L 402.8g/L Require 380g/L : piperonyl butoxide 420g/L pH1% 6.1 6.9 Nominally: 4.5 to 9.5 Persistent foaming OmL 0mL OmL 0mL Require: 560mL foam after 1 min Emulsion characteristics No cream; 0.2mL cream; Require: 52mL cream after 30 min, No oil; No oil; trace of oil after 30 min and complete Re-emulsifies/24h Re-emulsifies/24h re-emulsion after 24h

32

Jul 2020

Embodiment 6 - Recipe for a nominally 100g/L beta-cyfluthrin emulsifiable concentrate with 400g/L piperonyl butoxide, constructed and determined as having adequate active ingredient concentration, emulsion 2020204435 02

properties upon dilution in water prior to application, and physical and 5 5 chemical stability, at the point of manufacturing and again after accelerated aging to approximate two years of shelf life.

Composition as follows: Ingredient Role Concentration Beta-cyfluthrin Active 104.4g/L (CAS# 68359-37-5, Technical material, insecticidal (yields 100.7g/L beta 96.5%) ingredient cyfluthrin) Piperonyl butoxide Insecticidal 426.5g/L (CAS# 51-03-6, Technical material, synergist (yields 401.8g/L piperonyl 94.2%) butoxide) Alkoxylated alkylphenol Surfactant 17.9g/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Alkylbenzenesulfonic acid, calcium salt in Surfactant 17.9g/L 2-ethylhexanol (CAS# 68584-23-6 in 104-76-7, e.g. Ninate 60E) Solvent naphtha (petroleum), heavy Solvent 425.3g/L aromatic (to 992g/L total) (CAS# 64742-94-5, e.g. Recosol 150)

10 Chemical and physical parameters as follows: Test As- Accelerated Aged manufactured Result Assay: 103.1g/L 106.2g/L Require 90g/L 5 beta-cyfluthrin 110g/L Assay: 403.4g/L 406.7g/L Require 380g/L : piperonyl butoxide 420g/L pH1% 6.3 6.7 Nominally: 4.5 to 9.5 Persistent foaming OmL 1mL Require: 560mL foam after 1 min Emulsion characteristics No cream; 0.2mL cream; Require: 52mL cream after 30 min, No oil; No oil; trace of oil after 30 min and complete Re-emulsifies/24h Re-emulsifies/24h re-emulsion after 24h

33

Embodiment 7 - Recipe for a nominally 100g/L beta-cyfluthrin emulsifiable concentrate with 400g/L piperonyl butoxide, constructed and determined as having adequate active ingredient concentration, emulsion properties upon dilution in water prior to application, and physical and

chemical stability, at the point of manufacturing and again after accelerated aging to approximate two years of shelf life.

Composition as follows: Ingredient Role Role Concentration Concentration Beta-cyfluthrin Active 103.6g/L (CAS# 68359-37-5, Technical material, insecticidal (yields 100.0g/L beta 96.5%) ingredient cyfluthrin) Piperonyl butoxide Insecticidal 425.5g/L (CAS# 51-03-6, Technical material, synergist (yields 400.8g/L piperonyl 94.2%) butoxide) Alkoxylated alkylphenol Surfactant Surfactant 35.0g/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Alkylbenzenesulfonic acid, calcium salt in Surfactant 35.0g/L 2-ethylhexanol (CAS# 68584-23-6 in 104-76-7, e.g. Ninate 60E) Solvent naphtha (petroleum), heavy Solvent Solvent 398.8g/L aromatic (to 998g/L total) (CAS# 64742-94-5, e.g. Recosol 150)

Chemical and physical parameters as follows: Test As- Accelerated Aged manufactured Result Assay: 101g/L 104g/L Require 90g/L 5 beta-cyfluthrin 110g/L Assay: 393g/L 390g/L Require 380g/L : piperonyl butoxide 420g/L pH1% 7.1 7.1 7.0 7.0 Nominally: 4.5 to 9.5 Persistent foaming OmL 0mL 2mL 2mL Require: 560mL foam after 1 min Emulsion characteristics No cream; No cream; Require: 52mL cream after 30 min, No oil; No oil; trace of oil after 30 min and complete Re-emulsifies/24h Re-emulsifies/24h re-emulsion after 24h

34

Embodiment 8 - Recipe for a nominally 100g/L beta-cyfluthrin 2020204435 02 Jul emulsifiable concentrate with 200g/L piperonyl butoxide, constructed and determined as having adequate active ingredient concentration, emulsion properties upon dilution in water prior to application, and physical and 5 5 chemical stability, at the point of manufacturing and again after accelerated aging to approximate two years of shelf life.

Composition as follows: Ingredient Role Role Concentration Concentration Beta-cyfluthrin Active 104.0g/L (CAS# 68359-37-5, Technical material, insecticidal (yields 100.4g/L beta 96.5%) ingredient cyfluthrin) Piperonyl butoxide Insecticidal 212.9g/L (CAS# 51-03-6, Technical material, synergist (yields 200.6g/L piperonyl 94.2%) butoxide) Alkoxylated alkylphenol Surfactant Surfactant 35.0g/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Alkylbenzenesulfonic acid, calcium salt in Surfactant 35.0g/L 2-ethylhexanol (CAS# 68584-23-6 in 104-76-7, e.g. Ninate 60E) Solvent naphtha (petroleum), heavy Solvent Solvent 577.1g/L aromatic (to 964g/L total) (CAS# 64742-94-5, e.g. Recosol 150)

10 10 Chemical and physical parameters as follows: Test Test As- Accelerated Aged manufactured Result Assay: 103g/L 100g/L Require 90g/L 5 beta-cyfluthrin 11Og/L Assay: 200g/L 192g/L Require 188g/L : piperonyl butoxide 212g/L pH1% 7.2 7.2 7.0 7.0 Nominally: 4.5 to 9.5 Persistent foaming OmL 0mL OmL 0mL Require: 560mL foam after 1 min Emulsioncharacteristics Emulsion characteristics No cream; No cream; Require: 52mL cream after 30 min, No oil; No oil; trace of oil after 30 min and complete Re-emulsifies/24h Re-emulsifies/24h re-emulsion after 24h

35

Embodiment 9 - Recipe for a nominally 50g/L beta-cyfluthrin emulsifiable concentrate with 100g/L piperonyl butoxide, constructed and determined as having adequate active ingredient concentration, emulsion properties 2020204435 02

upon dilution in water prior to application, and physical and chemical 5 5 stability, at the point of manufacturing and again after accelerated aging to approximate two years of shelf life.

Composition as follows: Ingredient Role Role Concentration Concentration Beta-cyfluthrin Active 52.0g/L (CAS# 68359-37-5, Technical material, insecticidal (yields 50.2g/L beta 96.5%) ingredient cyfluthrin) Piperonyl butoxide Insecticidal 106.2g/L (CAS# 51-03-6, Technical material, synergist (yields 100.0g/L piperonyl 94.2%) butoxide) Alkoxylated alkylphenol Surfactant Surfactant 35.0g/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Alkylbenzenesulfonic acid, calcium salt in Surfactant Surfactant 35.1g/L 2-ethylhexanol (CAS# 68584-23-6 in 104-76-7, e.g. Ninate 60E) Solvent naphtha (petroleum), heavy Solvent Solvent 703.2g/L aromatic (to 931g/L total) (CAS# 64742-94-5, e.g. Recosol 150)

10 Chemical and physical parameters as follows: Test Test As- As- Accelerated Aged manufactured Result Assay: 50.3g/L 49.5g/L Require 45g/L 5 beta-cyfluthrin5 55g/L Assay: 98.5g/L 96.1g/L Require 90g/L piperonyl butoxide 110g/L pH1% 7.3 7.3 7.2 7.2 Nominally: 4.5 to 9.5 Persistent foaming OmL 0mL OmL 0mL Require: 560mL foam after 1 min Emulsion characteristics Emulsion characteristics No cream; 1mL of cream; Require: 52mL cream after 30 min, No oil; No oil; trace of oil after 30 min and complete Re-emulsifies/24h Re-emulsifies/24h re-emulsion after 24h

36

Embodiment 10 - Recipe for a nominally 25g/L beta-cyfluthrin emulsifiable concentrate with 50g/L piperonyl butoxide, constructed and determined as having adequate active ingredient concentration, emulsion properties upon dilution in water prior to application, and physical and 5 5 chemical stability, at the point of manufacturing and again after 2020204435

accelerated aging to approximate two years of shelf life.

Composition as follows: Ingredient Role Concentration Beta-cyfluthrin Active 26.0g/L (CAS# 68359-37-5, Technical material, insecticidal (yields 25.1g/L beta 96.5%) ingredient cyfluthrin) Piperonyl butoxide Insecticidal 53.1g/L (CAS# 51-03-6, Technical material, synergist (yields 50.0g/L piperonyl 94.2%) butoxide) Alkoxylated alkylphenol Surfactant 35.0g/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Alkylbenzenesulfonic acid, calcium salt in Surfactant 34.9g/L 2-ethylhexanol (CAS# 68584-23-6 in 104-76-7, e.g. Ninate 60E) Solvent naphtha (petroleum), heavy Solvent 766.6g/L aromatic (to 916g/L total) (CAS# 64742-94-5, e.g. Recosol 150)

10 Chemical and physical parameters as follows: Test As- Accelerated Aged manufactured Result Assay: 26.2g/L 26.1g/L Require 21.3g/L 5 beta-cyfluthrin 28.7g/L Assay: 49.4g/L 51.8g/L Require 45g/L piperonyl butoxide 55g/L pH1% 7.36 7.36 7.7 7.7 Nominally: 4.5 to 9.5 Persistent foaming OmL 0mL OmL 0mL Require:560mL foam after 1 min Emulsion characteristics No cream; Trace of cream; Require: 52mL cream after 30 min, No oil; No oil; trace of oil after 30 min and complete Re-emulsifies/24h Re-emulsifies/24h re-emulsion after 24h

37

Embodiment 11 - Recipe for a nominally 25g/L beta-cyfluthrin emulsifiable concentrate with 250g/L piperonyl butoxide, constructed and determined as having adequate active ingredient concentration, emulsion properties upon dilution in water prior to application, and physical and

chemical stability, at the point of manufacturing and again after accelerated aging to approximate two years of shelf life.

Composition as follows: Ingredient Role Role Concentration Concentration Beta-cyfluthrin Active 26.2g/L (CAS# 68359-37-5, Technical material, insecticidal (yields 25.3g/L beta 96.5%) ingredient cyfluthrin) Piperonyl butoxide Insecticidal 266.1g/L (CAS# 51-03-6, Technical material, synergist (yields 250.7g/L piperonyl 94.2%) butoxide) Alkoxylated alkylphenol Surfactant Surfactant 34.9g/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Alkylbenzenesulfonic acid, calcium salt in Surfactant 35.0g/L 2-ethylhexanol (CAS# 68584-23-6 in 104-76-7, e.g. Ninate 60E) Solvent naphtha (petroleum), heavy Solvent Solvent 587.8g/L aromatic (to 950g/L total) (CAS# 64742-94-5, e.g. Recosol 150)

Chemical and physical parameters as follows: Test As- Accelerated Aged manufactured Result Assay: 27.0g/L 26.3g/L Require 21.3g/L beta-cyfluthrin 28.7g/L Assay: 247g/L 242g/L Require 235g/L : piperonyl butoxide 265g/L pH1% 7.9 7.9 7.9 7.9 Nominally: 4.5 to 9.5 Persistent foaming OmL 0mL OmL Require: 560mL foam after 1 min Emulsion characteristics 1mL cream; Trace of cream; Require: 52mL cream after 30 min, No oil; No oil; trace of oil after 30 min and complete Re-emulsifies/24h Re-emulsifies/24h re-emulsion after 24h

38

Embodiment 12 - Recipe for a nominally 100g/L beta-cyfluthrin emulsifiable concentrate with 100g/L piperonyl butoxide, constructed and determined as having adequate active ingredient concentration, emulsion properties upon dilution in water prior to application, and physical and 5 5 chemical stability, at the point of manufacturing and again after 2020204435

accelerated aging to approximate two years of shelf life.

Composition as follows: Ingredient Role Role Concentration Concentration Beta-cyfluthrin Active 104.1g/L (CAS# 68359-37-5, Technical material, insecticidal (yields 100.5g/L beta 96.5%) ingredient cyfluthrin) Piperonyl butoxide Insecticidal 106.1g/L (CAS# 51-03-6, Technical material, synergist (yields 99.9g/L piperonyl 94.2%) butoxide) N-methyl-pyrolidone Solvent Solvent 335.9g/L (CAS# 872-50-4) Alkoxylated alkylphenol Surfactant Surfactant 35.2g/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Alkylbenzenesulfonic acid, calcium salt in Surfactant Surfactant 34.9g/L 2-ethylhexanol (CAS# 68584-23-6 in 104-76-7, e.g. Ninate 60E) Solvent naphtha (petroleum), heavy Solvent Solvent 385.6g/L aromatic (to 1002g/L total) (CAS# 64742-94-5, e.g. Recosol 150)

10 10 Chemical and physical parameters as follows: Test As- Accelerated Aged manufactured Result Assay: 100.1g/L 101.6g/L Require 90g/L 5 beta-cyfluthrin 5 110g/L Assay: 98.0g/L 97.6g/L Require 90g/L piperonyl butoxide 110g/L pH1% 6.3 6.2 Nominally: 4.5 to 9.5 Persistent foaming OmL OmL 0mL Require: 560mL foam after 1 min Emulsion characteristics No cream; No cream; Require: 52mL cream after 30 min, No oil; No oil; trace of oil after 30 min and complete Re-emulsifies/24h Re-emulsifies/24h re-emulsion after 24h

39

Embodiment 13 - Recipe for a nominally 100g/L beta-cyfluthrin emulsifiable concentrate with 100g/L piperonyl butoxide, constructed and determined as having adequate active ingredient concentration, emulsion properties upon dilution in water prior to application, and physical and

chemical stability, at the point of manufacturing and again after accelerated aging to approximate two years of shelf life.

Composition as follows: Ingredient Role Role Concentration Concentration Beta-cyfluthrin Active 107.0g/L (CAS# 68359-37-5, Technical material, insecticidal (yields 103.2g/L beta 96.5%) ingredient cyfluthrin) Piperonyl butoxide Insecticidal 106.1g/L (CAS# 51-03-6, Technical material, synergist (yields 99.9g/L piperonyl 94.2%) butoxide) Alkoxylated alkylphenol Surfactant Surfactant 35.6g/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Alkylbenzenesulfonic acid, calcium salt in Surfactant 34.9g/L 2-ethylhexanol (CAS# 68584-23-6 in 104-76-7, e.g. Ninate 60E) Acetic acid C6-8 brached alkyl ester Solvent 651.7g/L (e.g. CAS# 90438-79-2, Exxate 700) (to 935g/L total)

Chemical and physical parameters as follows: Test As- As- Accelerated Aged manufactured Result Assay: 104.1g/L 98.4g/L Require 90g/L 5 beta-cyfluthrin 110g/L Assay: 97.5g/L 91.2g/L Require 90g/L piperonyl butoxide 110g/L pH1% 5.8 5.8 4.9 Nominally: 4.5 to 9.5 Persistent foaming OmL 0mL 1mL 1mL Require: 560mL foam after 1 min Emulsion characteristics No cream; No cream; Require: 52mL cream after 30 min, No oil; No oil; trace of oil after 30 min and complete Re-emulsifies/24h Re-emulsifies/24h re-emulsion after 24h

40

Jul 2020

Embodiment 14 - Recipe for a nominally 100g/L beta-cyfluthrin emulsifiable concentrate with 100g/L piperonyl butoxide, constructed and determined as having adequate active ingredient concentration, emulsion 2020204435 02

properties upon dilution in water prior to application, and physical and 5 5 chemical stability, at the point of manufacturing and again after accelerated aging to approximate two years of shelf life.

Composition as follows: Ingredient Role Role Concentration Concentration Beta-cyfluthrin Active 104.2g/L (CAS# 68359-37-5, Technical material, insecticidal (yields 100.6g/L beta 96.5%) ingredient cyfluthrin) Piperonyl butoxide Insecticidal 106.0g/L (CAS# 51-03-6, Technical material, synergist (yields 99.9g/L piperonyl 94.2%) butoxide) Alkoxylated alkylphenol Surfactant Surfactant 36.6g/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Alkylbenzenesulfonic acid, calcium salt in Surfactant 35.3g/L 2-ethylhexanol (CAS# 68584-23-6 in 104-76-7, e.g. Ninate 60E) Isophorone Solvent Solvent 689.3g/L (CAS# 78-59-1) (to 971g/L total)

10 Chemical and physical parameters as follows: Test Test As- As- Accelerated Aged manufactured Result Assay: 100.8g/L 98.4g/L Require 90g/L 5 beta-cyfluthrin 110g/L Assay: 96.9g/L 94.7g/L Require 90g/L piperonyl butoxide 11Og/L pH1% 6.2 6.2 5.9 5.9 Nominally: 4.5 to 9.5 Persistent foaming 2mL 2mL 3mL 3mL Require:560mL foam after 1 min Emulsioncharacteristics Emulsion characteristics No cream; No cream; Require: 52mL cream after 30 min, No oil; No oil; trace of oil after 30 min and complete Re-emulsifies/24h Re-emulsifies/24h re-emulsion after 24h

41

Embodiment 15 - Recipe for a nominally 100g/L beta-cyfluthrin emulsifiable concentrate with 400g/L piperonyl butoxide, constructed and determined as having adequate active ingredient concentration, emulsion 2020204435 02

properties upon dilution in water prior to application, and physical and 5 5 chemical stability, at the point of manufacturing and again after accelerated aging to approximate two years of shelf life.

Composition as follows: Ingredient Role Role Concentration Concentration Beta-cyfluthrin Active 104.2g/L (CAS# 68359-37-5, Technical material, insecticidal (yields 100.6g/L beta 96.5%) ingredient cyfluthrin) Piperonyl butoxide Insecticidal 406.2g/L (CAS# 51-03-6, Technical material, synergist (yields 382.6g/L piperonyl 94.2%) butoxide) Castor oil ethoxylate Surfactant Surfactant 49.1g/L (CAS# 61791-12-6, e.g. Termul 1285) Alkylbenzenesulfonic acid, calcium salt in Surfactant Surfactant 21.3g/L 2-ethylhexanol (CAS# 68584-23-6 in 104-76-7, e.g. Ninate 60E) Solvent naphtha (petroleum), heavy Solvent Solvent 413.8g/L aromatic (to 995g/L total) (CAS# 64742-94-5, e.g. Recosol 150)

10 Chemical and physical parameters as follows: Test Test As- As- Accelerated Aged manufactured Result Assay: 102.2g/L 100.0g/L Require 90g/L 5 beta-cyfluthrin 110g/L Assay: 396.6g/L 398.5g/L Require 380g/L : piperonyl butoxide 420g/L pH1% 6.2 6.2 6.2 6.2 Nominally: 4.5 to 9.5 Persistent foaming 1mL 1mL 1mL 1mL Require:560mL foam after 1 min Emulsioncharacteristics Emulsion characteristics No cream; No cream; Require: 52mL cream after 30 min, No oil; No oil; trace of oil after 30 min and complete Re-emulsifies/24h Re-emulsifies/24h re-emulsion after 24h

42

Jul 2020

Embodiment 16 - Recipe for a nominally 100g/L beta-cyfluthrin emulsifiable concentrate with 400g/L piperonyl butoxide, constructed and determined as having adequate active ingredient concentration, emulsion 2020204435 02

properties upon dilution in water prior to application, and physical and 5 5 chemical stability, at the point of manufacturing and again after accelerated aging to approximate two years of shelf life.

Composition as follows: Ingredient Role Role Concentration Concentration Beta-cyfluthrin Active 105.8g/L (CAS# 68359-37-5, Technical material, insecticidal (yields 102.1g/L beta 96.5%) ingredient cyfluthrin) Piperonyl butoxide Insecticidal 426.0g/L (CAS# 51-03-6, Technical material, synergist (yields 401.3g/L piperonyl 94.2%) butoxide) Alkoxylated alkylphenol Surfactant Surfactant 35.1g/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Alkylbenzenesulfonic acid, calcium salt in Surfactant 34.9g/L 2-ethylhexanol (CAS# 68584-23-6 in 104-76-7, e.g. Ninate 60E) Methyl benzoate Solvent 504.7g/L (CAS# 93-58-3, e.g. Recosol 150) (to 1106g/L total)

10 Chemical and physical parameters as follows: Test Test As- As- Accelerated Aged manufactured Result Assay: 105.0g/L 105.1g/L Require 90g/L 5 beta-cyfluthrin 110g/L Assay: 405.2g/L 394.8g/L Require 380g/L : piperonyl butoxide 420g/L pH1% 6.3 6.3 6.0 Nominally: 4.5 to 9.5 Persistent foaming 2mL 2mL 4mL 4mL Require: 560mL foam after 1 min Emulsion characteristics No cream; No cream; Require: 52mL cream after 30 min, No oil; No oil; trace of oil after 30 min and complete Re-emulsifies/24h Re-emulsifies/24h re-emulsion after 24h

43

Embodiment 17 - Recipe for a nominally 100g/L beta-cyfluthrin emulsifiable concentrate with 400g/L piperonyl butoxide, constructed and determined as having adequate active ingredient concentration, emulsion properties upon dilution in water prior to application, and physical and 5 5 chemical stability, at the point of manufacturing and again after 2020204435

accelerated aging to approximate two years of shelf life.

Composition as follows: Ingredient Role Role Concentration Concentration Beta-cyfluthrin Active 104.0g/L (CAS# 68359-37-5, Technical material, insecticidal (yields 100.4g/L beta 96.5%) ingredient cyfluthrin) Piperonyl butoxide Insecticidal 426.3g/L (CAS# 51-03-6, Technical material, synergist (yields 401.6g/L piperonyl 94.2%) butoxide) N-methyl-2-pyrrolidone Solvent Solvent 231.5g/L (CAS# 872-50-4) Alkoxylated alkylphenol Surfactant Surfactant 36.9g/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Alkylbenzenesulfonic acid, calcium salt in Surfactant Surfactant 35.3g/L 2-ethylhexanol (CAS# 68584-23-6 in 104-76-7, e.g. Ninate 60E) Solvent naphtha (petroleum), heavy Solvent Solvent 199.9g/L aromatic (to 1034g/L total) (CAS# 64742-94-5, e.g. Recosol 150)

10 10 Chemical and physical parameters as follows: Test As- Accelerated Aged manufactured Result Assay: 104.2g/L 103.5g/L Require 90g/L 5 beta-cyfluthrin5 110g/L Assay: 398.8g/L 400.4g/L Require 380g/L : piperonyl butoxide 420g/L pH1% 6.2 6.1 Nominally: 4.5 to 9.5 Persistent foaming 4mL 4mL Require: 560mL foam after 1 min Emulsion characteristics No cream; No cream; Require: 52mL cream after 30 min, No oil; No oil; trace of oil after 30 min and complete Re-emulsifies/24h Re-emulsifies/24h re-emulsion after 24h

44

Claims (16)

1. An emulsifiable concentrate formulation comprising: beta-cyfluthrin at a concentration of at least about 100 g/L; 5 piperonyl butoxide at a concentration of at least about 50 g/L; a surfactant; and 2020204435

optionally a solvent.

2. The emulsifiable concentrate formulation of Claim 1, wherein 10 piperonyl butoxide is present at a concentration of at least about 400 g/L of the total weight of the formulation.

3. The emulsifiable concentrate formulation of Claim 1 or Claim 2, wherein the surfactant is present in an amount of at least about 20 g/L. 15

4. The emulsifiable concentrate formulation of Claim 3, wherein the surfactant is present in an amount ranging between about 25 g/L to about 100 g/L.

20

5. The emulsifiable concentrate formulation of any one of Claims 1 to 4, wherein the surfactant is selected from the group consisting of an alkylphenol, a polyoxyalkylene ether, an alkylbenzenesulphonate, an alkoxylated styryl phenol, an alkoxylated oil and any combination thereof.

25

6. The emulsifiable concentrate formulation of Claim 5, wherein the surfactant is selected from the group consisting of an alkoxylated alkylphenol, an alkyl polyoxyalkalene ether, calcium C10-16 alkylbenzyl sulphonate, an ethoxylated tristyryl phenol, an ethoxylated castor oil and any combination thereof. 30

7. The emulsifiable concentrate formulation of any one of Claims 1 to

6, wherein the solvent is present in an amount of at least about 200 g/L.

8. The emulsifiable concentrate formulation of Claim 7, wherein the solvent is present in an amount ranging between about 300 g/L to about 5 800 g/L. 2020204435

9. The emulsifiable concentrate formulation of any one of Claims 1 to 8, wherein the solvent is selected from the group consisting of a petroleum derivative, a carboxamide, a benzoate, a ketone and any combination 10 thereof.

10. The emulsifiable concentrate formulation of Claim 9, wherein the solvent is selected from the group consisting of a heavy aromatic hydrocarbon, a pyrrolidone, an alkyl benzoate, an alkyl ketone, an alkyl 15 ester and any combination thereof.

11. The emulsifiable concentrate formulation of Claim 10, wherein the solvent is selected from the group consisting of a heavy aromatic solvent naphtha (petroleum), N-methyl pyrrolidone, methyl benzoate, isophorone, 20 an acetate ester and any combination thereof.

12. A method of preparing an emulsifiable concentrate formulation including the steps of: (a) combining beta-cyfluthrin, piperonyl butoxide, a surfactant and 25 optionally a solvent, wherein beta-cyfluthrin is present at a concentration of at least 100 g/L; and (b) mixing the mixture of step (a) to thereby prepare the pesticide formulation.

30

13. The method of Claim 12, wherein the emulsifiable concentrate formulation is the emulsifiable concentrate formulation of any one of

Claims 1 to 11.

14. An emulsifiable concentrate formulation prepared by the method of Claim 12 or Claim 13. 5 15. A method of preventing and/or controlling a pest infestation in a 2020204435

target area, including the step of applying a pesticidally effective amount of the emulsifiable concentrate formulation of any one of Claims 1 to 11 mixed with water or a water-containing liquid to the target area to thereby 10 prevent and/or control the pest infestation.

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