AU2021105797A4 - Pesticide formulation comprising pyriproxyfen - Google Patents

Abstract

The present invention relates to a pesticide formulation comprising: pyriproxyfen, a synergist, a surfactant, and optionally a solvent. The invention also relates to a concentrate formulation, an emulsifiable concentrate, a method of preparing a pesticide formulation of the invention, and a method of preventing and/or controlling a pest infestation in a target area using the pesticide formulation of the invention.

Description

PESTICIDE FORMULATION COMPRISING PYRIPROXYFEN FIELD OF THE INVENTION

This invention relates to a pesticide formulation. In particular, the

present invention relates to a pesticide formulation containing pyriproxyfen

as an active agent and piperonyl butoxide as a synergist and to methods of

preparing and using said formulation. However, it will be appreciated that

the invention is not limited to this particular field of use.

BACKGROUND TO THE INVENTION

Pyriproxyfen is an insect growth regulator, which displays its action

as a juvenile hormone mimic with agonistic activity towards juvenile

hormone receptors. It has some ovicidal effect, meaning it is also effective

during the egg stage. As it mimics the juvenile hormone, pyriproxyfen also

has an antimetamorphic effect, preventing transformation to the adult

stage by inhibiting the gene regulation required to mature to the adult

phase. Pyriproxyfen has some activity during the adult phase, as it is also

known to suppress embryogenesis and inhibit reproduction.

Pyriproxyfen is commonly obtained and used as a racemic mixture

of two active stereoisomers 4-phenoxyphenyl (R)-2-(2-pyridyloxy)propyl

ether and 4-phenoxyphenyl (S)-2-(2-pyridyloxy)propyl ether. It is

commonly used to control insect pests of public health significance, such

as flies, beetles, midges and mosquitos, and agriculturally significant pests

such as whitefly and thrips. It is generally applied to breeding areas, such as swamps and livestock houses, or to agricultural crops such as cotton.

It is a known problem that acaricides and insecticides such as

pyriproxyfen, when administered alone, can display reduced efficacy in

populations of target pests that are treated multiple times, as the

populations tend to build resistance to the active ingredient. One approach

to counteract such resistance is to combine the pyriproxyfen with another

active ingredient. However, the efficacy of this active ingredient can also

diminish over time and with repeated exposure of the population.

Accordingly, it would be preferable, and a significant advance in the art, to

provide an acaricide composition that does not display reduced efficacy

over time or with repeated exposure to a target population.

Notwithstanding the commercial availability of a range of

pyriproxyfen formulations, there remains a need for improved pyriproxyfen

based formulations for use in an agricultural setting that overcomes one or

more of the inherent limitations of commercially available pyriproxyfen

formulations.

It is an object of the present invention to overcome or ameliorate at

least one of the disadvantages of the prior art, or to provide a useful

alternative.

It is a preferred object of at least one form of the present invention

to provide a solvent-free (or substantially solvent-free) pesticide

formulation comprising pyriproxyfen, or a solvent-borne pesticide

formulation comprising pyriproxyfen, or a pesticide concentrate comprising

pyriproxyfen.

SUMMARY OF THE INVENTION

In a first aspect, the invention provides a pesticide formulation

comprising:

pyriproxyfen;

a synergist;

a surfactant; and

optionally, a solvent.

In a second aspect, the invention provides a concentrate

formulation comprising:

pyriproxyfen at a concentration of at least about 100 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,

wherein the concentrate formulation is an emulsifiable concentrate

formulation or a dispersible concentrate formulation.

In one embodiment, the invention provides a concentrate

formulation comprising:

pyriproxyfen at a concentration of at least about 300 g/L;

piperonyl butoxide at a concentration of at least about 50 g/L;

a non-ionic surfactant and an anionic surfactant; and

a solvent.

In some embodiments, the surfactant is present in an amount of at

least about 40 g/L. More particularly, the surfactant is suitably present in an amount ranging between about 40 g/L to about 80 g/L.

Suitably, the surfactant is selected from the group consisting of an

alkylphenol, a polyoxyalkylene ether, an alkylbenzene sulphonate, an

alkoxylated styryl phenol, an oil ethoxylate and any combination thereof.

Preferably, 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, a vegetable oil

ethoxylate and any combination thereof.

In one embodiment, 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 250 g/L to about 600 g/L.

Suitably, when present the solvent is selected from the group

consisting of a petroleum derivative, a carboxamide, a benzoate, a ketone,

a glycol ether and any combination thereof. Preferably, the solvent is

selected from the group consisting of a heavy aromatic solvent naphtha

(petroleum), 1-butylpyrrolidin-2-one, methyl benzoate, ethyl benzoate,

MIBK, isophorone, acetophenone, propylene glycol monomethyl ether and

any combination thereof. In one particularly suitable embodiment, the

solvent is methyl benzoate.

In some embodiments, the addition of a solvent is not required and

is therefore absent, or substantially absent, whereby the pyriproxyfen is at

least partially solubilised in the synergist (e.g. piperonyl butoxide). In such

embodiments, referred to herein as "solvent-less" formulations, it is

understood that the synergist acts as a solvent and at least partially solubilises the active agent.

In a third aspect, the invention provides a method of preparing a

pesticide formulation including the steps of:

(a) combining pyriproxyfen, a synergist such as piperonyl butoxide,

a surfactant and optionally a solvent, wherein pyriproxyfen is present at a

of at least 100 g/L; 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

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

applying a pesticidally effective amount of the pesticide formulation of the

first or fourth aspects or the 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 some cases, it may be

preferable to sequentially, or concurrently apply the inventive pesticide

formulation described herein, with the emulsifiable or dispersible

concentrate formulations described herein (mixed with water or a water

containing liquid).

In one embodiment, the method of the present aspect further

includes the initial step of mixing the pesticide formulation or the emulsifiable 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

concentrated liquid form or a highly loaded concentrated liquid form,

having relatively high concentrations of active ingredient/s in proportion to

other excipients within the formulation, and which are stable in concentrate

form but readily dispersible in water when diluted for use. By way of

example, the treatment of a given volume of produce or target area (e.g.,

crop, land, commercial or residential premises etc) can be achieved with a

reduced amount of pesticide product being used. As such, these

concentrated 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 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 or dispersible

concentrate form of a pesticide product can further alleviate some or all of

the deficiencies of other product formulations or preparations of the

pesticide in question, such as suspensions or suspoemulsions. To this

end, the active ingredient in emulsifiable concentrate formulations and

dispersible concentrate formulations (including highly loaded concentrate

forms) is not in the solid phase but is dissolved in a liquid phase, and

thereby is not subject to settling or physical phase separation of solid from

liquid. Furthermore, the selection of appropriate solvents and other

excipients typically requires careful consideration so as to achieve a

passable emulsifiable or dispersible concentrate formulation, especially at

high relative concentrations of active ingredients.

In view of the foregoing, the present invention advantageously

provides a pyriproxyfen composition or formulation suitable for the

prevention, control or treatment of a range of pest infestations in an

agricultural or horticultural setting. Further, the pyriproxyfen formulation

may be ready for direct use, or it may be an emulsifiable concentrate or a

dispersible concentrate, or it may be a highly loaded concentrate.

Accordingly, in one broad form the invention resides in a pesticide

formulation comprising:

pyriproxyfen;

a synergist;

a surfactant; and

optionally, a solvent.

The term "pyriproxyfen" refers to a racemic mixture of 4

phenoxyphenyl (R)-2-(2-pyridyloxy)propyl ether and 4-phenoxyphenyl (S)

2-(2-pyridyloxy)propyl ether. By "racemic", it is meant that the proportions

of the two stereoisomers are relatively equivalent (i.e., the (R) and (S)

isomers are each approximately equal, or about 50% (R) and about 50%

(S)) although some variation may occur. It will be appreciated that use of

the term "pyriproxyfen" herein can refer to one or both of these

stereoisomers, including specific mixtures and/or ratios thereof, such as

racemic mixtures.

As generally used herein, the term "highly loaded" means that

pyriproxyfen and synergist (e.g., piperonyl butoxide) collectively occupy a

substantial portion of the pesticide formulation on a weight by volume (g/L)

basis. In the context of liquid pesticide formulations, inclusive of

emulsifiable concentrate formulations, for example, "highly loaded" refers

to a concentration level of pyriproxyfen pesticide therein on a weight by

volume basis (g/L) in the amount from at least about 150 g/L.

The term "synergist" as generally used herein refers to an agent

that synergizes the activity of a pesticide or an insecticide, such as an insect growth regulator and hormone mimic like pyriproxyfen. Synergists may include any that are known in the art, such as, for instance, 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,

molluscicidal and vermicidal activity in vitro and/or in vivo, by, for example,

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

(1998); Benchaoui H.A. et al. J. Pharm. Pharmacol. 1996, 48, 753-759;

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

cytochrome P450s.

The addition of a synergist, such as piperonyl butoxide, to the

present pesticide formulation thereby facilitates or potentiates the activity

of pyriproxyfen and thus advantageously increases the biological

effectiveness thereof, while achieving substantial savings on the cost of

the composition formulation. It is understood that whilst piperonyl butoxide

does not have any acaricidal activity per se, when used in conjunction with pyriproxyfen it does slow the affected pest's capacity to degrade and eliminate (that is, metabolise) the pyriproxyfen, thereby amplifying the acaricidal effect of the applied composition, relative to the same amount of pyriproxyfen applied without a synergist such as piperonyl butoxide.

As will be shown herein, it is understood that the emulsifiable

concentrates, dispersible concentrates and highly loaded concentrates of

the present invention are stabilized as a result of the interaction between

the surfactants and solvents present within the formulations. The

surfactant(s) and solvent(s) advantageously and surprisingly provide an

end product that achieves and maintains homogeneity after manufacture

and during storage, even at the equivalent of up to two years of storage

under accelerated conditions, even though the active constituents are at or

near their solubility limits. The term "solvent" in the context of the present

invention is understood to refer to additional solvents added to the

composition (such as methyl benzoate or isophorone). Compositions that

do not have added solvent, referred to as "solvent-less" formulations, may

be stabilised by the interaction between the synergist (such as piperonyl

butoxide) and the surfactant(s), whereby the synergist also at least

partially solubilises the active agent (such as pyriproxyfen). In other words,

in "solvent-less" formulations, the synergist may approximate the action of

a solvent or solvents. It will be appreciated that the term "solvent-free", or

substantially "solvent-free", neglects any minor amounts of solvent that

may be inherently introduced along with the other components of the formulation, such as any solvent that may inherently be included with the surfactant.

The solvent of the pesticide formulations herein, when present, may

comprise one solvent, or they may comprise two or more solvents. When

used, it is understood that at least one of the solvents of the formulation

dissolves at least the pyriproxyfen. In some embodiments, the solvent may

also dissolve the piperonyl butoxide. In some embodiments, the synergist

(such as piperonyl butoxide), alone or in combination with at least one

surfactant, may also act as a solvent and solubilise the pyriproxyfen

loading to produce an emulsifiable concentrate. Each solvent may be

aprotic (i.e., they are unable to donate a hydrogen atom). Each solvent

may be polar or it may be non-polar. In some embodiments, an emulsion

may be formed between a polar solvent and a non-polar solvent. In some

embodiments, additional solvent is not added to the composition as the

synergist also acts as a solvent. Embodiments that comprise only an

active agent (such as pyriproxyfen), a synergist (such as piperonyl

butoxide) and at least one surfactant may be referred to as a "solvent-less"

formulation, due to the absence of additional solvent added.

The surfactant of the pesticide formulations herein may comprise

one surfactant, or they may comprise two or more surfactants. The

surfactant may be an anionic surfactant, or it may be a non-ionic

surfactant. In one embodiment, the surfactant of the present invention may

comprise both an anionic surfactant and a non-ionic surfactant. It is

understood that a surfactant comprises a hydrophobic portion and hydrophilic portion, whereby an anionic surfactant has a negative charge on the hydrophilic portion, and a non-ionic surfactant has no formal charge. Anionic surfactants are regularly obtained as a salt with a metal cation, such as a sodium, potassium or calcium salt. It is expected that any surfactant suitable for use in pesticide formulations may be suitable for use in the formulations of the present invention. Suitable surfactants may be mixtures. They may be proprietary products.

It is envisaged that the pesticide formulation may take the form of

any liquid formulation known in the art. Exemplary liquid formulations

include oil-miscible liquids, soluble concentrates, ultra-low-volume (ULV)

liquids, dispersible concentrates, emulsifiable concentrates, emulsions

including oil-in-water and micro-emulsions, suspension concentrates and

suspoemulsions.

In one particular embodiment, the pesticide formulation is or

comprises an emulsifiable concentrate.

It will be well understood that the term "emulsifiable concentrate

formulation" or "emulsifiable concentrate" (EC) refers to a homogenous

liquid formulation or concentrate of an active agent, such as a pesticide,

which, on dilution in water or a water-containing liquid, forms an emulsion

such as a spontaneous milky white emulsion comprising a dispersed water

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 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.

In another particular embodiment, the pesticide formulation is or

comprises a dispersible concentrate.

It will be well understood that the term "dispersible concentrate

formulation" or "dispersible concentrate" (DC) refers to a homogenous

liquid formulation or concentrate of an active agent, such as a pesticide,

which, on dilution with water or a water-containing liquid, forms a

suspension or a solid dispersion phase within the water-based matrix. In

other words, the active agent, which is in liquid form in the dispersible

concentrate formulation, precipitates on contact with water or water

containing liquids and is dispersed throughout the water-containing phase

as solid particles. By way of example, a water insoluble active ingredient is

typically dissolved in a solvent that may be miscible, or at least partially

miscible, in water, which when in contact with water or the like and

agitated, the solvent mixes and dissolves into the water phase, leaving the

water insoluble active ingredient to contact the water and precipitate as

solid particles. The solid active ingredient may be dispersed in the water

matrix and suspended by action of the surfactant or surfactants also

present in the formulation.

In one aspect, the invention provides a concentrate formulation

comprising: pyriproxyfen at a concentration of at least about 100 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, wherein the concentrate formulation is an emulsifiable concentrate formulation or a dispersible concentrate formulation.

In a related aspect, the invention provides a method of preparing a

pesticide formulation including the steps of:

(a) combining pyriproxyfen, a synergist such as piperonyl butoxide

or an analogue or derivative thereof, a surfactant and optionally a solvent,

wherein pyriproxyfen 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.

The statements which follow apply equally to the aforementioned

aspects of the invention.

For the present invention, pyriproxyfen is suitably present in a

concentration (e.g., at least about 100 g/L) that provides a concentrate

pesticide formulation, such as an emulsifiable concentrate formulation or a

dispersible concentrate, or in a higher concentration (e.g., such as about

300 g/L) that provides a highly loaded pesticide 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

concentrate formulations or dispersible concentrate formulations, or highly

loaded formulations, pyriproxyfen may be present in an amount from about

50 g/L to about 500 g/L or any range therein such as, but not limited to,

about 100 g/L to about 250 g/L, about 150 g/L to about 350 g/L, or about

300 g/L to about 400 g/L of the liquid pesticide formulation. In particular

embodiments of the present invention, pyriproxyfen 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, 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 liquid

pesticide formulation. In certain embodiments of the present invention,

pyriproxyfen is present in an amount of about 100 g/L to about 425 g/L of

the liquid pesticide formulation.

Piperonyl butoxide (PBO) is a well-known insecticide synergist that

can enhance the potency of certain pesticides, such as carbamates,

pyrethrins, pyrethroids, diphenyl oxazolines, insect growth regulators 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 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 synergist activity of PBO.

In relation to liquid pesticide formulations, such as emulsifiable

concentrate formulations, dispersible concentrate formulations or highly

loaded formulations, the synergist (e.g., piperonyl butoxide) may be

present in an amount from about 10 g/L to about 600 g/L or any range

therein such as, but not limited to, about 25 g/L to about 300 g/L, about

100 g/L to about 500 g/L, or about 200 g/L to about 400 g/L of the liquid

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, 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, 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 the liquid pesticide formulation. In certain embodiments of

the present invention, piperonyl butoxide is present in an amount of about

50 g/L to 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. Embodiments comprising at least 150 g/L collectively of pyriproxyfen and synergist (e.g., piperonyl butoxide) may be considered to be highly loaded formulations. The ratio of pyriproxyfen to synergist (e.g., piperonyl butoxide) may be between about 20:1 and about

1:20 or any range therein, such as between 10:1 and 1:1, or between 5:1

and 1:5, or between 2:1 and 1:10, or between 1:1 and 1:15, or it may be

about 20:1, 19:1, 18:1, 17:1, 16:1, 15:1, 14:1, 13:1, 12:1, 11:1, 10:1, 9:1,

8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 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, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16,

1:17, 1:18, 1:19, 1:20 or any range therein in the liquid pesticide

formulation. In certain embodiments of the present invention, the ratio of

pyriproxyfen to synergist (e.g., piperonyl butoxide) may be between 1:5

and 10:1.

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 acetic acid C6-C8 branched 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 of alkyl benzoates (e.g., methyl benzoate, ethyl benzoate), 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 Glysolv PM), methanol, ethanol, isopropanol, decanol and paraffins.

In one particular embodiment, the solvent is selected from the

group consisting of a petroleum derivative, a carboxamide, a benzoate, a

ketone, a glycol ether and any combination thereof. More particularly, the

solvent is selected from the group consisting of a heavy aromatic

hydrocarbon, a pyrrolidone, an alkyl benzoate, an alkyl ketone, a cyclic

ketone, a propylene glycol ether and any combination thereof. Even more

particularly, the solvent is selected from the group consisting of a heavy

aromatic solvent naphtha (petroleum), 1-butylpyrrolidin-2-one, methyl

benzoate, ethyl benzoate, MIBK, isophorone, acetophenone, propylene

glycol monomethyl ether and any combination thereof.

In a particular embodiment, the synergist may also act, alone or in

concert with a surfactant, to solubilise the active ingredient. In other words,

the synergist may also act as a solvent to form a "solvent-less"

emulsifiable concentrate.

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

solvent known in the art.

For the present aspect, the ratio of the first solvent to the second

solvent may suitably be between 1 and 15 parts of the first solvent, and

between 1 and 15 parts of the second solvent. For example, the ratio may

be about 15:1, 14:1, 13:1, 12:1, 11:1, 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 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, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13,

1:14, 1:15 and any range therein. In one preferred embodiment, the ratio

of the first solvent to the second solvent is in the range of about 11:1 to

about 1:11.

For the above aspects, the solvent of a liquid pesticide formulation,

including an emulsifiable concentrate formulation or a dispersible

concentrate formulation or a highly loaded formulation, of the present

invention, may be present in an amount up to about 650 g/L or any range therein such as, but not limited to, about 350 g/L to about 650 g/L, or about 250 g/L to about 550 g/L, or about 100g/L to about 400 g/L, or about

5g/L to about 600 g/L of the liquid pesticide formulation. In particular

embodiments of the present invention, the solvent is present in an amount

ofabout 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60,

65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 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 g/L, or any range 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 250 g/L to about 650 g/L of the liquid pesticide formulation.

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 that is not unacceptably

damaging to a plant and/or its environment, and/or not unsafe to the user

or others that may be exposed to the solvent when used as described

herein.

As used herein, the term "surfactant" or surface-active agent refers

to an agent, usually an organic chemical compound that is at least partially

amphiphilic (i.e., typically containing a hydrophobic tail group and

hydrophilic polar head group). Given their structure, surfactants are generally capable of lowering the surface tension (or interfacial tension) between two liquids or between a liquid and a solid. Further to this, these properties typically allow solubility of the surfactant in organic solvents as well as in water, and allow the surfactant to promote solubilization or at least dispersal of fatty/waxy materials in water and water-containing solutions. In this regard, a surfactant may act as a detergent, a wetting agent, an emulsifying agent, a foaming agent and/or a dispersing agent.

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.

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

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 pyriproxyfen pesticide

formulation, such as an emulsifiable concentrate formulation, or

dispersible concentrate formulation, or a direct use formulation, or a highly

loaded 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., concentrate or highly loaded formulation), the particular active ingredient and/or synergist concentration(s) and the particular surfactant to be included therein.

With regard to liquid pesticide formulations, such as emulsifiable

concentrate formulations or dispersible concentrate formulations or highly

loaded formulations, the surfactant may be present in an amount from

about 20 g/L to about 100 g/L or any range therein such as, but not limited

to, about 25 g/L to about 75 g/L, or about 30 g/L to about 70 g/L 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 g/L, or any range therein, of the liquid pesticide formulation. In

certain embodiments of the present invention, the surfactant is present in

an amount of at least about 45 g/L of the liquid pesticide formulation. More

preferably, the surfactant is present in an amount ranging between about

45 g/L to about 80 g/L of the liquid pesticide 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 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,

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 pesticide formulation, including the emulsifiable

concentrate formulation described herein, the dispersible concentrate

described herein or the highly loaded formulation described herein, may

comprise an anionic surfactant. As generally used herein, the term

"anionic surfactant" refers to a surfactant comprising, as ionic or ionizable

groups, only anionic groups. Such anionic groups may include, for

example, -CO2H, -C2-, -S03H, -SO3-, -OS03H, -OS03-, -H2PO3, -HP03-,

-P03 2-, -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 anionic surfactants. In certain

embodiments, the one or more surfactants to be included in the pesticide

formulation, including the emulsifiable concentrate formulation described herein or the dispersible concentrate formulation described herein, may comprise a non-ionic surfactant. As generally used herein, the term "non ionic surfactant" refers to a surfactant that does not contain or comprise an ionic or ionizable group. Suitable non-ionic surfactants may include those hereinbefore described. Such non-ionic surfactants may be used alone or in combination as a mixture of two, three, four, five or more non-ionic surfactants. In certain embodiments, the surfactant may comprise a combination of one or more anionic surfactant and one or more non-ionic surfactant. In such embodiments, the ratio by weight of total anionic surfactant to total non-ionic surfactant may be between about 20:1 and about 1:20, or between 10:1 and 1:10, or between 15:1 and 1:1, or between 5:1 and 1:15, or between 5:1 and 1:5, or between 3:1 and 1:1, or between 2:1 and 1:2, or between 2:1 and 1:3, or about 1:1 or any range therein, or it may be about 20:1, 19:1, 18:1, 17:1, 16:1, 15:1, 14:1, 13:1,

12:1, 11:1, 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 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,

1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17,

1:18, 1:19, 1:20, or any range therein, in the liquid pesticide formulation.

It will be appreciated that the surfactant may be any suitable

surfactant know in the art. Exemplary surfactants include an alkylphenol

alkoxylate (e.g., Termul 200), a polyoxyalkylene ether (e.g., Termul 203),

an alkoxylated oil (e.g., -54 x ethoxylated (e.g., Termul 1285)), an alkylphenol alkoxylate (e.g., -10 x ethoxylated (e.g., TericNl10)), 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

TAABS-5), a silicone polymer, inclusive of polysiloxanes (e.g., Evonik

Break-Thru OE 446, Evonik Break-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 nonylphenol (e.g., Teric

N10), 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

alcohol ether sulphate, a tallowamine alkoxylated salt, and a mineral oil

(e.g., Rhodoline DF5888).

In particular embodiments, the surfactant is selected from the group

consisting of an alkylphenol alkoxylate (e.g., Termul 200), a

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), a glycol ether (e.g., propylene glycol monomethyl ether) and any combination thereof.

More particularly, the surfactant can be selected from the group

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

EVM70/2E, Kemmat HF60), an ethoxylated tristyryl phenol (e.g., Termul

3150), a propylene glycol ether (e.g., propylene glycol monomethyl ether)

and any combination thereof.

In particular embodiments, the ratio by weight of the total amount of

solvent to the total amount of surfactant may be between about 15:1 and

about 1:1, or between about 10:1 and about 3:1, or between about 10:1

and about 5:1 or any range therein, or it may be about 15:1, 14:1, 13:1,

12:1, 11:1, 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4.9:1, 4.8:1, 4.7:1, 4.6:1, 4.5:1,

4.4:1, 4.3:1, 4.2:1, 4.1:1, 4:1, 3.9:1, 3.8:1, 3.7:1, 3.6:1, 3.5:1, 3.4:1, 3.3:1.

3.2:1, 3.1:1. 3:1, 2:1, 1:1 or any range therein.

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 30 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 pyriproxyfen within the formulation of the invention.

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.

It will be understood that it is desirable for liquid forms of the

pesticide formulation, including the emulsifiable concentrate formulation,

dispersible concentrate formulation or highly loaded 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

temperature (i.e., 20 0C) of no more than 2000 cPs (e.g., 1, 5, 10, 20, 30,

40, 50, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200,

1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000 cPs and any range

therein), as viscosities above this typically make it difficult or impractical to

pump or pour the formulation. Preferably, the liquid pesticide 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 pesticide

formulation of pyriproxyfen, 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.

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

first mentioned aspect or the 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 or the emulsifiable concentrate

pyriproxyfen formulation or the dispersible concentrate pyriproxyfen

formulation or the highly loaded formulation with water or the water

containing liquid.

The terms "treat", "treating" 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

severity of the pest infestation in a target area. In one embodiment,

treatment with the pesticide formulation or the emulsifiable concentrate

formulation, or the dispersible concentrate formulation, or the highly

loaded 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

pesticide formulation 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 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 or the emulsifiable

concentrate formulation 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 pesticide formulation or the

emulsifiable concentrate formulation or the 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 pesticide formulation or the emulsifiable

concentrate formulation or the dispersible concentrate formulation or the

highly loaded formulation against a given 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.

As used herein, the terms "effective amount", "pesticidally effective

amount" and "insecticidally effective amount" refer to an amount of the pesticide formulation or the emulsifiable concentrate formulation 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 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, maturation inhibition and removal, destruction, or otherwise diminishing the occurrence and activity of these unwanted pests. An effective amount of the pesticide formulation or the emulsifiable concentrate formulation, dispersible concentrate formulation or highly loaded 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

pesticide formulation or the emulsifiable concentrate formulation,

dispersible concentrate formulation or highly loaded 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 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 or the emulsifiable

concentrate formulation or dispersible 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 the pesticide formulation or the

emulsifiable concentrate formulation 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 pesticide

formulation or the emulsifiable concentrate formulation, dispersible

concentrate formulation or highly loaded 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 a pesticide formulation or an emulsifiable

concentrate formulation or dispersible concentrate formulation or highly

loaded formulation comprising pyriproxyfen 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

pesticide formulation or the emulsifiable concentrate formulation or

dispersible concentrate formulation or the highly loaded 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

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,

bruchids, fleas, mealybugs, midges, thrips, weevils, butterflies, mosquitos

and cockroaches, which can cause significant damage to, for example, a

wide range of agricultural and horticultural crops and plants, or can be

pests of significance to public health.

In specific embodiments, the pest or pest infestation to be targeted,

prevented and/or controlled by the method for the present aspect are

pests relevant to public health, such as flies, beetles, midges, mosquitos

or which are agricultural pests, such as whitefly, scale and thrips.

The pesticide formulation or the emulsifiable concentrate

formulation or dispersible concentrate formulation or highly loaded

concentrate of the invention may be applied to the target crop or plant, or

to the breeding sites of interest (such as swamps or livestock housing), to

a part thereof, or to surroundings thereof. Methods and techniques for

applying the pesticide formulation or the emulsifiable concentrate

formulation or the dispersible concentrate or the highly loaded formulation

are known in the art and may include, for example, ground or aerial

spraying.

In one embodiment, liquid forms of the pesticide formulation or the

emulsifiable concentrate formulation or dispersible concentrate formulation

or the highly loaded formulation are applied at a rate of about 250 to

3750mL per hectare (e.g., about 250mL, 255mL, 260mL, 265mL, 270mL,

275mL, 280mL, 285mL, 290mL, 295mL, 300mL, 305mL, 310mL, 315mL,

320mL, 325mL, 330mL, 335mL, 340mL, 345mL, 350mL, 355mL, 360mL,

365mL, 370mL, 375mL, 380mL, 385mL, 390mL, 395mL, 400mL, 405mL,

410mL, 415mL, 420mL, 425mL, 430mL, 435mL, 440mL, 445mL, 450mL,

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

500mL, 510mL, 520mL, 530mL, 540mL, 550mL, 560mL, 570mL, 580mL,

590mL, 600mL, 620mL, 640mL, 660mL, 680mL, 700mL, 720mL, 740mL,

760mL, 780mL, 800mL, 820mL, 840mL, 860mL, 880mL, 900mL, 920mL,

940mL, 960mL, 980mL, 10OOmL, 1025mL, 1050mL, 1075mL, 11OOmL,

1150mL, 1200mL, 1250mL, 1300mL, 1400mL, 1500mL, 1600mL,

1700mL, 1800mL, 1900mL, 2000mL, 21OOmL, 2200mL, 2300mL,

2400mL, 2500mL, 2600mL, 2700mL, 2800mL, 2900mL, 3000mL,

31OOmL, 3200mL, 3300mL, 3400mL, 3500mL, 3600mL, 3700mL, 3750mL

per hectare and any range therein) and more preferably at a rate of about

250mL to about 11OOmL per hectare subsequent to dilution thereof in a

suitable spray liquid. Obviously, the amount of the pesticide formulation or

the emulsifiable concentrate or the dispersible concentrate or highly

loaded formulation to be applied per hectare will depend, at least in part,

upon the concentration of pyriproxyfen therein, the particular pest infestation to be targeted and the type of target crop or breeding site to which the formulation is to be applied.

Throughout the specification the aim has been to describe the

preferred embodiments of the invention without limiting the invention to

any one embodiment or specific collection of features. It will therefore be

appreciated by those of skill in the art that, in light of the instant disclosure,

various modifications and changes can be made in the particular

embodiments exemplified without departing from the scope of the present

invention.

With respect to the terms "comprising", "consisting of', and

"consisting essentially of", where one of these three terms is used herein,

the presently disclosed and claimed subject matter may include the use of

either of the other two terms. Thus, in some embodiments not otherwise

explicitly recited, any instance of "comprising" may be replaced by

"consisting of' or, alternatively, by "consisting essentially of'.

In the foregoing paragraphs, various ratios of components have

been disclosed. It will be appreciated that the following ratios of

components can be combined in any disclosed combination, namely:

• the ratio of pyriproxyfen to piperonyl butoxide may be between

about 20:1 and about 1:20 or any range therein, and

• the ratio of the first solvent to the second solvent (when present)

may be between about 3:1 and about 1:3 or any range therein, and

* the ratio of the total anionic surfactant to total non-ionic surfactant

may be between about 20:1 and about 1:20 or any range therein,

and

• the ratio by weight of the total amount of solvent (when present) to

the total amount of surfactant may be between about 15:1 and

about 1:1 or any range therein.

Any reference to publications cited in this specification is not an

admission that the disclosures constitute common general knowledge in

Australia.

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.

Example 1: Embodiments of a Pyriproxyfen Emulsifiable

Concentrate and Dispersible Concentrate Formulations

A number of embodiments of emulsifiable concentrate formulations,

dispersible concentrate formulations, or highly loaded formulations across

a range of pyriproxyfen concentrations, a range of overall pyriproxyfen and

piperonyl butoxide concentrations/proportions, and a range of solvents

and surfactants are provided below.

Embodiment 1 - Recipe for an emulsifiable concentrate combining 350g/L

Pyriproxyfen and 50g/L Piperonyl Butoxide. The concentrate is produced

as below in Table 1 and, as shown in Table 2, has been determined via assay as having: 1) adequate active ingredient concentration, even after accelerated aging; 2) acceptable emulsion properties upon dilution in water prior to application; and 3) physical and chemical stability (including at cold temperatures of 2°C for 7 days), at the point of manufacturing and again after accelerated aging to approximately two years of shelf life.

Composition of embodiment 1 is as follows in Table 1:

Table 1:

Ingredient Role Concentration Pyriproxyfen Active 361.1g/L (CAS# 95737-68-1, Technical material, insecticidal (yields 359.3g/L 99.5%) ingredient Pyriproxyfen) Piperonyl butoxide Insecticidal 52.9g/L (CAS# 51-03-6, Technical material, synergist (yields 48.7g/L 92.0%) Piperonyl butoxide) Alkoxylated alkylphenol Surfactant 30.0g/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Alkyl polyoxyalkylene ether Surfactant 10.2g/L (CAS# Proprietary, e.g. Termul 203) Alkylbenzenesulfonic acid, calcium salt in Surfactant 30.0g/L 2-ethylhexanol (CAS# 68584-23-6, 104 76-7, e.g. Ninate 60E) Solvent naphtha (petroleum), heavy Solvent 509.9g/L aromatic (to 994g/L total) (CAS# 64742-94-5, e.g. Recosol 150)

Chemical and physical parameters of embodiment 1 is as follows in Table

2:

Table 2:

Test As manufactured Accelerated Aged Result Presentation Clear, brown Clear, brown coloured liquid coloured liquid Assay: 360.4g/L 361.9g/L Require 333g/L Pyriproxyfen 367g/L Assay: 48.9g/L 48.0g/L Require 45g/L ! Piperonyl butoxide 55g/L pH1% 7.1 6.7 Nominally: 5.5 to 9.5 Persistent foaming 1mL 6mL Require: 60mL foam after 1 min Emulsion characteristics No cream; Trace of cream; Require: 2mL 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

Embodiment 2 - Recipe for an emulsifiable concentrate combining 300g/L

Pyriproxyfen and 300g/L Piperonyl Butoxide. The concentrate is produced

as below in Table 3 and, as shown in Table 4, has been determined via

assay as having: 1) adequate active ingredient concentration, even after

accelerated aging; 2) acceptable emulsion and dispersion properties upon

dilution in water prior to application; and 3) physical and chemical stability

(including at cold temperatures of 2 0C for 7 days), at the point of

manufacturing and again after accelerated aging to approximate two years

of shelf life.

Composition of embodiment 2 is as follows in Table 3:

Table 3:

Ingredient Role Concentration Pyriproxyfen Active 303.4g/L (CAS# 95737-68-1, Technical material, insecticidal (yields 301.9g/L 99.5%) ingredient Pyriproxyfen) Piperonyl butoxide Insecticidal 326.0g/L (CAS# 51-03-6, Technical material, 92.0%) synergist (yields 299.9g/L Piperonyl butoxide) Alkoxylated alkylphenol Surfactant 30.0g/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Alkyl polyoxyalkylene ether Surfactant 10.0g/L (CAS# Proprietary, e.g. Termul 203) Alkylbenzenesulfonic acid, calcium salt in Surfactant 30.1g/L 2-ethylhexanol (CAS# 68584-23-6, 104-76 7, e.g. Ninate 60E) Methyl benzoate Solvent 403.9g/L (CAS# 93-58-3) (to 1103g/L total)

Chemical and physical parameters of embodiment 2 is as follows in Table

4:

Table 4:

Test As Accelerated Aged manufactured Result Presentation Clear, brown Clear, brown coloured liquid coloured liquid Assay: 297.1g/L 295.2g/L Require 285g/L Pyriproxyfen 315g/L Assay: 297.4g/L 296.9g/L Require 285g/L Piperonyl butoxide 315g/L pH1% 7.0 6.9 Nominally: 5.5 to 9.5 Persistent foaming 9mL 5mL Require: 60mL foam after 1 min Emulsion characteristics Trace of cream; No cream; Require: 2mL cream after 30 min, No oil; No oil; trace of oil after 30 min and complete Re- Re-emulsifies/24h re-emulsion after 24h emulsifies/24h

Embodiment 3 - Recipe for an emulsifiable concentrate combining 300g/L

Pyriproxyfen and 300g/L Piperonyl Butoxide. The concentrate is produced

as below in Table 5 and, as shown in Table 6, has been determined via

assay as having: 1) adequate active ingredient concentration, even after

accelerated aging; 2) acceptable emulsion and dispersion properties upon

dilution in water prior to application; and 3) physical and chemical stability

(including at cold temperatures of 2°C for 7 days), at the point of

manufacturing and again after accelerated aging to approximate two years

of shelf life.

Composition of embodiment 3 is as follows in Table 5:

Table 5:

Ingredient Role Concentration Pyriproxyfen Active 303.6g/L (CAS# 95737-68-1, Technical material, insecticidal (yields 302.1g/L 99.5%) ingredient Pyriproxyfen) Piperonyl butoxide Insecticidal 326.1g/L (CAS# 51-03-6, Technical material, 92.0%) synergist (yields 300.0g/L Piperonyl butoxide) Alkoxylated alkylphenol Surfactant 29.9g/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Alkyl polyoxyalkylene ether Surfactant 10.Og/L (CAS# Proprietary, e.g. Termul 203) Alkylbenzenesulfonic acid, calcium salt in Surfactant 30.1g/L 2-ethylhexanol (CAS# 68584-23-6, 104-76 7, e.g. Ninate 60E) Ethyl benzoate Solvent 388.7g/L (CAS# 93-89-0) (to 1088g/L total)

Chemical and physical parameters of embodiment 3 is as follows in Table

6:

Table 6:

Test As Accelerated Aged manufactured Result Presentation Clear, brown Clear, brown coloured liquid coloured liquid Assay: 299.8g/L 297.4g/L Require 285g/L Pyriproxyfen 315g/L Assay: 303.6g/L 299.3g/L Require 285g/L Piperonyl butoxide 315g/L pH1% 6.7 7.1 Nominally: 5.5 to 9.5 Persistent foaming 11mL 12mL Require: 60mL foam after 1 min Emulsion characteristics Trace of cream; Trace of cream; Require: 2mL cream after 30 min, No oil; No oil; ;trace of oil after 30 min and complete Re- Re-emulsifies/24h re-emulsion after 24h emulsifies/24h

Embodiment 4 - Recipe for an emulsifiable concentrate combining 300g/L

Pyriproxyfen and 300g/L Piperonyl Butoxide. The concentrate is produced

as below in Table 7 and, as shown in Table 8, has been determined via

assay as having: 1) adequate active ingredient concentration, even after

accelerated aging; 2) acceptable emulsion and dispersion properties upon

dilution in water prior to application; and 3) physical and chemical stability

(including at cold temperatures of 2°C for 7 days), at the point of

manufacturing and again after accelerated aging to approximate two years

of shelf life.

Composition of embodiment 4 is as follows in Table 7:

Table 7:

Ingredient Role Concentration Pyriproxyfen Active 308.9g/L (CAS# 95737-68-1, Technical material, insecticidal (yields 307.4g/L 99.5%) ingredient Pyriproxyfen) Piperonyl butoxide Insecticidal 319.2g/L (CAS# 51-03-6, Technical material, 92.0%) synergist (yields 293.7g/L Piperonyl butoxide) Alkoxylated alkylphenol Surfactant 30.0g/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Alkyl polyoxyalkylene ether Surfactant 10.1g/L (CAS# Proprietary, e.g. Termul 203) Alkylbenzenesulfonic acid, calcium salt in Surfactant 30.4g/L 2-ethylhexanol (CAS# 68584-23-6, 104-76 7, e.g. Ninate 60E) Acetophenone Solvent 375.4g/L (CAS# 98-86-2) (to 1074g/L total)

Chemical and physical parameters of embodiment 4 is as follows in Table

8:

Table 8:

Test As Accelerated manufactured Aged Result Presentation Clear, brown Clear, brown coloured liquid coloured liquid Assay: 303.5g/L 307.1g/L Require 285g/L Pyriproxyfen 315g/L Assay: 291.0g/L 292.0g/L Require 285g/L Piperonyl butoxide 315g/L pH1% 7.1 6.8 Nominally: 5.5 to 9.5 Persistent foaming 7mL 12mL Require: 60mL foam after 1 min Emulsion characteristics No cream; Trace of cream; Require: 2mL cream after 30 min, trace No oil; No oil; of oil after 30 min and complete re- Re- Re emulsion after 24h emulsifies/24h emulsifies/24h

Embodiment 5 - Recipe for an emulsifiable concentrate combining 300g/L

Pyriproxyfen and 300g/L Piperonyl Butoxide. The concentrate is produced

as below in Table 9 and, as shown in Table 10, has been determined as

having: 1) adequate active ingredient concentration, even after

accelerated aging; 2) acceptable emulsion and dispersion properties upon

dilution in water prior to application; and 3) physical and chemical stability

(including at cold temperatures of 2°C for 7 days), at the point of

manufacturing and again after accelerated aging to approximate two years

of shelf life.

Composition of embodiment 5 is as follows in Table 9:

Table 9:

Ingredient Role Concentration Pyriproxyfen Active 303.6g/L (CAS# 95737-68-1, Technical material, insecticidal (yields 302.1g/L 99.5%) ingredient Pyriproxyfen) Piperonyl butoxide Insecticidal 326.4g/L (CAS# 51-03-6, Technical material, synergist (yields 300.3g/L 92.0%) Piperonyl butoxide) Ethyl benzoate Solvent 187.3g/L (CAS# 93-89-0) Alkoxylated alkylphenol Surfactant 30.1g/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Alkyl polyoxyalkylene ether Surfactant 10.2g/L (CAS# Proprietary, e.g. Termul 203) Alkylbenzenesulfonic acid, calcium salt Surfactant 30.0g/L in 2-ethylhexanol (CAS# 68584-23-6, 104-76-7, e.g. Ninate 60E) Acetophenone Solvent 196.1g/L (CAS# 98-86-2) (to 1084g/L total)

Chemical and physical parameters of embodiment 5 is as follows in Table

10:

Table 10:

Test As manufactured Accelerated Aged Result Presentation Clear, brown Clear, brown coloured liquid coloured liquid Assay: 301.2g/L 301.6g/L Require 285g/L Pyriproxyfen 315g/L Assay: 307.8g/L 302.2g/L Require 285g/L ! Piperonyl butoxide 315g/L pH1% 6.8 6.85 Nominally: 5.5 to 9.5 Persistent foaming 9mL 14mL Require: 60mL foam after 1 min Emulsion characteristics Trace of cream; Trace of cream; Require: 2mL cream after 30 min, No oil; No oil; <trace of oil after 30 min and complete Re-emulsifies/24h Re re-emulsion after 24h emulsifies/24h

Embodiment 6 - Recipe for an emulsifiable concentrate combining 300g/L

Pyriproxyfen and 300g/L Piperonyl Butoxide. The concentrate is produced

as below in Table 11 and, as shown in Table 12, has been determined via

assay as having: 1) adequate active ingredient concentration, even after

accelerated aging; 2) acceptable emulsion and dispersion properties upon

dilution in water prior to application; and 3) physical and chemical stability

(including at cold temperatures of 2 0C for 7 days), at the point of

manufacturing and again after accelerated aging to approximate two years

of shelf life.

Composition of embodiment 6 is as follows in Table 11:

Table 11:

Ingredient Role Concentration Pyriproxyfen Active 303.0g/L (CAS# 95737-68-1, Technical material, insecticidal (yields 301.5g/L 99.5%) ingredient Pyriproxyfen) Piperonyl butoxide Insecticidal 326.0g/L (CAS# 51-03-6, Technical material, synergist (yields 299.9g/L 92.0%) Piperonyl butoxide) 1-Butylpyrrolidin-2-one Solvent 112.4g/L (CAS# 3470-98-2, e.g. Genagen NBP) Alkoxylated alkylphenol Surfactant 30.4g/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Alkyl polyoxyalkylene ether Surfactant 10.0g/L (CAS# Proprietary, e.g. Termul 203) Alkylbenzenesulfonic acid, calcium salt in Surfactant 30.2g/L 2-ethylhexanol (CAS# 68584-23-6, 104 76-7, e.g. Ninate 60E) Acetophenone Solvent 262.4g/L (CAS# 98-86-2) (to 1074g/L total)

Chemical and physical parameters of embodiment 6 is as follows in Table

12:

Table 12:

Test As Accelerated Aged manufactured Result Presentation Clear, brown Clear, brown coloured liquid coloured liquid Assay: 295.4g/L 299.3g/L Require 285g/L Pyriproxyfen 315g/L Assay: 300.8g/L 301.0g/L Require 285g/L Piperonyl butoxide 315g/L plH1% 6.9 7.0 Nominally: 5.5 to 9.5 Persistent foaming 8mL 14mL Require: 60mL foam after 1 min Emulsion characteristics Trace of cream; Trace of cream; Require: 2mL cream after 30 min, No oil; No oil; trace of oil after 30 min and complete Re- Re-emulsifies/24h re-emulsion after 24h emulsifies/24h

Embodiment 7 - Recipe for an emulsifiable concentrate combining 200g/L

Pyriproxyfen and 500g/L Piperonyl Butoxide. The concentrate is produced

as below in Table 13 and, as shown in Table 14, has been determined via

assay as having: 1) adequate active ingredient concentration, even after

accelerated aging; 2) acceptable emulsion and dispersion properties upon

dilution in water prior to application; and 3) physical and chemical stability

(including at cold temperatures of 2°C for 7 days), at the point of

manufacturing and again after accelerated aging to approximate two years

of shelf life.

Composition of embodiment 7 is as follows in Table 13:

Table 13:

Ingredient Role Concentration Pyriproxyfen Active 205.9g/L (CAS# 95737-68-1, Technical material, insecticidal (yields 204.9g/L 99.5%) ingredient Pyriproxyfen) Piperonyl butoxide Insecticidal 532.1g/L (CAS# 51-03-6, Technical material, 92.0%) synergist (yields 489.5g/L Piperonyl butoxide) Alkoxylated alkylphenol Surfactant 37.Og/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Alkyl polyoxyalkylene ether Surfactant 10.5g/L (CAS# Proprietary, e.g. Termul 203) Alkylbenzenesulfonic acid, calcium salt in 2- Surfactant 30.1g/L ethylhexanol (CAS# 68584-23-6, 104-76-7, e.g. Ninate 60E) Acetophenone Solvent 253.0g/L (CAS# 98-86-2) (to 1069g/L total)

Chemical and physical parameters of embodiment 7 is as follows in Table

14:

Table 14:

Test As manufactured Accelerated Aged Result Presentation Clear, brown Clear, brown coloured liquid coloured liquid Assay: 203.4g/L 203.8g/L Require 188g/L Pyriproxyfen 212g/L Assay: 487.6g/L 490.3g/L Require 475g/L Piperonyl butoxide 525g/L pH1% 7.1 6.7 Nominally: 5.5 to 9.5 Persistent foaming 9mL 11mL Require: 60mL foam after 1 min Emulsion characteristics Trace of cream; Trace of cream; Require: 2mL 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

Embodiment 8 - Recipe for an emulsifiable concentrate combining 200g/L

Pyriproxyfen and 500g/L Piperonyl Butoxide. The concentrate is produced

as below in Table 15 and, as shown in Table 16, has been determined via

assay as having: 1) adequate active ingredient concentration, even after

accelerated aging; 2) acceptable emulsion and dispersion properties upon

dilution in water prior to application; and 3) physical and chemical stability

(including at cold temperatures of 2°C for 7 days), at the point of

manufacturing and again after accelerated aging to approximate two years

of shelf life.

Composition of embodiment 8 is as follows in Table 15:

Table 15:

Ingredient Role Concentration Pyriproxyfen Active 206.0g/L (CAS# 95737-68-1, Technical material, insecticidal (yields 205.0g/L 99.5%) ingredient Pyriproxyfen) Piperonyl butoxide Insecticidal 532.0g/L (CAS# 51-03-6, Technical material, 92.0%) synergist (yields 489.4g/L Piperonyl butoxide) Alkoxylated alkylphenol Surfactant 30.6g/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Alkyl polyoxyalkylene ether Surfactant 10.0g/L (CAS# Proprietary, e.g. Termul 203) Alkylbenzenesulfonic acid, calcium salt in Surfactant 30.2g/L 2-ethylhexanol (CAS# 68584-23-6, 104-76 7, e.g. Ninate 60E) Acetophenone Solvent 260.1g/L (CAS# 98-86-2) (to 1069g/L total)

Chemical and physical parameters of embodiment 8 is as follows in Table

16:

Table 16:

Test As Accelerated Aged manufactured Result Presentation Clear, brown Clear, brown coloured liquid coloured liquid Assay: 205.0g/L 203.1g/L Require 188g/L Pyriproxyfen 212g/L Assay: 488.2g/L 487.7g/L Require 475g/L Piperonyl butoxide 525g/L pH1% 7.4 7.0 Nominally: 5.5 to 9.5 Persistent foaming 9mL 10mL Require: 60mL foam after 1 min Emulsion characteristics 0.2mL of 0.2mL of cream; Require: 2mL cream after 30 min, cream; No oil; trace of oil after 30 min and complete No oil; Re-emulsifies/24h re-emulsion after 24h Re Iemulsifies/24h

Embodiment 9 - Recipe for an emulsifiable concentrate combining 1OOg/L

Pyriproxyfen and 250g/L Piperonyl Butoxide. The concentrate is produced

as below in Table 17 and, as shown in Table 18, has been determined via

assay as having: 1) adequate active ingredient concentration, even after

accelerated aging; 2) acceptable emulsion and dispersion properties upon

dilution in water prior to application; and 3) physical and chemical stability

(including at cold temperatures of 2°C for 7 days), at the point of

manufacturing and again after accelerated aging to approximate two years

of shelf life.

Composition for embodiment 8 is as follows in Table 17:

Table 17:

Ingredient Role Concentration Pyriproxyfen Active 103.1g/L (CAS# 95737-68-1, Technical material, insecticidal (yields 102.6g/L 99.5%) ingredient Pyriproxyfen) Piperonyl butoxide Insecticidal 266.2g/L (CAS# 51-03-6, Technical material, 92.0%) synergist (yields 244.9g/L Piperonyl butoxide) Alkoxylated alkylphenol Surfactant 30.Og/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Alkyl polyoxyalkylene ether Surfactant 10.3g/L (CAS# Proprietary, e.g. Termul 203) Alkylbenzenesulfonic acid, calcium salt in Surfactant 30.Og/L 2-ethylhexanol (CAS# 68584-23-6, 104-76 7, e.g. Ninate 60E) Acetophenone Solvent 603.5g/L (CAS# 98-86-2) (to 1043g/L total)

Chemical and physical parameters of embodiment 8 is as follows in Table

18:

Table 18:

Test As Accelerated Aged manufactured Result Presentation Clear, brown Clear, brown coloured liquid coloured liquid Assay: 102.Og/L 104.0g/L Require 90g/L Pyriproxyfen 110g/L Assay: 242.4g/L 245.2g/L Require 235g/L Piperonyl butoxide 265g/L pH1% 7.2 6.8 Nominally: 5.5 to 9.5 Persistent foaming 3mL 9mL Require: 60mL foam after 1 min Emulsion characteristics No cream; Trace of cream; Require: 2mL cream after 30 min, No oil; No oil; trace of oil after 30 min and complete Re- Re-emulsifies/24h re-emulsion after 24h emulsifies/24h . _I

Embodiment 10 - Recipe for a dispersible concentrate combining 1OOg/L

Pyriproxyfen and 400g/L Piperonyl Butoxide. The concentrate is produced

as below in Table 19 and, as shown in Table 20, has been determined via

assay as having: 1) adequate active ingredient concentration, even after

accelerated aging; 2) acceptable emulsion and dispersion properties upon

dilution in water prior to application; and 3) physical and chemical stability

(including at cold temperatures of 2°C for 7 days), at the point of

manufacturing and again after accelerated aging to approximate two years

of shelf life.

Composition of embodiment 10 is as follows in Table 19:

Table 19:

Ingredient Role Concentration Pyriproxyfen Active 103.1g/L (CAS# 95737-68-1, Technical material, insecticidal (yields 102.6g/L 99.5%) ingredient Pyriproxyfen) Piperonyl butoxide Insecticidal 427.2g/L (CAS# 51-03-6, Technical material, 92.0%) synergist (yields 393.0g/L Piperonyl butoxide) Vegetable oil ethoxylate Surfactant 35.6g/L (CAS# 61791-12-6, e.g. Termul 1285) Alkyl polyoxyalkylene ether Surfactant 10.0g/L (CAS# Proprietary, e.g. Termul 203) Propylene glycol monomethyl ether Solvent 429.2g/L (CAS# 107-98-2) (to 1005g/L total)

Chemical and physical parameters of embodiment 10 is as follows in

Table 20:

Table 20:

Test As Accelerated Aged manufactured Result Presentation Clear, brown Clear, brown coloured liquid coloured liquid Assay: 102.8g/L 103.4g/L Require 90g/L Pyriproxyfen 110g/L Assay: 395.6g/L 399.8g/L Require 380g/L Piperonyl butoxide 420g/L pH1% 7.2 6.9 Nominally: 5.5 to 9.5 Persistent foaming 1mL 5mL Require: 60mL foam after 1 min Dispersion stability 2.0mL of 2.0mL of cream; Require: 2mL cream after 30 min, trace cream; No oil; of oil after 30 min and complete re- No oil; Re-emulsifies/24h emulsion after 24h Re emulsifies/24h

Embodiment 11 - Recipe for an emulsifiable concentrate combining

100g/L Pyriproxyfen and 400g/L Piperonyl Butoxide. The concentrate is produced as below in Table 21 and, as shown in Table 22, has been determined via assay as having: 1) adequate active ingredient concentration, even after accelerated aging; 2) acceptable emulsion and dispersion properties upon dilution in water prior to application; and 3) physical and chemical stability (including at cold temperatures of 20C for 7 days), at the point of manufacturing and again after accelerated aging to approximate two years of shelf life.

Composition of embodiment 11 is as follows in Table 21:

Table 21:

Ingredient Role Concentration Pyriproxyfen Active 103.1g/L (CAS# 95737-68-1, Technical material, insecticidal (yields 102.6g/L 99.5%) ingredient Pyriproxyfen) Piperonyl butoxide Insecticidal 437.9g/L (CAS# 51-03-6, Technical material, 92.0%) synergist (yields 402.9g/L Piperonyl butoxide) Alkoxylated alkylphenol Surfactant 39.9g/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Alkylbenzenesulfonic acid, calcium salt in Surfactant 30.2g/L 2-ethylhexanol (CAS# 68584-23-6, 104-76 7, e.g. Ninate 60E) Methyl isobutyl ketone Solvent 348.1g/L (CAS# 108-10-1) (to 959g/L total)

Chemical and physical parameters of embodiment 11 is as follows in

Table 22:

Table 22:

Test As manufactured Accelerated Aged Result Presentation Clear, brown Clear, brown coloured liquid coloured liquid Assay: 104.0g/L 100.5.9g/L Require 90g/L Pyriproxyfen 110g/L Assay: 404.1g/L 409.9g/L Require 380g/L Piperonyl butoxide 420g/L pH1% 7.2 6.9 Nominally: 5.5 to 9.5 Persistent foaming 10mL 14mL Require: 60mL foam after 1 min Emulsion characteristics Trace of cream; Trace of cream; Require: 2mL 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

Embodiment 12 - Recipe for an emulsifiable concentrate combining

100g/L Pyriproxyfen and 400g/L Piperonyl Butoxide. The concentrate is

produced as below in Table 23 and, as shown in Table 24, has been

determined via assay as having: 1) adequate active ingredient

concentration, even after accelerated aging; 2) acceptable emulsion and

dispersion properties upon dilution in water prior to application; and 3)

physical and chemical stability (including at cold temperatures of 20C for 7

days), at the point of manufacturing and again after accelerated aging to

approximate two years of shelf life.

Composition of embodiment 12 is as follows in Table 23:

Table 23:

Ingredient Role Concentration Pyriproxyfen Active 102.8g/L (CAS# 95737-68-1, Technical material, insecticidal (yields 102.3g/L 99.5%) ingredient Pyriproxyfen) Piperonyl butoxide Insecticidal 426.3g/L (CAS# 51-03-6, Technical material, synergist (yields 392.2g/L 92.0%) Piperonyl butoxide) Alkoxylated alkylphenol Surfactant 30.1g/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Tristyrylphenol ethoxylate Surfactant 10.0g/L (CAS# 99734-09-5, e.g. Termul 3150) Alkylbenzenesulfonic acid, calcium salt in Surfactant 30.1g/L 2-ethylhexanol (CAS# 68584-23-6, 104 76-7, e.g. Ninate 60E) Isophorone Solvent 410.4g/L (CAS# 78-59-1) (to 1010g/L total)

Chemical and physical parameters of embodiment 12 is as follows in

Table 24:

Table 24:

Test As Accelerated manufactured Aged Result Presentation Clear, brown Clear, brown coloured liquid coloured liquid Assay: 102.3g/L 100.1g/L Require 90g/L Pyriproxyfen 110g/L Assay: 387.7g/L 387.5g/L Require 380g/L Piperonyl butoxide 420g/L pH1% 7.4 7.0 Nominally: 5.5 to 9.5 Persistent foaming 8mL 11mL Require: 60mL foam after 1 min Emulsion characteristics Trace of Trace of cream; Require: 2mL cream after 30 min, trace cream; No oil; of oil after 30 min and complete re- No oil; Re emulsion after 24h Re- emulsifies/24h emulsifies/24h

Embodiment 13 - Recipe for an emulsifiable concentrate combining

100g/L Pyriproxyfen and 400g/L Piperonyl Butoxide. The concentrate is

produced as below in Table 25 and, as shown in Table 26, has been

determined via assay as having: 1) adequate active ingredient

concentration, even after accelerated aging; 2) acceptable emulsion and

dispersion properties upon dilution in water prior to application; and 3)

physical and chemical stability (including at cold temperatures of 20C for 7

days), at the point of manufacturing and again after accelerated aging to

approximate two years of shelf life.

Composition of embodiment 13 is as follows in Table 25:

Table 25:

Ingredient Role Concentration Pyriproxyfen Active 103.Og/L (CAS# 95737-68-1, Technical material, insecticidal (yields 102.5g/L 99.5%) ingredient Pyriproxyfen) Piperonyl butoxide Insecticidal 426.3g/L (CAS# 51-03-6, Technical material, 92.0%) synergist (yields 392.2g/L Piperonyl butoxide) Alkoxylated alkylphenol Surfactant 30.1g/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Alkyl polyoxyalkylene ether Surfactant 10.Og/L (CAS# Proprietary, e.g. Termul 203) Alkylbenzenesulfonic acid, calcium salt in Surfactant 30.Og/L 2-ethylhexanol (CAS# 68584-23-6, 104-76 7, e.g. Ninate 60E) Acetophenone Solvent 454.7g/L (CAS# 98-86-2) (to 1054g/L total)

Chemical and physical parameters of embodiment 13 is as follows in

Table 26:

Table 26:

Test As manufactured Accelerated Aged Result Presentation Clear, brown Clear, brown coloured liquid coloured liquid Assay: 103.8g/L 102.8g/L Require 90g/L ! Pyriproxyfen ! 110g/L Assay: 391.6g/L 386.9g/L Require 380g/L ! Piperonyl butoxide 420g/L pH1% 7.3 7.0 Nominally: 5.5 to 9.5 Persistent foaming 7mL 7mL Require: 60mL foam after 1 min Emulsion characteristics Trace of cream; Trace of cream; Require: 2mL cream after 30 min, <trace No oil; No oil; of oil after 30 min and complete re- Re- Re emulsion after 24h emulsifies/24h emulsifies/24h

Embodiment 14 - Recipe for a solvent-less emulsifiable concentrate

combining 425g/L Pyriproxyfen and 525g/L Piperonyl Butoxide. The

concentrate is produced as below in Table 27 and, as shown in Table 28,

has been determined via assay as having: 1) adequate active ingredient

concentration, even after accelerated aging; 2) acceptable emulsion and

dispersion properties upon dilution in water prior to application; and 3)

physical and chemical stability (including at cold temperatures of 20 C for 7

days), at the point of manufacturing and again after accelerated aging to

approximate two years of shelf life.

Composition of embodiment 14 is as follows in Table 27:

Table 27:

Ingredient Role Concentration Pyriproxyfen Active 428.5g/L (CAS# 95737-68-1, Technical material, insecticidal (yields 426.4g/L 99.5%) ingredient Pyriproxyfen) Alkoxylated alkylphenol Surfactant 39.6g/L (CAS# 37251-69-7, e.g. Termul 200, Antarox 724/P) Alkyl polyoxyalkylene ether Surfactant 13.9g/L (CAS# Proprietary, e.g. Termul 203) Alkylbenzenesulfonic acid, calcium salt in 2- Surfactant 40.3g/L ethylhexanol (CAS# 68584-23-6, 104-76-7, e.g. Ninate 60E) Piperonyl butoxide Insecticidal 573.8g/L (CAS# 51-03-6, Technical material, 92.0%) synergist (yields 527.9g/L Piperonyl butoxide) (to 1096g/L total)

Chemical and physical parameters of embodiment 14 is as follows in

Table 28.

Table 28:

Test As manufactured Accelerated Aged Result Presentation Clear, yellow to Clear, yellow to brown liquid brown liquid Assay: 425.0g/L 429.Og/L Require 404g/L Pyriproxyfen 446g/L Assay: 525.0g/L 528.Og/L Require 500g/L Piperonyl butoxide 550g/L pH1% 7.6 7.4 Nominally: 5.5 to 9.5 Persistent foaming 10mL 12mL Require: 60mL foam after 1 min Emulsion characteristics 0.2mL of cream; 0.3mL of cream; Require: 2mL 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

Example 2: Pyriproxyfen 300 g/L + Piperonyl butoxide 300 g/L EC

Raw Material Identities

An example formulation combining 300g/L Pyriproxyfen and 300g/L

Piperonyl Butoxide is provided below in Table 27, which includes the purity

(where known), source and technical details of the components. The

Pyriproxyfen technical and Piperonyl Butoxide technical are the same as

that used in the formulations of Example 1.

0~ 6t 6) C 6Y) C) CN C0 co_ Cl) CO~

E

00- 0000 ON CUC 0 0 U) U).n

Oc C N- C: C0 a)0 0) U)0) ) co 751 0) C C < >) 0 0 ~ C 0)C CN 2-. (N LOU C: 0)r- 0 r- 0 00 0. coCe) 0 (0 0 NCU~oU U) mU U)O 5 0. C: - CN CU0 a) E 0< Eun 0< C: m 000 0 E -U -b C -V w c A ) 0-W CU) UCO C: C) C C C)U a) =3 c C) ca U- E 0)c) ) c) C) -U CE .0 a~C LO) 0) CN c LO

Ue) 0 a) mE-- CC U 1 U () C O- >C) ~E E EEEE m 0 ) (UVC C- C0) CUV01) CV1 CU 0. co C1)n-FTt 0 0 - Co~C C NC-e C-e C- - I~ IC >< C O- mUUC mU mE a) E CU

x~ 0 a)

0 0 zc z z =3) 0 N ~ (1) (1, ccac 0 nm o c o a 4-1 W- W-~ 0 3 Ni ---0 c 3= C- Z c 0 mC 2 M c

0c a) -- C

C ____ _ _ _m_ C_

Example 3: Method of Manufacture of Pyriproxyfen Emulsifiable

Concentrate Formulation

Formulation of a 1,000L batch of product, inclusive of quality control

measures, is as follows:

Formulation Procedure

1. Ensure formulation vessel is empty and clean

2. Charge solvent component(s), holding a small proportion back (e.g.

-10%) for subsequent addition, to the formulation vessel with the

agitator operating

3. Charge active ingredients (pyriproxyfen and synergists, e.g. piperonyl

butoxide) to the formulation vessel with continuous agitation

4. Charge the surfactant(s) and other excipients clearing residual

components from any pumps or process lines used with the remaining

complement of solvent

5. Continue agitating for a minimum of 30 minutes following the last

ingredient's addition

Quality Control Procedure

1. Sample approximately 1L of product, ensuring it is representative

2. Sub-sample 250mL from the original 1L sample, and subject it to the

following testing regime.

2.1. Specific gravity (CIPAC MT3.1)

If specific gravity is within the bounds of the acceptable range listed in

the specification, record the value and proceed to the next test. If

specific gravity is outside of the bounds of the acceptable range listed in the specification, agitate the formulation charge until specific gravity is constant. If still outside of the bounds of the acceptable range, quarantine batch for further investigations and possible rework.

2.2. pH 1% aqueous (CIPAC MT75.3)

If pH 1% aqueous is satifactory, record results and proceed to the next

test. If pH 1% aqueous is outside the bounds of the acceptable range

listed in the specification, quarantine the batch for further

investigations and possible rework.

2.3. Emulsion characteristics (CIPAC MT36.1)

If emulsion stability in standard hard water is satifactory, record results

and proceed to the next test. If emulsion stability is outside the bounds

of the acceptable range listed in the specification, adjust the contents

of surfactants. After suitable agitation time to ensure homogeneity,

resample and retest. Repeat adjustment process until emulsion

stability is within the bounds of the acceptable range.

2.4. Persistent foam (CIPACMT47.2)

If persistent foaming characteristics are satifactory, record results and

proceed to the next test. If persistent foaming characteristics are

outside the bounds of the acceptable range quarantine the batch for

further investigations and possible rework.

2.5. Active constituent (pyriproxyfen) content (appropriately

validated method: specificity; linearity of response with correlation

coefficient R>0.99; accuracy of mean measured assay as a proportion of true content 100±2%; reproducibility of response 2% relative standard deviation).

If active constituent level is satifactory, record results. If active

constituent level is outside the bounds of the acceptable range listed in

the specification, adjust the level accordingly by adding additional

solvent and/or surfactants and/or other excipients (for a high active

constituent content), or additional pyriproxyfen technical (for a low

active content). After suitable agitation time to ensure homogeneity,

resample and retest. Repeat adjustment process until active

constituent levels are within the bounds of the acceptable range.

2.6. Active constituent (synergist, e.g. Piperonyl butoxide) content

(appropriately validated method: specificity; linearity of response with

correlation coefficient R>0.99; accuracy of mean measured assay as a

proportion of true content 100±2%; reproducibility of response 2%

relative standard deviation).

If active constituent level is satifactory, record results. If active

constituent level is outside the bounds of the acceptable range listed in

the specification, adjust the level accordingly by adding additional

solvent and/or surfactants and/or other excipients (for a high active

constituent content), or additional synergist (for a low active

constituent content). After suitable agitation time to ensure

homogeneity, resample and retest. Repeat adjustment process until

active constituent levels are within the bounds of the acceptable

range.

3. Catalogue and store a retention sample of approximately 200mL

4. Generate a certificate of analysis noting results of testing

5. Issue quality clearance giving authority to package goods

6. Package the finished goods ensuring both the batch number and

manufacturing date is noted on the label.

Example 4: Method of Manufacture of Pyriproxyfen Dispersible

Concentrate Formulation

Formulation of a 1,000L batch of product, inclusive of quality control

measures, is as follows:

Formulation Procedure

1. Ensure formulation vessel is empty and clean

2. Charge solvent component(s), holding a small proportion back (e.g.

-10%) for subsequent addition, to the formulation vessel with the

agitator operating

3. Charge active ingredients (pyriproxyfen and synergist, e.g. piperonyl

butoxide) to the formulation vessel with continuous agitation

4. Charge the surfactant(s) and other excipients clearing residual

components from any pumps or process lines used with the remaining

complement of solvent

5. Continue agitating for a minimum of 30 minutes following the last

ingredient's addition

Quality Control Procedure

1. Sample approximately 1L of product, ensuring it is representative

2. Sub-sample 250mL from the original 1L sample, and subject it to the

following testing regime.

2.1. Specific gravity (CIPAC MT3.1)

If specific gravity is within the bounds of the acceptable range listed in

the specification, record the value and proceed to the next test. If

specific gravity is outside of the bounds of the acceptable range listed

in the specification, agitate the formulation charge until specific gravity

is constant. If still outside of the bounds of the acceptable range,

quarantine batch for further investigations and possible rework.

2.2. pH 1% aqueous (CIPAC MT75.3)

If pH 1% aqueous is satifactory, record results and proceed to the next

test. If pH 1% aqueous is outside the bounds of the acceptable range

listed in the specification, quarantine the batch for further

investigations and possible rework.

2.3. Dispersion stability (CIPAC MT180)

If dispersion stability in standard hard water is satifactory, record

results and proceed to the next test. If dispersion stability is outside

the bounds of the acceptable range listed in the specification, adjust

the contents of surfactants. After suitable agitation time to ensure

homogeneity, resample and retest. Repeat adjustment process until

dispersion stability is within the bounds of the acceptable range.

2.4. Persistent foam (CIPACMT47.2)

If persistent foaming characteristics are satifactory, record results and

proceed to the next test. If persistent foaming characteristics are outside the bounds of the acceptable range quarantine the batch for further investigations and possible rework.

2.5. Active constituent (pyriproxyfen) content (appropriately

validated method: specificity; linearity of response with correlation

coefficient R>0.99; accuracy of mean measured assay as a proportion

of true content 100±2%; reproducibility of response 2% relative

standard deviation).

If active constituent level is satifactory, record results. If active

constituent level is outside the bounds of the acceptable range listed in

the specification, adjust the level accordingly by adding additional

solvent and/or surfactants and/or other excipients (for a high active

constituent content), or additional pyriproxyfen technical (for a low

active content). After suitable agitation time to ensure homogeneity,

resample and retest. Repeat adjustment process until active

constituent levels are within the bounds of the acceptable range.

2.6. Active constituent (Synergist, e.g. Piperonyl butoxide) content

(appropriately validated method: specificity; linearity of response with

correlation coefficient R>0.99; accuracy of mean measured assay as a

proportion of true content 100±2%; reproducibility of response 2%

relative standard deviation).

If active constituent level is satifactory, record results. If active

constituent level is outside the bounds of the acceptable range listed in

the specification, adjust the level accordingly by adding additional

solvent and/or surfactants and/or other excipients (for a high active constituent content), or additional Synergist (for a low active constituent content). After suitable agitation time to ensure homogeneity, resample and retest. Repeat adjustment process until active constituent levels are within the bounds of the acceptable range.

3. Catalogue and store a retention sample of approximately 200mL

4. Generate a certificate of analysis noting results of testing

5. Issue quality clearance giving authority to package goods

6. Package the finished goods ensuring both the batch number and

manufacturing date is noted on the label.

Claims (18)

1. A pesticide formulation comprising:

pyriproxyfen;

a synergist;

a surfactant; and

optionally, a solvent.

2. A concentrate formulation comprising:

pyriproxyfen 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,

wherein the concentrate formulation is an emulsifiable concentrate

formulation or a dispersible concentrate formulation.

3. The concentrate formulation of Claim 2, comprising:

pyriproxyfen at a concentration of at least about 300 g/L;

piperonyl butoxide at a concentration of at least about 50 g/L;

a non-ionic surfactant and/or an anionic surfactant; and

a solvent.

4. The concentrate formulation of Claims 2 or Claim 3, wherein the

surfactant is present in an amount of at least about 40 g/L.

5. The concentrate formulation of Claim 4, wherein the surfactant is

present in an amount ranging between about 40 g/L to about 80 g/L.

6. The concentrate formulation of any one of Claims 2 to 5, wherein

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

polyoxyalkylene ether, an alkylbenzene sulphonate, an alkoxylated styryl

phenol, an oil ethoxylate and any combination thereof.

7. The concentrate formulation of Claim 6, 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, a vegetable oil ethoxylate and any

combination thereof.

8. The concentrate formulation of any one of Claims 2 to 7, wherein

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

9. The concentrate formulation of Claim 8, wherein the solvent is

present in an amount ranging between about 250 g/L to about 600 g/L.

10. The concentrate formulation of any one of Claims 2 to 9, wherein

the solvent is selected from the group consisting of a petroleum derivative,

a carboxamide, a benzoate, a ketone, a glycol ether and any combination thereof.

11. The concentrate formulation of Claim 10, wherein the solvent is

selected from the group consisting of a heavy aromatic hydrocarbon, a

pyrrolidone, an alkyl benzoate, an alkyl ketone, a cyclic ketone, a

propylene glycol ether and any combination thereof.

12. The concentrate formulation of Claim 10 or Claim 11, wherein the

solvent is selected from the group consisting of a heavy aromatic solvent

naphtha (petroleum), 1-Butylpyrrolidin-2-one, methyl benzoate, ethyl

benzoate, MIBK, isophorone, acetophenone, propylene glycol monomethyl

ether and any combination thereof.

13. The emulsifiable concentrate of claim 2, wherein the solvent

comprises methyl benzoate.

14. An emulsifiable concentrate, comprising:

pyriproxyfen at a concentration of at least about 300 g/L;

piperonyl butoxide at a concentration of at least about 50 g/L;

a non-ionic surfactant comprising an alkyl polyoxyalkylene ether

and an alkoxylated alkylphenol;

an anionic surfactant comprising a calcium salt of an alkylbenzene

sulfonate; and

a solvent comprising methyl benzoate.

15. A method of preparing a pesticide formulation including the steps

of:

(a) combining pyriproxyfen, a synergist such as piperonyl butoxide,

a surfactant and optionally a solvent, wherein pyriproxyfen is present at a

concentration of at least 100 mg/L; and

(b) mixing the mixture of step (a) to thereby prepare the pesticide

formulation.

16. The method of Claim 15, wherein the pesticide formulation is the

concentrate formulation of any one of Claims 2 to 14.

17. A pesticide formulation prepared by the method of Claim 15 or

Claim 16.

18. 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 Claim 1 or Claim 17 or the concentrate

formulation of any one of Claims 2 to 14 mixed with water or a water

containing liquid, to the target area to thereby prevent and/or control the

pest infestation.