AU2021105351A4 - Pesticide formulation comprising deltamethrin - Google Patents

Abstract

The present invention provides a pesticide formulation comprising deltamethrin, piperonyl butoxide, a non-ionic surfactant and an anionic surfactant and a solvent, wherein the solvent comprises methyl salicylate 5 which is present in an amount of at least 150 g/L of the total volume of the formulation, as well as methods for producing a pesticide formulation and methods of using a pesticide formulation to prevent or treat a pest infestation.

Description

PESTICIDE FORMULATION COMPRISING DELTAMETHRIN FIELD OF THE INVENTION

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

present invention relates to a pesticide formulation containing deltamethrin

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

preparing and using said formulation. In preferred embodiments, the

formulation is a concentrate for dilution and subsequent application to

stored grains as a protectant against insecticidal attack. However, it will be

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

BACKGROUND TO THE INVENTION

Deltamethrin is a member of the pyrethroid class of insecticides. Like

all pyrethroids, it is a sodium channel antagonist with fast-acting, non

systemic contact and stomach activity. It is known to be effective against

agricultural pests in cereals and a wide range of various foliar crops, such

as citrus, vines, and vegetables, and soil surface spraying can protect

against Noctuidae species. It is also used in industrial and veterinary

settings to control, for example, flies, crawling insects and flying insects in

indoor settings, pests in stored grains and timber, and ectoparasites and

pests that effect agricultural animals when prepared as a dip or spray-on

formulation.

Deltamethrin is the compound (S)-a-cyano-phenoxybenzyl (1R,3R)

3-(2,2-dibromovinyl)-2,2-dimethylcyclopropanecarboxylate. It is commonly

used to control Coleoptera, Heteroptera, Homoptera, Lepidoptera and

Thysanoptera spp. in cereals (including stored grains) and other crops, as well as Blattodea, Culicidae and Muscidae in stored timber. It is especially preferred for controlling Acrididae and Noctuidae spp. It can also be used to control Muscidae, Tabanidae, Ixodidae and Acari spp in animals such as cattle, sheep and pigs. It is commonly used to control pests on a wide variety of agriculturally relevant crops.

It is a known problem that insecticides such as deltamethrin, 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 deltamethrin with other active ingredients.

However, the efficacy of such combinations 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 a pesticide

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

deltamethrin formulations, there remains a need for improved deltamethrin

based formulations for use in agriculture and/or industry that overcomes one

or more of the inherent limitations of commercially available deltamethrin

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.

SUMMARY OF THE INVENTION

In a first aspect, the invention provides a pesticide formulation

comprising:

deltamethrin;

piperonyl butoxide;

a non-ionic surfactant and an anionic surfactant; and

a solvent,

wherein the solvent comprises methyl salicylate which is present in an

amount of at least 150 g/L of the total volume of the formulation.

In another embodiment, the solvent consists of, or consists

essentially of, or substantially comprises, or substantially completely

comprises methyl salicylate which is present in an amount of at least 150

g/L of the total volume of the formulation. In another embodiment, the

solvent is methyl salicylate to the exclusion of any other solvents.

In some embodiments, the deltamethrin is present at a concentration

of at least about 10 g/L of the total weight of the formulation. Particularly,

the deltamethrin can be present in an amount between about 10 g/L to about

75 g/L.

In certain embodiments, the piperonyl butoxide is present at a

concentration of at least about 10 g/L of the total weight of the formulation.

Particularly, the piperonyl butoxide can be present in an amount between

about 10 g/L to about 500 g/L. Accordingly, the ratio of deltamethrin to

piperonyl butoxide may be between about 1:1 and about 1:8.

In some embodiments, the non-ionic surfactant may be selected from an alkoxylated styryl phenol, an alkoxylated oil or a mixture thereof, and the anionic surfactant may be an alkylbenzene sulphonate. The total surfactants may be present in an amount of at least 50 g/L. Particularly, the surfactants present are in a total concentration of between about 50 g/L and 150 g/L.

Preferably, the non-ionic surfactant is selected from the group

consisting of an ethoxylated tristyryl phenol and an ethoxylated castor oil or

a combination thereof, and the anionic surfactant may be calcium C10-16

alkylbenzyl sulphonate.

In certain embodiments, the solvent comprises methyl salicylate,

which is present in an amount of at least 150 g/L, or at least 250 g/L, of the

total volume of the formulation. In embodiments that include at least one

additional solvent, the additional solvent may be selected from the group

consisting of petroleum hydrocarbons (such as a heavy aromatic solvent

naphtha (petroleum)), a pyrrolidone (such as N-methyl-pyrrolidone), an

arylketone (such as acetophenone) or combinations thereof. In other

words, at least 150 g/L (i.e., 15% w/v) of the formulation is methyl salicylate,

although other solvents may also be present and hence the total solvent

may be greater than 150 g/L. The total amount of solvent present in the

emulsifiable concentrate formulation may be between about 350 g/L and

about 1150 g/L.

In a second aspect, the present invention provides pesticide

formulation, comprising:

deltamethrin at a concentration of about 50 g/L;

piperonyl butoxide at a concentration of about 400 g/L; a non-ionic surfactant comprising an ethoxylated tristyryl phenol at a concentration of about 88 g/L; an anionic surfactant comprising a calcium salt of an alkylbenzene sulfonate at a concentration of about 38 g/L; and a solvent consisting of technical methyl salicylate or a mixture of Oil of Wintergreen and at least one of heavy aromatic petroleum solvent naphtha, acetophenone and N-methyl-pyrrolidone.

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

producing a pesticide formulation of the first or second aspects, comprising

the steps of (a) combining the deltamethrin, the piperonyl butoxide, a

surfactant and a solvent, and (b) mixing to form a pesticide formulation

In a fourth aspect, the present invention provides a method of

preventing and/or controlling a pest infestation in a storage area,

comprising:

mixing the concentrate formulation of the first or second aspects with

water or a water-containing liquid to obtain a pesticide composition, and

applying the pesticide composition to a material for storage in the

storage area to thereby prevent and/or control the pest infestation,

wherein the material for storage is selected from the group consisting

of grain, fruit, vegetables and timber.

Suitably, the mixing step and the applying step in the method of the

third aspect may utilise any suitable equipment or mode for carrying out

these steps. For example, the mixing step may be carried out by stirring or

agitation, and the applying step may be carried out by spraying,

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 liquid form

as a concentrate having a relatively high concentration of active ingredient/s

in proportion to other excipients within the formulation and which are stable

in concentrate form but readily dispersible in water or a water-containing

liquid when diluted for use. By way of example, using a concentrate liquid

formulation allows for the treatment of a given volume of produce or target

area (e.g., crop, land, commercial or residential premises etc.) with a

reduced amount of the concentrated 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 concentrate,

emulsion-in-water concentrate, or ULV liquid 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, in emulsifiable concentrate formulations,

emulsion-in-water concentrate formulations and ULV liquid formulations,

the active ingredient 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.

The selection of appropriate solvents and other excipients typically

requires careful consideration so as to achieve a passable emulsifiable

concentrate formulation with good stability, acceptable shelf life and the

desired dispersibility of the formulation in water or a water-containing liquid

before use. However, additional commercial factors also need to be taken

into consideration during product development and when selecting solvents

and other excipients for emulsifiable concentrate formulations. These

factors may include: cost of the solvents and excipients and if a cheaper

alternative is available that is of comparable effectiveness (for instance,

whether an organic extract is necessary, or if a cheaper, synthetic solvent

could be used); any environmental impact of the solvents and excipients;

and whether certain solvents may have additional advantageous effects,

such as also being active against at least one pest species.

In view of the foregoing, the present invention advantageously

provides a pesticide formulation comprising deltamethrin that is suitable for

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

agricultural, horticultural, industrial or domestic setting. Advantageously, the

pesticide formulations of the present invention include methyl salicylate as

a substantial component of the solvent, either as a high purity synthetic

methyl salicylate (CAS No. 119-36-8) or as an essential oil extract of the

herb wintergreen, otherwise known as Oil of Wintergreen (CAS No. 68917

75-9). The inventors have surprisingly found that not only does methyl

salicylate result in a stable emulsifiable concentrate formulation comprising

deltamethrin and piperonyl butoxide, and hence an enduring alternative to

other commercially available combination formulations, but methyl

salicylate is understood to also provide compounding insecticidal benefits

to extend efficacy as a protectant of stored grains.

In one embodiment, formulations described herein may be suitable

for application to stored grains as a protectant against insecticidal attack.

Further, the deltamethrin formulation may be an emulsifiable concentrate,

an emulsion-in-water concentrate or a ULV liquid, particularly an

emulsifiableconcentrate.

Accordingly, in one broad form the invention resides in an

emulsifiable concentrate formulation comprising:

deltamethrin;

piperonyl butoxide;

a non-ionic surfactant and an anionic surfactant; and a solvent, wherein the solvent comprises methyl salicylate which is present in an amount of at least 150 g/L of the total volume of the formulation.

The term "deltamethrin" as used herein refers specifically to the

compound (S)-a-cyano-phenoxybenzyl (1R,3R)-3-(2,2-dibromovinyl)-2,2

dimethylcyclopropanecarboxylate (CAS# 52918-63-5). It is understood that

other stereoisomers do not display pesticidal activity, and only the above

isomer is effective.

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

synergizes the activity of a pesticide or an insecticide, such as a pyrethroid

like deltamethrin. 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. In a

preferred embodiment, the synergist is piperonyl butoxide.

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. By way of

example, piperonyl butoxide is capable of interacting with and inhibiting

phase 1 metabolic enzymes, specifically esterases and cytochrome P450.

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

pesticide formulation thereby facilitates or potentiates the activity of deltamethrin and thus advantageously increases the biological effectiveness thereof, while achieving substantial savings on the effective treatment cost. It is understood that whilst piperonyl butoxide does not have any insecticidal activity per se, when used in conjunction with deltamethrin it slows the affected pest's capacity to degrade and eliminate (that is, metabolise) the deltamethrin, thereby amplifying the pesticidal effect of the applied composition, relative to the same amount of deltamethrin applied without a synergist such as piperonyl butoxide.

Further, the addition of methyl salicylate as a solvent, which forms a

substantial portion of the pesticide formulations of the present invention, has

also been found surprisingly to further provide a pesticidal effect. In other

words, the use of methyl salicylate as a solvent, either as a synthetic solvent

or a component of the essential oil extract Oil of Wintergreen, provides the

dual activities of stabilising the formulation and providing some pesticidal

activity.

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

formulations of the present invention are stabilized, at least in part, as a

result of the interaction between the surfactant(s) and solvent(s) 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. It is understood that,

in some formulations, the synergist may also partially dissolve the deltamethrin, and/or stabilize the deltamethrin in solution, in combination with the solvent(s) and surfactant(s).

The solvent of the pesticide formulations herein may comprise one

solvent, or they may comprise two or more solvents. At least one of the

solvents comprises methyl salicylate. It is understood that at least one of

the solvents of the formulation dissolves at least some of the pesticidally

active deltamethrin. In some embodiments, the solvent may also dissolve

the piperonyl butoxide. In other embodiments, the piperonyl butoxide may

also act as a solvent and at least partially dissolve the deltamethrin. 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, or between a polar solvent/water mixture and a non-polar solvent,

or between a polar solvent/water mixture and the synergist, or between

water and a non-polar solvent. The emulsion may be stabilised by the

surfactant(s) present. Formulations of the present invention that comprise

water as the most abundant component by weight are referred to herein as

"emulsion-in-water" formulations. Emulsion-in-water formulations described

herein can comprise concentrations of deltamethrin that are suitable for use

as a concentrate (i.e., that requires at least some dilution with water before

application).

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 generally 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

suitable liquid formulation known in the art. Exemplary liquid formulations

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

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

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 one or more active agents, 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 and agitation with water, a water-containing liquid, or the like, 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.

It will also be well understood to the skilled person that the term "ultra

low volume liquid", or "ULV liquid" as used herein refers to a liquid

formulation that is suitable for direct use without further dilution or

combination with other liquids. Use of ULV liquids is characterised by the

low volume of the liquid formulation to be delivered to a relatively broad

area. As such, ULV liquids typically require specific application equipment

to facilitate delivery of the liquid to the target area. Such equipment can

range from small handheld devices to aircraft-mounted machinery. An

example of suitable equipment for applying a ULV liquid is a fogging

machine, which converts ULV liquid formulations into fine particulates or

mist. This is achieved via high power, low pressure gas streams (most

commonly air) coupled with specialist nozzles. The resulting fine droplets

formed by a fogging machine can cover a relatively large target area per

unit volume of ULV liquid delivered, compared to other liquid formulations.

In addition to the active ingredient and a solvent system in which the active

is very soluble, ULV products often contain surface-active agents and drift

control substances. Advantages of ULV products include:

• High concentration leads to low material-handling requirements,

• Easy to transport and to use; no dilution is required,

• Optimum biological activity enabled for active ingredient, and

• Good penetration of foliage and into less accessible areas.

In one aspect, the invention provides an emulsifiable concentrate

formulation, wherein:

the deltamethrin is present at a concentration of at least about 10 g/L,

or between about 10 g/L to about 75 g/L, of the total weight of the

formulation; and/or

the piperonyl butoxide and is present at a concentration of at least

about 10 g/L, or between about 10 g/L to about 500 g/L, of the total weight

of the formulation; and/or

the non-ionic surfactant is an alkoxylated styryl phenol, an

alkoxylated oil or a mixture thereof, and the anionic surfactant is an

alkylbenzene sulphonate, wherein the surfactant is present in a total amount

of at least 50 g/L, or between about 50 g/L and 150 g/L, of the total weight

of the formulation; and/or

the solvent further comprises N-methyl-pyrrolidone, acetophenone,

heavy aromatic petroleum solvent naphtha, or any combination thereof, and

the solvent is present in a total amount ranging between about 350 g/L to

about 1150 g/L of the total volume of the formulation.

In a related aspect, the invention provides pesticide formulation,

comprising:

deltamethrin at a concentration of about 50 g/L;

piperonyl butoxide at a concentration of about 400 g/L;

a non-ionic surfactant comprising an ethoxylated tristyryl phenol at a concentration of about 88 g/L; an anionic surfactant comprising a calcium salt of an alkylbenzene sulfonate at a concentration of about 38 g/L; and a solvent consisting of technical methyl salicylate or a mixture of oil of wintergreen and at least one of heavy aromatic petroleum solvent naphtha, acetophenone and N-methyl-pyrrolidone.

By "emulsion-in-water" as used herein, it is meant that the pesticide

formulation is a homogeneous liquid formulation of active agents, such as

pesticides. An emulsion-in-water pesticide formulation comprises a water

immiscible phase in which the active agents are dissolved, which is

dispersed throughout a water-containing matrix. In other words, it is

understood that such formulations comprise an oily organic phase

dispersed as small droplets throughout a bulk water-containing, or aqueous,

phase. An alternate term for an emulsion-in-water formulation may be an

oil-in-water formulation. Such formulations of the present invention may be

in concentrate form (i.e., comprising a high enough concentration of

deltamethrin that requires dilution before application).

The statements which follow apply equally to the aforementioned

aspects of the invention.

For the present invention, deltamethrin is suitably present in a

concentration (e.g., at least about 10 g/L) that provides a concentrated

pesticide formulation, such as an emulsifiable concentrate formulation, an

emulsion-in-water concentrate or a ULV liquid, 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, emulsion-in-water concentrate formulations or

ULV liquid formulations, deltamethrin may be present in an amount from

about 10 g/L to about 75 g/L or any range therein such as, but not limited

to, about 20 g/L to about 50 g/L, about 10 g/L to about 60 g/L, about 15 g/L

to about 25 g/L, or about 25 g/L to about 40 g/L of the liquid pesticide

formulation. In particular embodiments of the present invention,

deltamethrin is present in an amount of about 10, 11, 12, 13, 14, 15, 16, 17,

18,19,20,21,22,23,24,25,26,27,28,29,30,31,32,33,34,35,36,37,

38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 55, 60, 65, 70, 75 g/L, or

any range therein, of the liquid pesticide formulation. In certain

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

of about 10 g/L, or about 13 g/L, or about 50 g/L of the liquid pesticide

formulation.

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

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

pyrethroids, diphenyl oxazolines, thiazolidines, organophosphates 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 emulsion-in-water

concentrate formulations, emulsifiable concentrate formulations or ULV

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

in an amount from about 10 g/L to about 500 g/L or any range therein such

as, but not limited to, about 50 g/L to about 300 g/L, about 100 g/L to about

400 g/L, or about 200 g/L to about 450 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 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 10

g/L, about 100 g/L or about 400 g/L of the liquid pesticide formulation. The

ratio of the total amount of deltamethrin to synergist (e.g., piperonyl

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

such as between 1:1 and 1:8, or it may be about 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 deltamethrin to synergist (e.g. piperonyl butoxide) may be about 1:1 or about and 1:8.

The term "solvent" refers to any liquid capable of maintaining another

substance in solution. The solvent may comprise an alkyl salicylate (e.g.,

methyl salicylate), a petroleum derivative or hydrocarbon, such as a heavy

aromatic solvent naphtha (petroleum) (e.g., Recosol 150 or Recosol 200),

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, 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 comprises, substantially

comprises, consists of, or is, methyl salicylate. More particularly, the solvent

may be synthetic or purified methyl salicylate, or it may be an essential oil extract of wintergreen, known as Oil of Wintergreen. In some embodiments, the solvent may further comprise a solvent that is miscible with methyl salicylate or Oil of Wintergreen extract.

When additional solvents are used (i.e., in addition to the solvent

comprising methyl salicylate), each may be selected from the group

consisting of a pyrrolidone, such as N-methyl pyrrolidone, and/or an

arylketone (such as acetophenone), and/or a petroleum derivative or

hydrocarbon, such as a heavy aromatic solvent naphtha (petroleum).

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 may comprise a first and a second solvent. It will be appreciated that

the first and second solvents may be or comprise any solvent known in the

art, including water.

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

solvent may suitably be between 1 and 300 parts of the first solvent, and

about 1 part of the second solvent. For example, the ratio may be about

300:1, 295:1, 290:1, 285:1, 280:1, 275:1. 270:1, 265:1, 260:1, 255:1, 250:1,

245:1, 240:1, 235:1, 230:1, 225:1, 220:1, 215:1, 210:1, 205:1, 200:1, 195:1,

190:1, 185:1, 180:1, 175:1, 170:1, 165:1, 160:1, 155:1, 150:1, 145:1, 140:1,

135:1, 130:1, 125:1, 120:1, 115:1, 110:1, 105:1, 100:1, 95:1, 90:1, 85:1,

80:1, 75:1, 70:1, 65:1, 60:1, 55:1, 50:1, 45:1, 40:1, 35:1, 30:1, 25:1, 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, 1:1 and any range therein. In one preferred embodiment,

the ratio of the first solvent to the second solvent is in the range of about 1:1 to about 220:1.

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

including an emulsifiable concentrate formulation, a ULV liquid formulation

and an emulsion-in-water concentrate formulation, of the present invention,

may be present in a total amount from about 350 g/L to about 1150 g/L or

any range therein such as, but not limited to, about 350 g/L to about 750

g/L, about 500 g/L to about 650 g/L, or about 400 g/L to about 850 g/L of

the liquid pesticide formulation. In particular embodiments of the present

invention, the solvent is present in an amount of about 350, 360, 370, 380,

390,400,410,420,430,440,450,460,470,480,490,500,510,520,530,

540,550,560,570,580,590,600,610,620,630,640,650,660,670,680,

690,700,710,720,730,740,750,760,770,780,790,800,810,820,830,

840,850,860,870,880,890,900,910,920,930,940,950,960,970,980,

990,1000,1010,1020,1030,1040,1050,1060,1070,1080,1090m 1100,

1110, 1120, 1130, 1140 or 1150 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 350 g/L of the liquid

pesticide formulation. More particularly, the solvent is present in an amount

ranging about 450 g/L, or about 512 g/L, or about 913 g/L, or about 1053

g/L, or about 1090 g/L, or about 1125 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, a solubilising 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. In some embodiments, the

surfactant may be a solubilising agent and act as a solvent in the

formulations described herein. In such embodiments, the surfactant may

replace at least a portion of the solvent required to form a stable formulation.

In some embodiments, the surfactant may replace a substantial portion of

solvent, or it may replace all of the solvent (e.g., the formulation may comprise minimal or no solvent).

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 pesticide formulation comprising

deltamethrin, such as an emulsifiable concentrate formulation, or ULV liquid

formulation, or an emulsion-in-water concentrate formulation. In this regard,

it will be apparent that an amount of the surfactant of the pesticide

formulation can vary, for example, depending on the specific form of the

pesticide formulation (e.g., liquid or solid formulation), the particular 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, ULV liquid formulations or emulsion-in-water

formulations, the surfactant may be present in a total amount of surfactant

from about 20 g/L to about 150 g/L or any range therein such as, but not

limited to, about 25 g/L to about 100 g/L, or about 30 g/L to about 75 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, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150

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 50 g/L of the liquid pesticide formulation. More

preferably, the surfactant is present in an amount of about 60 g/L, or about

100, or about 126 g/L of the liquid pesticide formulation.

For the present invention, the surfactant is suitably selected from the

group consisting of non-ionic surfactants and anionic surfactants and any

combination thereof. Suitable non-ionic surfactants may include an

alkoxylated styryl phenol, 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. 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 ULV liquid described herein or the emulsion-in-water concentrate formulation, 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, -C02-, -SO3H,

S03-, -OSO3H, -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 ULV liquid formulation described herein

or the emulsion-in-water formulations 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 10:1 and

about 1:10, 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 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, or any range therein,

in the liquid pesticide formulation.

It will be appreciated that the surfactant may be any suitable

surfactant known 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 1284 or 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), Termul 3150), 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 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) and an alkoxylated oil, such as an

alkoxylated vegetable oil (e.g., Termul 1284 and Termul 1285) and any

combination thereof.

More particularly, the surfactant can be selected from the group

consisting of an ethoxylated tristyryl phenol (e.g., Termul 3150), an

ethoxylated castor oil (e.g., Termul 1284) and calcium C10-16 alkylbenzyl

sulphonate (branched or linear chain in solvent) (e.g., Ninate 60E, NANSA

EVM70/2E, Kemmat HF60) or a 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 20:1 and

about 1:1, or between about 15:1 and about 3:1, or between about 10:1 and

about 5:1 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, 4.9:1, 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. In

particular embodiments, the ratio of solvent to surfactant may be about 19:1, or about 10:1, or about 7:1, or about 4:1, or about 3:1.

It will be apparent in light of the foregoing that one or more

surfactants may be introduced into the formulation of the invention as a

soluble concentration in a further solvent (e.g., calcium dodecylbenzene

sulfonate in ethyl hexanol) and the latter may equate, for example, to

amounts up to about 10 g/L to about 25 g/L or more of the formulation. Given

the above, it will be appreciated that such amounts of the further solvent

may make little or no contribution to the solvency of active ingredients 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, emulsion-in-water concentrate

formulation and the ULV liquid formulation as required.

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

formulation, including the emulsifiable concentrate formulation or ULV liquid

formulation or emulsion-in-water concentrate formulation, provided herein

to be readily or easily pumped or poured from a storage vessel. Preferably,

the liquid pesticide formulation has a viscosity at room 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 deltamethrin, 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 a further aspect, the invention resides in a method of preventing

and/or controlling a pest infestation in a storage area, comprising: mixing

the concentrate formulation described above with water or a water

containing liquid to obtain a pesticide composition, and applying the

pesticide composition to a material for storage in the storage area to thereby

prevent and/or control the pest infestation. The material for storage may be

selected from the group consisting of grain, fruit, vegetables and timber.

Suitably, the method of this aspect includes the initial step of mixing

the pesticide formulation or the emulsifiable concentrate formulation, the

ULV liquid formulation or the emulsion-in-water concentrate 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 ULV liquid or the emulsion-in-water 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, including stored crops or timber, or

animal irritation) 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, animal, stored material 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 the emulsion-in-water concentrate formulation or

the ULV liquid 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

emulsion-in-water concentrate formulations or the ULV liquid 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 emulsion-in-water concentrate formulation or the emulsifiable concentrate formulation or the ULV liquid 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. A "target area' may include

a "storage area".

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 ULV

liquid 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,

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 or ULV liquid

formulation or emulsion-in water concentrate formulation of the invention

may vary according to the prevailing conditions such as desired pesticidal

and/or pestistatic effect and duration, weather, target species, habitat, mode

of application, and the like.

In particular embodiments, an effective amount is the amount of the

pesticide formulation or the emulsifiable concentrate formulation or ULV

liquid formulation or the emulsion-in-water concentrate formulation of the invention that has an adverse effect (e.g., reproduction inhibition, knockdown and/or death) on at least 25% (e.g., 25%, 30%, 35%, 40%, 45%,

50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 100% or any

range therein) of the pests treated or contacted therewith, more preferably

at least 50% of the 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 ULV liquid formulation or the emulsion-in-water

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 ULV

liquid formulation or the emulsion-in-water 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 emulsion-in-water concentrate formulation or the

emulsifiable concentrate formulation or ULV liquid 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 grain in storage, an effective amount of a pesticide formulation (including an emulsion-in-water formulation) or an emulsifiable concentrate formulation or ULV liquid formulation or emulsion-in-water concentrate formulation comprising deltamethrin is administered to the storage area, or to the grain before or during storage in the storage area. 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

ULV liquid formulation or emulsion-in-water formulations 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, ticks,

beetles, bugs, moths, springtails, caterpillars, loopers, bruchids, fleas,

mealybugs, midges, thrips, weevils, termites, butterflies and cockroaches,

which can cause significant damage to, for example, a wide range of

agricultural and horticultural crops, plants, animals and products.

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

prevented and/or controlled by the method for the present aspect include,

for example, Coleoptera, Homoptera, Lepidoptera, Muscidae, Anopheles,

Noctuidae, Heteroptera, Thysanoptera, Blattodea, Culicidae, Acrididae,

Tabanidae and Ixodidae spp. These pests can attack a wide variety of

horticultural crops, including citrus (for example, lemon, orange, grapefruit and the like), cotton, grapes, maize, canola and soya beans; harvested and stored horticultural products such as cereals, grains and timber; and agricultural animals, such as cattle, sheep and pigs. In a particular embodiment, the pesticide formulation or the emulsifiable concentrate formulation or ULV liquid formulation or emulsion-in-water concentration formulation of the invention are to be applied to stored grain in order to target, prevent and/or control grain storage pests, including Saw-toothed

Grain beetle (Oryzaephilus surinamensis), Flat Grain Beetles (Cryptolestes

spp.), Lesser Grain Borer (Rhyzopertha dominica), Tropical Warehouse

Moth (Ephestia cautella), Rust-red Flour Beetle (Tribolium castaneum),

Confused Four Beetle (Tribolium confusum) Rice Weevil (Sitophilus

oryzae), Granary Weevil (Sitophilus granarius) and Maize Weevil (Sitophilus

zeamais).

The pesticide formulation or the emulsifiable concentrate formulation

or ULV liquid formulation or emulsion-in-water concentration formulation of

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

interest, to a part thereof (such as the leaf or seed, stored grain or timber,

or animal skin), or to surroundings thereof. Methods and techniques for

applying the emulsifiable concentrate formulation, the ULV liquid

formulation or emulsion-in-water concentrate formulation are known in the

art and may include, for example, ground or aerial spraying after dilution in

water or a water-containing liquid.

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

emulsifiable concentrate formulation or ULV liquid formulation or the emulsion-in-water concentrate formulation are applied at a rate of about 250 to 3750 mL 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, 1000mL, 1025mL, 1050mL, 1075mL, and 11OOmL,

1150mL, 1200mL, 1250mL, 1300mL, 1350mL, 1400mL, 1450mL, 1500mL,

1600mL, 1700mL, 1800mL, 1900mL, 2000mL, 2100mL, 2200mL, 2300mL,

2400mL, 2500mL, 2600mL, 2700mL, 2800mL, 2900mL, 3000mL, 3250mL,

3500mL, 3750mL per hectare and any range therein) and more preferably

at a rate of about 250mL to about 750mL per hectare subsequent to dilution

thereof in a suitable spray liquid.

The pesticide formulation or the emulsifiable concentrate formulation

or ULV liquid formulation or emulsion-in-water concentration formulation of

the invention may also be applied to harvested grain before storage, in order

to obtain treated grain to be stored. Methods and techniques for applying

the emulsifiable concentrate formulation, the ULV liquid formulation or

emulsion-in-water concentrate formulation are known in the art and may

include, for example, spraying.

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

emulsifiable concentrate formulation or ULV liquid formulation or the

emulsion-in-water concentrate formulation are applied at a rate of about

10mL to about 1L pertonne of grain (e.g., about 10mL, 15mL, 20mL, 25mL,

30mL, 35mL, 40mL, 45mL, 50mL, 55mL, 60mL, 65mL, 70mL, 75mL, 80mL,

85mL, 90mL, 95mL, 100mL, 105mL, 110mL, 115mL, 120mL, 125mL,

130mL, 135mL, 140mL, 145mL, 150mL, 155mL, 160mL, 165mL, 170mL,

175mL, 180mL, 185mL, 190mL, 195mL, 200mL, 205mL, 210mL, 215mL,

220mL, 225mL, 230mL, 235mL, 240mL, 245mL, 250mL, 255mL, 260mL,

265mL, 270mL, 275mL, 280mL, 285mL, 290mL, 295mL, 300mL, 305mL,

310mL, 315mL, 320mL, 325mL, 330mL, 335mL, 340mL, 345mL, 350mL,

355mL, 360mL, 365mL, 370mL, 375mL, 380mL, 385mL, 390mL, 395mL,

400mL, 405mL, 410mL, 415mL, 420mL, 425mL, 430mL, 435mL, 440mL,

445mL, 450mL, 455mL, 460mL, 465mL, 470mL, 475mL, 480mL, 485mL,

490mL, 495mL, 500mL, 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, or 1000mL per tonne and any

range therein). In one embodiment, the emulsifiable concentrate formulation

or ULV liquid formulation or the emulsion-in-water concentrate formulation

is applied at a rate of about 40mL per tonne of grain, applied before storage

of the grain.

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 total active ingredient (i.e., total weight of deltamethrin) to

piperonyl butoxide may be between about 1:1 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 1:1 and about 1:300 or any range therein, and

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

may be between about 10:1 and about 1:10 or any range therein, and

• the ratio by weight of the total amount of solvent to the total amount

of surfactant may be between about 20:1 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 Emulsifiable Concentrate

Formulations Comprising Deltamethrin

A number of embodiments of emulsifiable concentrate formulations across

a range of deltamethrin concentrations, a range of overall deltamethrin and

piperonyl butoxide concentrations/proportions, and a range of

solvents/proportions and surfactants are provided below.

Embodiment 1 - Recipe for an emulsifiable concentrate nominally

combining 50g/L deltamethrin and 400g/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 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 Deltamethrin Active 51.4g/L (CAS# 52918-63-5, Technical material, ingredient (yields 50.5g/L 98.2%) insecticide deltamethrin) Piperonyl butoxide Insecticidal 435.3g/L (CAS# 51-03-6, Technical material, 92.0%) synergist (yields 400.5g/L piperonyl butoxide) Tristyrylphenol ethoxylate Surfactant 88.3g/L (CAS# 99734-09-5, e.g. Termul 3150) Alkylbenzenesulfonic acid, calcium salt in Surfactant 38.3g/L 2-ethylhexanol (CAS# 68584-23-6 in 104 76-7, e.g. Ninate 60E) Methyl salicylate Solvent 512.6g/L (CAS# 119-36-8) (to 1126g/L total)

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

2:

Table 2:

Test As manufactured Accelerated Aged Result Presentation: Yellow to brown Yellow to brown liquid liquid Assay: 49.6g/L 49.6g/L Require 45.0g/L! deltamethrin 5 55.0g/L Assay: 399.5g/L 380.9g/L Require 380g/L! piperonyl butoxide 5 420g/L pH1% 7.4 7.9 Nominally: 5.5 to 9.5 Persistent foaming 3mL 3mL Require:560mL foam after1 min Emulsion characteristics Trace of cream; Trace of cream; Require:52mL cream after 30 min, No oil; No oil; trace of oil after 30 min and complete Re-emulsifies/24h Re-emulsifies/24h re-emulsion after 24h

Embodiment 2 - Recipe for an emulsifiable concentrate nominally

combining 50 g/L deltamethrin and 400 g/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 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 Deltamethrin Active 51.8g/L (CAS# 52918-63-5, Technical material, ingredient (yields 50.9g/L 98.2%) insecticide deltamethrin) Piperonyl butoxide Insecticidal 435.3g/L (CAS# 51-03-6, Technical material, 92.0%) synergist (yields 400.5g/L piperonyl butoxide) Tristyrylphenol ethoxylate Surfactant 88.0g/L (CAS# 99734-09-5, e.g. Termul 3150) Alkylbenzenesulfonic acid, calcium salt in Surfactant 38.6g/L 2-ethylhexanol (CAS# 68584-23-6 in 104 76-7, e.g. Ninate 60E) Solvent naphtha (petroleum), heavy Solvent 196.6g/L aromatic (CAS# 64742-94-5,e.g.Recosol150) Methyl salicylate Solvent 254.7g/L (CAS# 119-36-8) (to 1065g/L total)

Chemical and physical parameters of embodiment 2 is as follows in Table 4: Table 4:

Test As Accelerated Aged manufactured Result Presentation: Yellow to brown Yellow to brown liquid liquid Assay: 50.5g/L 50.7g/L Require 45.0g/L deltamethrin 5 55.0g/L Assay: 398.3g/L 391.3g/L

Require 380g/L piperonyl butoxide 420g/L pH1% 7.4 7.9 Nominally: 5.5 to 9.5 Persistent foaming 5mL 4mL 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-emulsifies/24h emulsion after 24h emulsifies/24h

Embodiment 3 - Recipe for an emulsifiable concentrate nominally

combining 12.5g/L deltamethrin and 100g/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 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 Deltamethrin Active 13.0g/L (CAS# 52918-63-5, Technical material, ingredient (yields 12.8g/L 98.2%) insecticide deltamethrin) Piperonyl butoxide Insecticidal 109.0g/L (CAS# 51-03-6, Technical material, 92.0%) synergist (yields 100.3g/L piperonyl butoxide) Tristyrylphenol ethoxylate Surfactant 88.1g/L (CAS# 99734-09-5, e.g. Termul 3150) Alkylbenzenesulfonic acid, calcium salt in Surfactant 38.0g/L 2-ethylhexanol (CAS# 68584-23-6 in 104 76-7, e.g. Ninate 60E) N-methyl-pyrolidone Solvent 5.0g/L

(CAS# 872-50-4) Solvent naphtha (petroleum), heavy Solvent 20.0g/L aromatic (CAS# 64742-94-5,e.g.Recosol200) Methyl salicylate Solvent 882.9g/L (CAS# 119-36-8) (to 1156g/L total)

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

6:

Table 6:

Test As manufactured Accelerated Aged Result Presentation: Yellow to brown Yellow to brown liquid liquid Assay: 11.2g/L 11.0g/L Require 10.7g/L!5 deltamethrin 14.3g/L Assay: 99.7g/L 97.7g/L Require 90.0g/L! piperonyl butoxide 5 110g/L pH1% 7.4 7.7 Nominally: 5.5 to 9.5 Persistent foaming 8mL 6mL Require:!560mL foam after1 min Emulsion characteristics 0.1mL of cream; Trace of cream; Require: 52mL cream after 30 min, trace of No oil; Trace of oil; oil after 30 min and complete re-emulsion Re-emulsifies/24h Re after 24h I emulsifies/24h

Embodiment 4 - Recipe for an emulsifiable concentrate nominally

combining 12.5g/L deltamethrin and 1OOg/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 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 Deltamethrin Active 13.0g/L (CAS# 52918-63-5, Technical material, ingredient (yields 12.8g/L 98.2%) insecticide deltamethrin) Piperonyl butoxide Insecticidal 109.0g/L (CAS# 51-03-6, Technical material, synergist (yields 100.3g/L 92.0%) piperonyl butoxide) Tristyrylphenol ethoxylate Surfactant 88.1g/L (CAS# 99734-09-5, e.g. Termul 3150) Alkylbenzenesulfonic acid, calcium salt in Surfactant 38.0g/L 2-ethylhexanol (CAS# 68584-23-6 in 104 76-7, e.g. Ninate 60E) N-methyl-pyrrolidone Solvent 5.3g/L (CAS# 872-50-4) Solvent naphtha (petroleum), heavy Solvent 20.3g/L aromatic (CAS# 64742-94-5,e.g.Recosol200) Oil of Wintergreen Solvent 879.7g/L (CAS# 68917-75-9) (to 1153g/L total)

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

8:

Table 8:

Test As manufactured Accelerated Aged Result Presentation: Yellow to brown Yellow to brown liquid liquid Assay: 12.Og/L 11.6g/L Require 10.7g/L: deltamethrin !

14.3g/L Assay: 99.5g/L 98.7g/L Require 90.0g/L s piperonyl butoxide 5 110g/L plH 1% 7.6 7.1

Nominally: 5.5 to 9.5 Persistent foaming 4mL 4mL Require:!560mL foam after 1 min Emulsion characteristics No cream; 0.2mL of cream; Require: 52mL cream after 30 min, Trace of oil; No oil; trace of oil after 30 min and complete Re-emulsifies/24h Re-emulsifies/24h re-emulsion after 24h

Embodiment 5 - Recipe for an emulsifiable concentrate nominally

combining 1Og/L deltamethrin and 1Og/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 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 Deltamethrin Active 10.3g/L (CAS# 52918-63-5, Technical material, ingredient (yields 10.1g/L 98.2%) insecticide deltamethrin) Piperonyl butoxide Insecticidal 11.6g/L (CAS# 51-03-6, Technical material, synergist (yields 10.7g/L piperonyl 92.0%) butoxide) Tristyrylphenol ethoxylate Surfactant 72.8g/L (CAS# 99734-09-5, e.g. Termul 3150) Alkylbenzenesulfonic acid, calcium salt Surfactant 27.7g/L in 2-ethylhexanol (CAS# 68584-23-6 in 104-76-7, e.g. Ninate 60E) Acetophenone Solvent 5.0g/L (CAS# 98-86-2) Methyl salicylate Solvent 1048.Og/L (CAS# 119-36-8) (to 1175g/L total)

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

10:

Table 10:

Test As Accelerated manufactured Aged Result Presentation: Yellow to brown Yellow to brown liquid liquid Assay: 9.9g/L 9.7g/L Require 8.5g/L deltamethrin 11.5g/L Assay: 10.6g/L 10.2g/L Require 8.5g/L piperonyl butoxide 11.5g/L pH1% 7.9 7.6 Nominally: 5.5 to 9.5 Persistent foaming 2mL 2mL Require: 60mL foam after 1 min Emulsion characteristics Trace of cream; Trace of cream; Require: 2mL cream after 30 min, ;trace of No oil; No oil; oil after 30 min and complete re-emulsion Re-emulsifies/24h Re-emulsifies/24h after 24h

Embodiment 6 - Recipe for an emulsifiable concentrate nominally

combining 10 g/L deltamethrin and 10g/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 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

Deltamethrin Active 10.2g/L (CAS# 52918-63-5, Technical material, ingredient (yields 10.0g/L 98.2%) insecticide deltamethrin) Piperonyl butoxide Insecticidal 11.0g/L (CAS# 51-03-6, Technical material, 92.0%) synergist (yields 10.1g/L piperonyl butoxide) Castor oil ethoxylate Surfactant 30.0g/L (CAS# 61791-12-6, e.g. Termul 1284 Alkylbenzenesulfonic acid, calcium salt in Surfactant 30.0g/L 2-ethylhexanol (CAS# 68584-23-6 in 104 76-7, e.g. Ninate 60E) Acetophenone Solvent 5.1g/L (CAS# 98-86-2) Oil of Wintergreen Solvent 1085.8g/L (CAS# 68917-75-9) (to 1172g/L total)

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

12:

Table 12:

Test As manufactured Accelerated Aged Result Presentation: Yellow to brown Yellow to brown liquid liquid Assay: 9.0g/L 9.0g/L Require 8.5g/L! deltamethrin 5 11.5g/L Assay: 10.5g/L 10.2g/L Require 8.5g/L: piperonyl butoxide 5 11.5g/L pH1% 7.7 7.4 Nominally: 5.5 to 9.5 Persistent foaming 6mL 2mL Require:560mL foam after1 min Emulsion characteristics No cream; No cream; Require:52mL cream after 30 min, Trace of oil; Trace of oil; trace of oil after 30 min and complete Re-emulsifies/24h Re-emulsifies/24h re-emulsion after 24h

Embodiment 7 - Recipe for an emulsifiable concentrate nominally

combining 10 g/L deltamethrin and 1Og/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 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 13:

Table 13:

Ingredient Role Concentration Deltamethrin Active 10.2g/L (CAS# 52918-63-5, Technical material, ingredient (yields 10.0g/L 98.2%) insecticide deltamethrin) Piperonyl butoxide Insecticidal 10.9g/L (CAS# 51-03-6, Technical material, 92.0%) synergist (yields 10.0g/L piperonyl butoxide) Castor oil ethoxylate Surfactant 29.9g/L (CAS# 61791-12-6, e.g. Termul 1284) Alkylbenzenesulfonic acid, calcium salt in Surfactant 30.0g/L 2-ethylhexanol (CAS# 68584-23-6 in 104 76-7, e.g. Ninate 60E) Acetophenone Solvent 4.9g/L (CAS# 98-86-2) Methyl salicylate Solvent 1120.0g/L (CAS# 119-36-8) (to 1206g/L total)

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

14:

Table 14:

Test As manufactured Accelerated Aged Result Presentation: Yellow to brown Yellow to brown liquid liquid Assay: 10.2g/L 10.2g/L Require 8.5g/L deltamethrin ! 11.5g/L I

Assay: 10.5g/L 10.2g/L Require 8.5g/L! piperonyl butoxide 5 11.5g/L pH1% 7.5 7.8 Nominally: 5.5 to 9.5 Persistent foaming 7mL 6mL Require:!560mL foam after1 min Emulsion characteristics No cream; No cream; Require: 52mL cream after 30 min, Trace of oil; Trace of oil; trace of oil after 30 min and complete Re-emulsifies/24h Re-emulsifies/24h re-emulsion after 24h

Example 2: Deltamethrin 50 g/L + Piperonyl Butoxide 400 g/L EC Raw

Material Identities

An example formulation nominally combining 50 g/L deltamethrin and

400g/L piperonyl butoxide is provided below in Table 15, which includes the

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

deltamethrin technical and piperonyl butoxide technical are the same as that

used in the formulations of Example 1.

-CJ 'I

coC c Lo

" !E U

CU 0 U)> ? C.0 " 0) N I

U) c CUU co -. ~ a)t CL > c

CL :CU (D U) U)C 75OL E C9 Cl) <U.)CU

00 U) C: E CO ~ CUO ~0 CLC CD :CU3 -0 (0. LO C W a) A. a) m T- :3 )CC Lo . c Lo C) :7-LO Ccn m0 - * - .

0~~U 4t-7 ) 0o Cj)LC C: C- S E 0 Z CLO ) U) a) U) 0) Cl C S ~I _../ v UUC < CU '0 EU) C ) C SE ~ E cu~ -E E E E 0~ > :6- COCD--CU -CU .0 '-0-0 70 70 ) .~

CDU~ 7, C_) CU CU LCU CU M 70 M c E C/O a) .

0~ - C) CUC U) CU 2- CU 2 C

E CUU) C CU) oo CU C>U CU a) cu C a) ) CC o ) 44

0 .x - - U o 4- CoC 0 U)E.

0. U) CC U)C%

0c C 0

0. U)

Example 3: Method of Manufacture of Deltamethrin and Piperonyl

Butoxide Emulsifiable Concentrate Formulation

Formulation of a 10,OOOL 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.

-5%) for subsequent addition, to the formulation vessel with the

agitator operating

3. Charge active ingredients (deltamethrin and 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 (deltamethrin) content (appropriately

validated method. 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 deltamethrin 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). 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 piperonyl butoxide (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 200g

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: Bio-efficacy of Emulsifiable Concentrate

Formulations Comprising Deltamethrin

Trials have been carried out to compare the activity and efficacy of an

emulsifiable concentrate formulation of the present invention with a currently

available product for controlling an infestation of Rust Red Flour Beetle

(Tribolium castaneum).

A. Rust Red Flour Beetle

In this trial, a formulation of Embodiment 1 (as described above) was

compared to K-Obiol EC Combi Synergised Grain Protectant (APVMA No.

66921; Bayer CropScience Pty Ltd). Both concentrate formulations were

diluted in water at the amounts of 0.25, 0.5, 1 and 2 mL per litre of water to

form pesticide compositions for application. Clean wheat samples of 500 g

each were added 4L polyethylene tubs and mixed. The wheat samples were

then treated with 0.5 mL aliquots of these pesticide compositions via an

airbrush gun and whilst under agitation. After further agitation for 1 minute,

100g subsamples were taken and added to 1L polyethylene tubs to simulate

silos. After treatment, each 100 g subsample was infested with 20 individual

Rust Red Flour Beetles to simulate a natural incursion. Each of the sealed

microcosms (simulating a sealed silo) containing treated wheat and 20

individual beetles were then analysed after 1, 3 and 6 days after treatment

(DAT) for mortality. Results of these trials are provided below in Table 16,

which shows the mean number of dead beetles per microcosm and the %

corrected mortality using Abbott's Formula (Mortality % = (1-Tn after

treatment/ Cn after treatment) * 100, where Tn = number of live insects in treatment and Cn = number of live insects in control).

Table 16:

No. Formulation 1 DAT 3 DAT 3 DAT 6 DAT 6 DAT and Application %

% Rate Corrected Corrected Mortality Mortality) 1 Untreated - 0 0.3 - 2.8 0 g.ai/t grain 2 Embodiment 1 - 2.3 7.5 37.2% 19.8 98.7% 0.125 g.ai/t grain 3 K-Obiol Combi - 0.5 2.8 12.6% 17.8 88.7% 0.125 g.ai/t grain 4 Embodiment 1- 3.5 6.0 29.0% 20.0 100% 0.25 g.ai/t grain 5 K-Obiol Combi - 2.8 4.8 23.0% 20.0 100% 0.25 g.ai/t grain 6 Embodiment 1 - 5.5 9.8 48.2% 20.0 100% 0.50 g.ai/t grain 7 K-Obiol Combi - 4.3 7.0 34.4% 20.0 100% 0.5 g.ai/t grain 8 Embodiment 1 - 6.3 9.8 48.0% 20.0 100% 1 g.ai/t grain 9 K-Obiol Combi - 4.5 6.8 32.8% 20.0 100% 1 g.ai/t grain I I I I P value <0.001 <0.001 0.019 <0.001 <0.001 LSD 13.75 19.01 20.05 4.87 2.76 FACTORIAL ANALYSIS 1 DAT 3 DAT 3 DAT 6 DAT 6 DAT (%CM) (%CM) Embodiment 1 4.4 8.3 40.6% 19.9 99.7% K-Obiol Combi 3.0 5.3 25.7% 19.4 97.2% P value 0.002 0.039 0.005 <0.001 <0.001 LSD 10.37 14.32 10.02 1.97 1.96

The treatment analysis in Table 16 clearly shows that all treatments

provided significant control of Rust Red Flour Beetles when compared to the Untreated control throughout the duration of the trial. However, as seen in the factorial analysis, significant differences were exhibited between treatments at the 3 DAT assessment, where Embodiment 1 was significantly superior in controlling Rust Red Flour Beetle. This shows that the formulations of the present invention (comprising methyl salicylate) show a faster initial activity after infestation of a wheat silo by Rust Red Flour Beetle, compared to the currently available K-Obiol Combi product (which does not comprise methyl salicylate).

Claims (5)

1. A pesticide formulation comprising:

deltamethrin;

piperonyl butoxide;

a non-ionic surfactant and an anionic surfactant; and

a solvent,

wherein the solvent comprises methyl salicylate which is present in

an amount of at least 150 g/L of the total volume of the formulation.

2. The pesticide formulation of claim 1, wherein:

the deltamethrin is present at a concentration of at least about 10 g/L,

or between about 10 g/L to about 75 g/L, of the total weight of the

formulation; and/or

the piperonyl butoxide and is present at a concentration of at least

about 10 g/L, or between about 10 g/L to about 500 g/L, of the total weight

of the formulation; and/or

the non-ionic surfactant is an alkoxylated styryl phenol, an

alkoxylated oil or a mixture thereof, and the anionic surfactant is an

alkylbenzene sulphonate, wherein the surfactant is present in a total amount

of at least 50 g/L, or between about 50 g/L and 150 g/L, of the total weight

of the formulation; and/or

the solvent further comprises N-methyl-pyrrolidone, acetophenone,

heavy aromatic petroleum solvent naphtha, or any combination thereof, and the solvent is present in a total amount ranging between about 350 g/L to about 1150 g/L of the total volume of the formulation.

3. A pesticide formulation, comprising:

deltamethrin at a concentration of about 50 g/L;

piperonyl butoxide at a concentration of about 400 g/L;

a non-ionic surfactant comprising an ethoxylated tristyryl phenol at a

concentration of about 88 g/L;

an anionic surfactant comprising a calcium salt of an alkylbenzene

sulfonate at a concentration of about 38 g/L; and

a solvent consisting of technical methyl salicylate or a mixture of oil

of wintergreen and at least one of heavy aromatic petroleum solvent

naphtha, acetophenone and N-methyl-pyrrolidone.

4. A method of producing a pesticide formulation of any one of claims 1

to 3, comprising the steps of (a) combining the deltamethrin, the piperonyl

butoxide, a surfactant and a solvent, and (b) mixing to form a pesticide

formulation.

5. A method of preventing and/or controlling a pest infestation in a

storage area, comprising:

mixing the pesticide formulation of any one of claims 1 to 3 with water

or a water-containing liquid to obtain a pesticide composition, and

applying the pesticide composition to a material for storage in the storage area to thereby prevent and/or control the pest infestation, wherein the material for storage is selected from the group consisting of grain, fruit, vegetables and timber.

Imtrade Australia Pty Ltd

Patent Attorneys for the Applicant/Nominated Person SPRUSON&FERGUSON