AU2017202221B2 - High load steroid demethylation (ergosterol biosynthesis) inhibition formulation - Google Patents

Abstract

Provided is an emulsifiable concentrate formulation comprising: propiconazole at a concentration of at least about 650g/L; an agriculturally acceptable surfactant including one or more of an alkoxylated alkylphenol, an alkoxylated tristyryl phenol, an alkyl or aryl or alkylaryl sulfonate, an alkoxylated amine, an alkoxylated alkyl amine, an alkoxylated tallow amine, an alkoxylated oleil amine and an ether sulphate; and an agriculturally acceptable solvent selected from one or more of a hydrocarbon, a lactam and a ketone. A method of preparing such an emulsifiable concentrate formulation as well as methods of controlling fungal growth in a target crop by applying said emulsifiable concentrate formulation are also provided.

Description

HIGH LOAD STEROID DEMETHYLATION (ERGOSTEROL BIOSYNTHESIS) INHIBITION FORMULATION FIELD OF THE INVENTION

[0001] This invention relates to liquid formulations of the systemic anti-fungal agent propiconazole 1-[ [2-(2,4-dichlorophenyl)-4-propyl-1,3 dioxolan-2-yl]methyl]-1H-1,2,4-triazole. In particular, the invention relates to emulsifiable concentrate formulations of propiconazole that contain a high level of propiconazole as active agent and methods of preparing said formulations.

BACKGROUND OF THE INVENTION

[0002] Propiconazole is widely used as a systemic foliar fungicide with a broad range of activity. It is used on grasses grown for seed, mushrooms, corn, wild rice, peanuts, almonds, sorghum, oats, pecans, apricots, peaches, nectarines, plums, prunes and wheat. Propiconazole was developed in 1979 by Janssen Pharmaceuticals.

[0003] Propiconazole's mode of action is demethylation of C-14 during ergosterol biosynthesis, leading to the accumulation of C-14 methyl sterols. The biosynthesis of these ergosterols is critical to the formation of cell walls of fungi. This lack of normal sterol production slows or stops the growth of the fungus, effectively preventing further infection and/or invasion of host tissues.

[0004] Propiconazole, its synthesis and its antifungal properties are described in U.S. Pat. No. 4,079,062, incorporated herein by reference.

[0005] The use of antidotes/safeners for propiconazole has been described in US 20090048319 Al. Some synergistic herbicidal combinations that include propiconazole have been described in US 5397795 A and CN101543216 A.

[0006] Nonetheless, there remains a need for emulsifiable concentrate formulations that contain a high concentration of propiconazole as an active agent.

SUMMARY

[0007] The present invention is directed to an emulsifiable concentrate formulation, methods of making same and methods ofuse thereof

[0008] In a first aspect is provided an emulsifiable concentrate formulation comprising:

propiconazole at a concentration of at least about 650g/L;

at least one agriculturally acceptable surfactant selected from the group consisting of an alkoxylated alkylphenol, an alkoxylated tristyryl phenol, an alkyl or aryl or alkylaryl sulfonate, an alkoxylated amine, an alkoxylated alkyl amine, an alkoxylated tallow amine, an alkoxylated oleil amine, an ether sulphate and any combination thereof; and

at least one agriculturally acceptable solvent selected from the group consisting of a hydrocarbon, a lactam, a ketone and any combination thereof

[0009] Suitably, the surfactant is selected from the group consisting of an alkoxylated nonylphenol, an ethoxylated tristyryl phenol, a calcium dodecylbenzene sulfonate, an ethoxylated alkyl amine, an alkylphenol ether sulphate, an ethoxylated tallow amine, an ethoxylated oleil amine and any combination thereof

[0010] Suitably, the solvent is selected from the group consisting of an aromatic hydrocarbon, a pyrrolidone, a cyclic ketone, and any combination thereof Preferably, the agriculturally acceptable solvent is selected from the group consisting of solvent naphtha (petroleum) heavy aromatic, N-methyl pyrrolidone, isophorone, and any combination thereof

[0011] In one embodiment, the weight ratio of propiconazole to a non herbicide portion of the emulsifiable concentrate formulation is at least 2.

[0012] In one embodiment, the weight ratio of propiconazole to the solvent is at least 2.5.

[0013] In one embodiment, the weight ratio of propiconazole to the surfactant is at least 4.

[0014] Suitably, the concentration of the solvent is about 50 to about 350 g/L. Preferably, the concentration of the solvent is about 200 to about 300 g/L.

[0015] Suitably, the concentration of the surfactant is about 25 to about 200 g/L. Preferably, the concentration of the surfactant is about 40 to about 150 g/L.

[0016] Suitably, the surfactant is selected from the group consisting of a non-ionic surfactant, an anionic surfactant, a cationic surfactant, a zwitterionic surfactant, a cation-anion composite surfactant and any combination thereof. In one embodiment, the surfactant comprises at least one anionic surfactant and at least one non-ionic surfactant. In an alternative embodiment, the surfactant comprises at least one cation-anion composite surfactant and at least one non ionic surfactant.

[0017] In particular embodiments, the concentration of the non-ionic surfactant is about 10 to about 80 g/L.

[0018] In certain embodiments, the concentration of the cationic-anionic composite surfactant is about 20 to about 150 g/L.

[0019] In other embodiments, the concentration of the anionic surfactant is about 20 to about 150 g/L.

[0020] In a second aspect, the invention provides a method of preparing an emulsifiable concentrate formulation according to the first aspect including the steps of:

(a) adding propiconazole to a vessel;

(b) adding at least one agriculturally acceptable solvent to the vessel;

(c) adding at least one agriculturally acceptable surfactant to the vessel; and

(d) mixing the vessel so as to facilitate uniformity of the emulsifiable concentrate formulation..

[0021] In a third aspect, the invention provides an emulsifiable concentrate formulation prepared by the method of the second aspect..

[0022] In a fourth aspect, the invention provides a method of controlling fungal growth in a target crop including the step of applying to the target crop a fungicidally-effective amount of an emulsifiable concentrate formulation according to the first or third aspects.

[0023] 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.

[0024] 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

[0025] To overcome the aforementioned deficiencies it would be desirable to provide for an emulsifiable concentrate (EC) including a high load of propiconazole. There is a tendency for prior art EC formulations to contain significant quantities of non-herbicidal elements, such as solvents and surfactants, which contribute to the weight and volume of the formulation. As such, it would be beneficial for the ratio of herbicidal components to non herbicidal components, such as solubilising agents (e.g., one or more surfactants and/or solvents) to be as high as possible.

[0026] In view of the above, the present invention is at least partly predicated on the surprising discovery that emulsifiable concentrate formulations including high levels of propiconazole (e.g., greater than 650g/L) are achievable with particular agriculturally acceptable surfactants and solvents. This is important because the level ofuse of agriculturally acceptable solubilising agents, such as surfactants and solvents, in the formulations can be significantly decreased relative to lower concentration formulations.

[0027] Emulsifiable concentrates (ECs) of propiconazole have been sold in Australia and elsewhere under trade names such as Tilt, Orbit, Banner GL, Bumper and Wocosen. Tilt has been sold as an emulsifiable concentrate with 250g/L of propiconazole. Cracker Jack 550 (sold by Imtrade Australia) has been sold as an emulsifiable concentrate with 550g/L of propiconazole. Bumper has been sold as an emulsifiable concentrate with 625g/L of propiconazole (sold by Adama as Bumper 625). Note that in Bumper 625 the solvent content is 335.5g/L of liquid hydrocarbon so that the ratio of propiconazole to agriculturally acceptable solvent is 1.86. Banner GL has been sold as an emulsifiable concentrate with 418g/L propiconazole. Wettable powder formulations of propiconazole have been sold under the names Orbit W and Tilt 45W.

[0028] Many general characteristics of emulsifiable concentrate formulations have been described in US 2003/0072776 (Sun et al.). The Sun specification provides the following teachings about emulsifiers, solvents and optional ingredients.

Emulsifiers (according to Sun)

[0029] The emulsifiers of the emulsifiable concentrates comprise at least one emulsifier, which may be a non-ionic surfactant, an ionic surfactant, or a blend of both types of surfactants. It is also possible that an emulsifier in an emulsifiable concentrate may be a cationic surfactant. Useful non-ionic surfactants are said to include alkoxylated block polymers, alkoxylated alcohols, alkoxylated alkylphenols, alkoxylated amines, alkoxylated amides, alkoxylated fatty esters, alkoxylated oils, fatty esters, alkoxylated fatty acids, sorbitan derivatives, and the like.

[0030] Typical ionic surfactants found in emulsifiers include alkylaryl sulfonates; alkylarylsulfonic acids; carboxylated alcohol ethoxylates and carboxylated alkylphenol ethoxylates; carboxylic acids/fatty acids; diphenyl sulfonate derivatives; olefin sulfonates; phosphate esters; phosphorus organic derivatives; quaternary surfactants; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; sulfates of ethoxylated alcohols; sulfates of fatty esters; sulfonates of dodecyl and tridecylbenzenes; sulfonates of naphthalene and alkyl naphthalene; sulfonates of petroleum; sulfosuccinamates; alkanolamides; alkoxylated amines (with low EO values); sarcosine derived surfactants such as, ammonium lauroyl sarcosinate, and the like.

[0031] Preferred emulsifiers may be alkoxylated alcohols and alkyphenols, preferably of from about 4 to about 50 ethylene oxide units and a hydrophobe of from about 4 to about 16 carbon atoms. Other preferred surfactants may be alkylphenol EO/PO block copolymers, e.g., that sold under the trade name WITCONOL NS 108 LQ, and alkoxylated amine salts of ethoxylated alkylphenol sulfates, e.g., that supplied under the trade name WITCOLATE 1335 by Crompton Corporation, Witco Group.

[0032] Developing an effective emulsifier package (blend of emulsifiers) requires careful screening of potential emulsifiers (surfactants), conducting emulsion tests according to prescribed methods or established laboratory protocols, and optimizing the performance of the most promising emulsifier(s). The screening of potential emulsifier packages is dependent upon pesticide active type, and solvents. Those skilled in the art of EC technology understand the importance of hydrophilic-lipophilic balance and surfactant choice and concentration for such formulations. The emulsifier (surfactant) is preferably present at from about 1 to about 50 weight percent of the emulsifiable concentrate, more preferably from about 3 to about 10 weight percent. It is difficult to predict whether a surfactant system appropriate for a particular emulsifiable concentrate will also be appropriate for a different emulsifiable concentrate (e.g. with different active ingredient, different solvent etc.).

Solvents

[0033] The selection of a suitable solvent system is made by taking into consideration the solubility of the active(s) and the chemical and toxicological profiles of the solvent(s). The solvents include all EPA approved solvents, and the list of suitable solvents may include aliphatic paraffinic oils, such as kerosene or refined paraffins; aromatic solvents, such as xylenes; C 9-C 12

aromatic solvents, such as supplied under the trade names AROMATIC 100, 150, and 200 (as sold by Exxon Chemical), ISOPARL, SOLVESSO 100, 150, and 200; chlorinated hydrocarbons, such as chlorobenzene; alcohols, such as butanol and benzyl alcohol; ketones, such as cyclohexanone and N-methyl pyrollidone; and ethers, such as diethylene glycol and diethoxol. In addition, the solvent may include vegetable oils, methylated vegetable oils, petrol-oils, sugar esters of fatty acids, e.g., sucrose esters, and the like.

[0034] Preferred solvents may beC 9-C 12 hydrocarbon solvents because of their low cost and their ability to solubilize many pesticide toxicants.

[0035] In some embodiments, the solvent may be present at from 0 to about 95 weight percent of the emulsifiable concentrate, preferably from about to about 50 weight percent.

Optional Ingredients

[0036] Other additives may be included in emulsifiable concentrate formulations at levels less than about 5 weight percent. Such additives can include, for example, an antifreeze, a pH buffer or a finely divided hydrophobic filler.

[0037] Emulsifiable concentrates can be diluted with water to a desired level of active ingredients and applied to the targets using suitable means. Typically, the amount of active component in the formulations as applied to targets is from about 1 to about 95 weight percent.

[0038] There are a significant number of commercially available formulations of propiconazole in Australia. They are usually in the form of emulsifiable concentrates (EC). The above-identified commercially available propiconazole EC formulations contain at most 625g/L of propiconazole active ingredient, which suggests that 625g/L represents an upper practical limit in the amount of propiconazole that can be packaged in EC form using methods known to the art.

[0039] In this specification, the term "solubilising agent for propiconazole" is to be taken to refer to any agent, such as liquid agents and liquid systems in which propiconazole is miscible, including liquid agents and systems that include conventional agriculturally acceptable solvents and also liquid agents and systems that include conventional agriculturally acceptable liquid, or liquid-containing, surfactants, provided that propiconazole dissolves in said agent. A solubilising agent for propiconazole may contain one, two, or even more liquid components (e.g., surfactants and/or solvents).

[0040] The weight of a solubilising agent for propiconazole is taken to be the sum of weights of liquid components, being the components that are liquid at 200 C, that constitute the solubilising agent for propiconazole. For the avoidance of doubt, if a solubilising agent for propiconazole happens to include one or more solubilised solids (e.g., a solid dissolved surfactant), the weight of the solubilising agent for propiconazole is taken to be the sum of the weights of the liquid components of the solubilising agent for propiconazole, but does not include the weights of non-propiconazole solid components that may also be dissolved therein.

[0041] The term "agriculturally acceptable" means registered or otherwise approved for use in agriculture in at least one country. In this regard, agriculturally acceptable compounds (e.g., surfactants and solvents) may be applied to a particular soil or crop situation without causing unacceptable levels of soil damage or phytotoxicity in the crop.

[0042] The "propiconazole/solubilising agent ratio" in a propiconazole EC, which may be calculated by dividing the weight of propiconazole active ingredient in a given weight of a propiconazole EC formulation by the weight of the solubilising agent (e.g., surfactant, solvent) for propiconazole (as defined hereinbefore) in the same weight of the propiconazole EC formulation, is an important ratio as it affects:

[0043] 1. The quantity of solvent released to the environment as a consequence of applying a given amount of propiconazole formulation to a cultivation zone;

[0044] 2. The amount of high-quality packaging material that is utilised in carrying a given amount of propiconazole active ingredient to a cultivation zone;

[0045] 3. The amount ofused packaging material that needs to be recycled or otherwise disposed of after applying a given amount of propiconazole active ingredient to a cultivation zone;

[0046] 4. The contact toxicity of the propiconazole EC formulation to a farm worker;

[0047] 5. The flammability of the propiconazole EC formulation;

[0048] 6. The amount and speed of release of solvent (frequently aromatic hydrocarbon) to air in a given time after a spill has occurred;

[0049] 7. The weight of goods that must be carried by a farm worker in applying a given amount of propiconazole active ingredient to a cultivation zone;

[0050] 8. The cost of freight (volume and weight basis) in transporting the propiconazole formulation from factory to field;

[0051] 9. The capacity to demonstrate superior formulation expertise to farmers.

[0052] All of the issues mentioned above should be affected advantageously when a given amount of propiconazole in an EC formulation is associated with a lesser amount of solubilising agent, i.e., when the propiconazole/solubilising agent ratio is greater.

[0053] As an illustration of current propiconazole formulations, it may be instructive to consider a conventional commercial propiconazole EC formulation consisting of the following ingredients:

TABLE 1

Component Parts by Weight g/L Propiconazole 95% technical 263.2 Aromatic 150 solvent (Solvesso 150) 600 Calcium docecylbenzene sulphonate in 2- 23 ethylhexanol (e.g., Rhodocal 70/B) Ethoxylated amine moiety 41.9 Cetyl oleyl alcohol - ethoxylate 11.9 Polyethylene glycol 50

[0054] As another illustration of available propiconazole formulations, one may consider a conventional commercial propiconazole EC formulation consisting of the following ingredients:

TABLE2

Component Parts by Weight g/L Propiconazole 95% technical 578.9 Aromatic solvent 292.1 Anionic surfactant (60% solid in 40% 2- 97 ethylhexanol) Non-ionic surfactant (solvent-free solid) 97

[0055] In the formulation of table 2, propiconazole is present at 0.95x578.9= 550 parts by weight and solubilising agent for propiconazole is present at 292.1+0.4x97=330.9 parts by weight. The propiconazole/solubilising agent ratio is 550/330.9=1.66. However, if the non-ionic surfactant (97g/L) is not a solid at ambient temperature, then the propiconazole/solubilising moiety ratio falls, i.e., 550/(330.9 + 97) = 1.29. The latter can occur if, for example, Teric N13 is the non-ionic surfactant used, the melting point of Teric N13 being 14°C.

[0056] In the formulation of table 2, propiconazole is present at 0.95x578.9=550 parts by weight and solvent is present at 292.1 parts by weight. The propiconazole/solvent ratio is 550/292.1=1.88.

[0057] For the commercially available product Bumper 625 (Adama), propiconazole is present at 625g/L and liquid hydrocarbon solvent is present at 335.5g/L. The propiconazole/solvent ratio is 625/335.5 =1.86.

[0058] According to one aspect of the invention there is provided an emulsifiable concentrate formulation of propiconazole comprising propiconazole in at least 650g/L of the emulsifiable concentrate formulation, at least one solid, liquid-containing, or liquid agriculturally acceptable surfactant, and, optionally, at least one agriculturally acceptable solvent; wherein the liquid components of the emulsifiable concentrate formulation form a solubilizing moiety for propiconazole.

[0059] With respect to the concentrate of the present aspect, propiconazole may be present in a concentration of about 650 g/L to about 900 g/L propiconazole or any range therein, such as, but not limited to, about 675 g/L to about 825 g/L, about 700 g/L to about 800 g/L, or about 725 g/L to about 775 g/L. In particular embodiments, prosulfocarb is present in a concentration of about 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 g/L or any range therein. In certain embodiments of the present invention, prosulfocarb is present in a concentration of about 700 g/L to about 800 g/L.

[0060] The propiconazole may comprise at least 700g/L of the emulsifiable concentrate formulation.

[0061] According to another aspect of the invention there is provided an emulsifiable concentrate formulation of propiconazole including: propiconazole, wherein the propiconazole comprises at least 650g/L of the emulsifiable concentrate formulation; at least one solid, liquid-containing, or liquid, agriculturally acceptable surfactant; optionally, at least one agriculturally acceptable solvent; wherein the liquid components of the emulsifiable concentrate formulation form a solubilising agent for propiconazole, and wherein the propiconazole /solubilising agent weight ratio is greater than 1.8.

[0062] Suitably, the propiconazole /solubilising agent weight ratio is greater than 2.0.

[0063] Preferably, the propiconazole /solubilising agent weight ratio is greater than 2.2.

[0064] In one embodiment is provided a emulsifiable concentrate formulation comprising:

propiconazole at a concentration of at least about 650g/L;

at least one agriculturally acceptable surfactant selected from the group consisting of an alkoxylated alkylphenol, an alkoxylated tristyryl phenol, an alkyl or aryl or alkylaryl sulfonate, an alkoxylated amine, an alkoxylated alkyl amine, an alkoxylated tallow amine, an alkoxylated oleil amine, an ether sulphate and any combination thereof; and

at least one agriculturally acceptable solvent selected from the group consisting of a hydrocarbon, a lactam, a ketone and any combination thereof

[0065] Suitably, the weight ratio of propiconazole to a non-herbicide portion of the emulsifiable concentrate formulation is at least 1.8 (e.g., 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5 or any range therein). It will be appreciated that the non-herbicide portion of the emulsifiable concentrate formulation refers to those component agents, such as, but not limited to, one or more solvents, surfactants and carrier materials, which has insignificant or no herbicidal activity of its own. In particular embodiments, the weight ratio of propiconazole to the non-herbicide portion of the formulation is at least 2.0, more preferably at least 2.1, and even more preferably at least 2.2.

[0066] Preferably, the weight ratio of propiconazole to the agriculturally acceptable surfactant in the concentrate is at least 3 (e.g., 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0 or any range therein). In further embodiments, the weight ratio of propiconazole to the agriculturally acceptable surfactant in the concentrate is at least 3.5 and even more preferably at least 4.0.

[0067] Preferably, the weight ratio of propiconazole to the agriculturally acceptable solvent in the concentrate is at least 2 (e.g., 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0 or any range therein). In further embodiments, the weight ratio of propiconazole to the agriculturally acceptable surfactant in the concentrate is at least 2.5 and even more preferably at least 3.0.

[0068] When the agriculturally acceptable solvent is present it may comprise at least one solvent selected from the group consisting of petroleum based aromatic hydrocarbons (such as solvent naphtha (petroleum) heavy aromatic and including Solvesso 150 and Solvesso 200 or analogous materials), glycol ethers, adipate esters, succinate esters, pyrrolidones and substituted pyrrolidones including N-substituted pyrrolidones, cyclic ketones, alpha-beta unsaturated cyclic ketones, isophorone, alkane solvents, aromatic solvents, alkylaryl solvents, alcohol-containing solvents, aldehyde-containing solvents, ether-containing solvents, ester-containing solvents, ketone containing solvents, lactam-containing solvents, amide-containing solvents, chlorinated solvents and xylene.

[0069] Preferably the agriculturally acceptable solvent comprises at least one solvent selected from the group consisting of aromatic hydrocarbons with a boiling range of about 160-290 deg C, cyclic ketones, isophorone, N alkylpyrrolidone and aromatic hydrocarbons with a boiling range of about 160 240°C. N-methylpyrrolidone and aromatic hydrocarbons with a boiling range

of about 180-210°C, specific gravity about 0.89, flash point about 67°C and aromatic content of about 99% are highly preferred.

[0070] In particular embodiments, the propiconazole to solvent ratio may be greater than 2.5 (e.g., 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0 or any range therein)..In certain embodiments, the propiconazole to solvent ratio is greater than 2.7, preferably greater than 2.8, more preferably greater than 2.9, even more preferably greater than 3.0.

[0071] For the formulation of the present invention, the solvent may be present in a concentration of about 20 to about 400 g/L in the formulation, or any range therein, such as, but not limited to, about 100 g/L to about 300 g/L, about 125 g/L to about 250 g/L, or about 150 g/L to about 200 g/L. In particular embodiments of the present invention, the solvent is present in a concentration of about 20, 30, 40, 50, 60, 70, 80, 90, 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 g/L or any range therein. In particular embodiments, the solvent is present in a concentration of about 250 g/L to about 350 g/L and more preferably about 275 g/L to about 325 g/L..

[0072] In preferred embodiments, the at least one optional agriculturally acceptable solvent may be present in the range of from 100 to 300g/L of the formulation, including 200 to 300g/L and 230 to 290g/L.

[0073] For the present aspect, the at least one agriculturally acceptable solid, liquid or liquid-containing surfactant is suitably selected from the group consisting of a non-ionic surfactant, an anionic surfactant, a cationic surfactant, a zwitterionic surfactant, a cation-anion composite surfactant and any combination thereof In one preferred embodiment, the at least one agriculturally acceptable solid, liquid or liquid-containing surfactant comprises at least one anionic surfactant and at least one non-ionic surfactant, such as those described herein. In another preferred embodiment, the at least one agriculturally acceptable solid, liquid or liquid-containing surfactant comprises at least one cation-anion composite surfactant and at least one non-ionic surfactant, such as those described herein.

[0074] In embodiments, the at least one solid, liquid-containing, or liquid agriculturally acceptable surfactant is selected from the group of non ionic surfactants consisting of: alkylphenol alkoxylates, block polymer alkoxylates, alcohol alkoxylates, amine alkoxylates, amide alkoxylates, sorbitan derivatives, fatty acid alkoxylates, alkoxylated triglycerides and EO/PO di-block and tri-block and multi-block materials. In certain embodiments, 'alkoxylate' includes ethoxylate, propoxylate, and mixed ethoxylate-propoxylate, including multi-block ethoxylate/propoxylate materials.

[0075] Suitably, the at least one agriculturally acceptable surfactant is selected from the group consisting of an alkoxylated alkylphenol, an alkoxylated tristyryl phenol, an alkyl or aryl or alkylaryl sulfonate, an alkoxylated amine, an alkoxylated alkyl amine, an alkoxylated tallow amine, an alkoxylated oleil amine, an ether sulphate and any combination thereof. Preferably, the surfactant is selected from the group consisting of an alkoxylated nonylphenol (e.g., Termul 200), an ethoxylated tristyryl phenol (e.g., Termul 3150), a calcium dodecylbenzene sulfonate (e.g., Rhodameen RAM/7), an ethoxylated alkyl amine (e.g., Rhodameen RAM/7), an alkylphenol ether sulphate (e.g., Toximul TANS 5), an ethoxylated tallow amine (e.g., Toximul TANS 5), an ethoxylated oleil amine, such as those neutralized with dodecylbenzenesulphonic acid (e.g., Rhodameen RAM/7) and any combination thereof

[0076] In particular embodiments, the at least one agriculturally acceptable solid, liquid or liquid-containing surfactant is not a calcium dodecylbenzene sulfonate (e.g., Ninate 60E, Kemmat HF60, Rhodacal 70), a nonylphenol ethoxylate (e.g., a nonylphenol-20-EO, such as Teric N20, a nonylphenol-30-EO, such as Teric N30), a castor oil ethoxylate, such as a castor oil-54-EO (e.g., Termul 1285), a EO/PO block copolymer nonylphenol ethoxylate (e.g., Teric PE64 and Teric PE68), an alkoxylated polypropyleneglycol (e.g., Termul 203).

[0077] Suitably, the at least one agriculturally acceptable solvent selected from the group consisting of a hydrocarbon, a lactam, a ketone and any combination thereof. Preferably, the at least one agriculturally acceptable solvent selected from the group consisting of an aromatic hydrocarbon, a pyrrolidone, a cyclic ketone, and any combination thereof. Even more preferably, the at least one agriculturally acceptable solvent is selected from the group consisting of solvent naphtha (petroleum) heavy aromatic, N-methyl pyrrolidone, isophorone, and any combination thereof.

[0078] In particular embodiments, the at least one agriculturally acceptable solid, liquid or liquid-containing solvent is not a simple ketone, such as acetone, an ester, such as methyl benzoate and ethyl benzoate, an aryl ketone, such as propiophenone, an aromatic ketone, such as acetophenone, an alkyl ester, such as Exxate 700 (i.e., a C-Cs branched alkyl ester).

[0079] In certain embodiments, the non-ionic surfactant is selected from the group consisting of alkoxylated alkylphenols, alkoxylated styrene substituted phenols. More preferably, the non-ionic surfactant comprises nonylphenol alkoylate and/or tristyryl phenolalkoxylate.

[0080] The at least one surfactant may be selected from the group consisting of alkoxylated triglycerides, including alkoxylated castor oils (including castor oil 36 EO (on an average basis) and castor oil 54 EO (on an average basis)), and alkoxylated coconut oils.

[0081] The at least one surfactant may be chosen from EO/PO diblock and tri-block materials having EO block lengths in the range 12-35 and HLB values in the range 5-20.

[0082] The at least one surfactant may be selected from the group consisting of nonylphenol EO-PO diblock materials with one block having 7 11 EO (on an average basis) and the other block having 8-12 PO (on an average basis).

[0083] In particular embodiments, the non-ionic surfactant is present at a concentration of about 10 to about 150 g/L in the formulation, or any range therein, such as, but not limited to, about 20 g/L to about 130 g/L, about 25 g/L to about 80 g/L, or about 40 g/L to about 60 g/L. In particular embodiments of the present invention, the non-ionic surfactant is present in a concentration 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, ,51,52,53,54,55,56,57,58,59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69,70, 71,72,73,74,75,76,77,78,79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92,93,94,95,96,97,98,99, 100, 105, 110,115,120, 125, 130, 135, 140, 145, 150 g/L or any range therein. In particular embodiments, the non-ionic surfactant is present in a concentration of about 20 g/L to about 100 g/L and more preferably about 35 g/L to about 60 g/L and even more preferably about g/L to about 55 g/L.

[0084] In one embodiment, the concentration of the non-ionic surfactant is about 10 to about 80 g/L.

[0085] In certain embodiments, the at least one solid, liquid-containing or liquid agriculturally acceptable surfactant includes an anionic surfactant, including for example, a surfactant such as calcium alkylbenzene sulfonic acid in liquid concentrate form. Suitably, the anionic surfactant is selected from the group consisting of alkylaryl sulfonates; alkylarylsulfonic acids; carboxylated alcohol ethoxylates and carboxylated alkylphenol ethoxylates; carboxylic acids/fatty acids; diphenyl sulfonate derivatives; olefin sulfonates; phosphate esters; phosphorus organic derivatives; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; sulfates of ethoxylated alcohols; sulfates of fatty esters; sulfonates of dodecyl and tridecylbenzenes; sulfonates of naphthalene and alkyl naphthalene; sulfonates of petroleum; and sulfosuccinamates.

[0086] The anionic surfactant may be selected from the group consisting of calcium alkylbenzene sulfonic acid salt in solution form wherein the alkyl moiety, which may be straight or branched, is Cs-C 1 4 alkyl.

[0087] With respect to the calcium alkylbenzene sulfonate salt surfactants provided herein (i.e., Ninate 60E, Kemmat HF60 and Rhodacal 70) these all nominally comprise about 60% surfactant (i.e., calcium alkylbenzenesulfonate) by weight blended in 2-ethylhexanol.

[0088] Suitably, the alkyl moiety, which may be straight or branched, may be CO-C 1 2 alkyl.

[0089] In particular embodiments, the anionic surfactant is present at a concentration of about 20 to about 200 g/L in the formulation, or any range therein, such as, but not limited to, about 20 g/L to about 130 g/L, about 25 g/L to about 80 g/L, or about 40 g/L to about 60 g/L. In particular embodiments of the present invention, the anionic surfactant is present in a concentration of about 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39,40,41,42,43,44,45,46,47,48,49,50,51,52,53,54,55,56,57,58,59, , 61, 62, 63, 64, 65, 66, 67, 68, 69,70,71,72,73,74,75,76,77,78,79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 160, 170, 180, 190, 200 g/L or any range therein. In particular embodiments, the anionic surfactant is present in a concentration of about 20 g/L to about 100 g/L and more preferably about 60 g/L to about 80 g/L and even more preferably about 65 g/L to about 75 g/L.

[0090] In one embodiment, the concentration of the anionic surfactant is about 20 to about 150 g/L.

[0091] In one embodiment, the at least one solid, liquid-containing or liquid agriculturally acceptable surfactant includes a cationic surfactant selected from fatty amine lower-mole ethoxylates (which may be incompatible with anionic surfactants), alkylquaternary amine surfactants, and a zwitterionic surfactant (i.e., a surfactant which simultaneously carries anionic and cationic charge).

[0092] Examples of suitable zwitterionic surfactants include betaine surfactants and calcium alkylbenzene sulfonic acid in liquid concentrate form.

[0093] The at least one solid-liquid-containing or liquid surfactant may include a cation-anion composite surfactant. Cation-anion composite surfactants include an amine surfactant that has been neutralised (or participated in a proton-exchange reaction) with an alkyl or aryl or alkylaryl acid such as an alkyl or aryl sulphate or sulphonate. Examples of cation-anion composite surfactants include alkylphenol ether sulfate/tallowamine ethoxylate salts (including materials sold under the trade names Toximul TANS-5, Toximaul TANS-6, Toximul TANS-8, Toximul TANS-15), and alcohol ether sulphate/tallowamine ethoxylate salts (including materials sold under the trade names Toximul TAABS-5, Toximul TAABS-8). Another cation-anion composite includes rhodameen/RAM 7 (by Solvay) which consists of ethoxylated oleil (oleyl) amine neutralised with dodecylbenzenesulphonic acid - this results in the creation of oleil (oleyl) amine dodecylbenzenesulphonic salt (which may be liquid in character). The term "A neutralised with B" shall be taken to mean that A and B have exchanged a proton.

[0094] In particular embodiments, the cation-anion composite surfactant is present at a concentration of about 20 to about 200 g/L in the formulation, or any range therein, such as, but not limited to, about 20 g/L to about 130 g/L, about 25 g/L to about 80 g/L, or about 40 g/L to about 60 g/L. In particular embodiments of the present invention, the cation-anion composite surfactant is present in a concentration of about 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, 49,50,51,52,53,54,55,56,57,58,59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, ,71,72,73,74,75,76,77,78,79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91,92,93,94,95,96,97,98,99, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 160, 170, 180, 190, 200 g/L or any range therein. In particular embodiments, the cation-anion composite surfactant is present in a concentration of about 20 g/L to about 100 g/L and more preferably about 40 g/L to about 95 g/L and even more preferably about 55 g/L to about 90 g/L.

[0095] In one embodiment, the concentration of the cationic-anionic composite surfactant is about 20 to about 150 g/L.

[0096] According to an embodiment of the present invention there is provided an emulsifiable concentrate formulation of propiconazole including: propiconazole, wherein the propiconazole comprises at least 650g/L of the emulsifiable concentrate formulation; at least one solid, liquid-containing, or liquid, agriculturally acceptable surfactant and also at least one agriculturally acceptable solvent; wherein the liquid components of the emulsifiable concentrate formulation form a solubilising agent for propiconazole, and wherein the propiconazole solubilising agent weight ratio is greater than 2.

[0097] The agriculturally acceptable solvent may comprise at least one solvent selected from the group consisting of alkane compounds, aromatic compounds, alkylaryl compounds, alcohol-containing compounds, aldehyde containing compounds, ether-containing compounds, ester-containing compounds, ketone-containing compounds, lactam-containing compounds, amide-containing compounds, cyclic ketones, alpha-beta unsaturated cyclic ketones, isophorone, aromatic hydrocarbons with a boiling range of about 160 290 deg C and chlorinated compounds.

[0098] The agriculturally acceptable solvent may comprise at least one solvent selected from the group consisting of solvent naphtha (petroleum), heavy aromatic, cyclic ketone, xylene, toluene, pyrrolidones including N alkylated pryrrolidones such as N-methyl pyrrolidone, cyclohexanone, acetone, glycol ethers such as diethyleneglycol monomethyl ether (including the material sold under the trade name Carbitol), ethyleneglycolmonobutylethers (including the material sold under the trade name Butyl Glysolv), propylene glycol monomethyl ether (including the material sold under the trade name Glysolv PM), methanol, ethanol, isopropanol, decanol, paraffins, hexane, acetic acid C6 -Cs branched alkyl ester ((including the material sold under the trade name Exxate 700).

[0099] The agriculturally acceptable solvent may comprise at least one solvent selected from the group consisting of aromatic solvent 150 (such as Solvesso 150 or Recosol 150, typically characterised as having a specific gravity of 0.89; an open cup flashpoint of >65.6°C; a boiling range of 182-

205°C; an aromatic content of 99%), solvent 200 (such as Solvesso 200 and Recosol 200), isophorone and N-methyl pyrrolidone (typically characterised as having a specific gravity of 1.033; a boiling point of 396°F; a flashpoint range between 187-204°F).

[0100] The at least one agriculturally acceptable solvent may be present in the range of from 50 to 350 g/L of the formulation, preferably, in the range from to 180 to 320g/L, more preferably in the range from 210 to 280g/L.

[0101] The at least one agriculturally acceptable surfactant may comprise a non-ionic surfactant.

[0102] The at least one agriculturally acceptable non-ionic surfactant, may be selected from the group consisting of alkoxylated block polymers, alkoxylated alcohols, alkoxylated alkylphenols, alkoxylated amines, alkoxylated amides, alkoxylated fatty esters, alkoxylated oils, fatty esters, alkoxylated fatty acids, and sorbitan derivatives.

[0103] In one embodiment, the agriculturally acceptable non-ionic surfactant may be selected from the group consisting of nonylphenol ethoxylate (including materials sold under the trade name Teric N9, Teric N15, Teric N30), octylphenol ethoxylate (including materials sold under the trade name Teric X5, Terix X8, Teric X1O), alkoxylated alkylphenol (including materials sold under the trade name Termul 200, Orisurf 200), vegetable oil ethoxylate (including materials sold under the trade name Termul 1284, Termul 1285), tristyryl phenol ethoxylates (including material sold under the trade name Termul 3150), alcohol ethoxylates such as tridecyl alcohol -9EO (including material sold under the trade name Teric 13A9), C 1 2-C 14 alcohols reacted with 2 moles EO (including material sold under the trade name Teric 12A2N), block copolymers such as polyoxyethylene/polyoxypropylene block copolymer (including materials sold under the trade names Teric PE62, Teric PE64, Teric PE 68), and fatty amine higher-mole ethoxylates (such as tallowamine ethoxylates and oleyl amine ethoxylate) which have non-ionic characteristics such as cloud point and compatibility with anionic surfactants (including materials sold under the trade name Terwet 3780).

[0104] The preferred non-ionic surfactants can be selected from alkoxyated alkylphenols (e.g., Termul 200) and alkoxylated tristyryl phenols (e.g., Termul 3150).

[0105] In one embodiment, the non-ionic surfactant is present in the range from 10- 80g/L, preferably from 15-60g/L of the formulation.

[0106] Alternatively the at least one agriculturally acceptable surfactant comprises an anionic surfactant.

[0107] The at least one agriculturally acceptable anionic surfactant may be selected from alkylaryl sulfonates; alkylarylsulfonic acids; carboxylated alcohol ethoxylates and alkylphenol ethoxylates; carboxylic acids/fatty acids; diphenyl sulfonate derivatives; olefin sulfonates; phosphate esters; phosphorus organic derivatives; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; sulfates of ethoxylated alcohols; sulfates of fatty esters; sulfonates of dodecyl and tridecylbenzenes; sulfonates of naphthalene and alkyl naphthalene; sulfonates of petroleum; sulfosuccinamates; alkoxylated amines; sarcosine derived surfactants such as, ammonium lauroyl sarcosinate; alkoxylates as above other than ethoxylates (such a propoxylates, butoxylates).

[0108] The at least one agriculturally acceptable anionic surfactant may be selected from the group consisting of linear and branched alkylbenzenesulphonates and salts thereof which may be provided as a non aqueous solution, (such as calcium Cio-C1 4 alkylbenzenesulfonate) (including materials sold under the trade name NANSA EVM70/2E which is carried in 2 ethylhexanol), alkyl sulphates such as sodium lauryl sulphate (including material sold under the trade name Empicol LX/N), alkyl ether sulfates such as sodium lauryl ether (2EO) sulphate (including material sold under the trade name Emipmin KESM70/AU), alkyl phosphates (including material sold under the trade names Alkanate PA100, Alkanate PG30, and Alkanate PL50), alkyl ether phosphates (including material sold under the trade name Alkanate PK100).

[0109] In particular embodiments, the at least one agriculturally acceptable surfactant is or comprises at least one cationic surfactant, including fatty amine lower-mole ethoxylates (which may be incompatible with anionic surfactants).

[0110] In another embodiment, the at least one agriculturally acceptable surfactant may be at least one zwitterionic surfactant (i.e., a surfactant which simultaneously carries anionic and cationic charge). Examples of zwitterionic surfactants include betaine surfactants.

[0111] The at least one agriculturally acceptable surfactant may include a cationic-anionic composite surfactant, wherein an amine surfactant is neutralised with a hydrophobic acid such as an alkyl or aryl sulphate or sulphonate. Examples of these cation-anion composite surfactants may be selected from alkylphenol ether sulfate/tallowamine ethoxylate salts (including materials sold under the trade names Toximul TANS-5, Toximaul TANS-6, Toximul TANS-8, Toximul TANS-15), and alcohol ether sulphate/tallowamine ethoxylate salts (including materials sold under the trade names Toximul TAABS-5, Toximul TAABS-8). Another cation-anion composite surfactant includes rhodameen/RAM 7 (by Solvay) which consists of ethoxylated oleil amine neutralised with dodecylbenzenesulphonic acid - this results in the creation of oleil amine dodecylbenzenesulphonic salt, which is a liquid even in the absence of a solvent.

[0112] The cation-anion composite surfactant preferably includes a cation-anion composite selected from ethoxylated oleil amine/dodecylsulfonic (e.g. rhodameen RAM 7) acid salt and tallowamine ethoxylate/alkylphenol ether sulfate (e.g., Toximul TANS 5).

[0113] Preferably the, cation-anion composite surfactant is present in the range from 20-150g/L, more preferably 30-100g/L of the formulation.

[0114] In one embodiment, the propiconazole emulsifiable concentrate formulation includes at least two surfactants, a first non-ionic surfactant and a second cation-anion composite surfactant.

[0115] In one preferred embodiment, the first non-ionic surfactant is selected from the group consisting of nonylphenol ethoxylate (including materials sold under the trade name Teric N9, Teric N15, Teric N30), octylphenol ethoxylate (including materials sold under the trade name Teric X5, Terix X8, Teric X10), alkoxylated alkylphenol (including materials sold under the trade name Termul 200, Orisurf 200), vegetable oil ethoxylate (including materials sold under the trade name Termul 1284, Termul 1285), tristyryl phenol ethoxylates (including material sold under the trade name Termul 3150), alcohol ethoxylates such as tridecyl alcohol -9EO (including material sold under the trade name Teric 13A9), C 1 2-C 1 4 alcohols reacted with 2 moles EO (including material sold under the trade name Teric 12A2N), block copolymers such as polyoxyethylene/polyoxypropylene block copolymer (including materials sold under the trade names Teric PE62, Teric PE64, Teric PE 68), and fatty amine higher-mole ethoxylates (such as tallowamine ethoxylates and oleyl amine ethoxylate) which have non-ionic characteristics such as cloud point and compatibility with anionic surfactants (including materials sold under the trade name Terwet 3780), and wherein the amount of non-ionic surfactant is at least 10-80g/L, and a second cation-anion composite surfactant wherein an amine surfactant is neutralised with a hydrophobic acid such as an alkyl or aryl sulphate or sulphonate. Examples of these cation-anion composite surfactants include alkylphenol ether sulfate/tallowamine ethoxylate salts (including materials sold under the trade names Toximul TANS-5, Toximul TANS-6, Toximul TANS-8, Toximul TANS-15), and alcohol ether sulphate/tallowamine ethoxylate salts (including materials sold under the trade names Toximul TAABS-5, Toximul TAABS-8). Another cation-anion composite surfactant includes rhodameen/RAM 7 (by Solvay) which consists of ethoxylated oleil amine neutralised with dodecylbenzenesulphonic acid this results in the creation of oleil amine dodecylbenzenesulphonic salt, which is a liquid even in the absence of a solvent.

[0116] Suitably, the cationic-anionic composite surfactant is present in the formulation in at least 20-150g/L.

[0117] In one preferred embodiment, the first non-ionic surfactant is selected from alkoxyated alkylphenols (e.g., Termul 200) and alkoxylated tristyryl phenols (e.g., Termul 3150) and is present in the range from 10-80g/L preferably from 15-60g/L and the second cation-anion composite surfactant is chosen from the set ethoxylated oleil amine/dodecylsulfonic (e.g., rhodameen RAM 7) acid salt and tallowamine ethoxylate/alkylphenol ether sulfate (e.g., TANS 5) and is present in the range from 20-150g/L more preferably 30 100g/L, of the formulation.

[0118] In one embodiment, the first non-ionic surfactant is present in the formulation in the range between 10-80g/L, preferably from 15-60g/L , and the second cation-anion composite surfactant is present within the range between 20-150g/L, preferably 30-100g/L.

[0119] An emulsifiable concentrate formulation of propiconazole according to the present invention may also contain, for example, a perfume, an antifoam agent, a stenching agent, an embittering agent (the latter two agents to discourage ingestion), and any other agriculturally acceptable additives and excipients as are known in the art.

[0120] It will be appreciated that the utilizable ranges of agriculturally acceptable solvents and/or agriculturally acceptable surfactants will vary according to the desired propiconazole to solvent ratio and/or the desired propiconazole to surfactant ratio. The higher the propiconazole to solvent and/or propiconazole to surfactant ratios, the more restricted are the ranges of utilizable agriculturally acceptable solvents and agriculturally acceptable surfactants.

[0121] The density of the emulsifiable concentrate is at least 1.05 g/ml (e.g., 1.05, 1.06, 1.07, 1.08,. 1.09, 1.10, 1.11, 1.12, 1.13, 1.14, 1.15, 1.16, 1.17, 1.18, 1.19, 1.20 and any range therein), preferably at least 1.1 g/ml, and more preferably at least 1.14 g/ml.

[0122] In a related aspect, the invention provides a method of preparing an emulsifiable concentrate formulation according to the aforementioned aspect including the steps of:

(a) adding propiconazole to a vessel;

(b) adding at least one agriculturally acceptable solvent to the vessel to the vessel;

(c) adding at least one agriculturally acceptable surfactant to the vessel; and

(d) mixing the vessel so as to facilitate uniformity of the emulsifiable concentrate formulation.

[0123] Preferably, at step (d) the vessel is mixed, such as by agitation, for at least 30 minutes (e.g., 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 minutes). To this end, the combination of propiconazole, surfactant and solvent may be mixed by any means known in the art.

[0124] Suitably, the at least one agriculturally acceptable surfactant is that hereinbefore described. Preferably, the at least one agriculturally acceptable surfactant is selected from the group consisting of an alkoxylated nonylphenol (e.g., Termul 200), an ethoxylated tristyryl phenol (e.g., Termul 3150), a calcium dodecylbenzene sulfonate (e.g., Rhodameen RAM/7), ethoxylated alkyl amine (e.g., Rhodameen RAM/7), an alkylphenol ether sulphate (e.g., Toximul TANS 5), an ethoxylated tallow amine (e.g., Toximul TANS 5) and any combination thereof

[0125] Suitably, the at least one agriculturally acceptable solvent is that hereinbefore described. Preferably, the at least one agriculturally acceptable solvent is selected from the group consisting of of an aromatic hydrocarbon, a pyrrolidone, a cyclic ketone, and any combination thereof Even more preferably, the agriculturally acceptable solvent is selected from the group consisting of solvent naphtha (petroleum) heavy aromatic, N-methyl pyrrolidone, isophorone, and any combination thereof.

[0126] Suitably, the method of the present aspect is performed at about °C or above so as to facilitate melting of the triallate.

[0127] It will be appreciated that the propiconazole, surfactant and solvent may be added to the vessel in any order. By way of example, propiconazole may be added to the vessel after the addition of solvent.

[0128] Preferably, a representative sample is taken and tested according to a testing regime for specific gravity, pH, foam persistence and content of active agents.

[0129] In a further related aspect, the invention further provides an emulsifiable concentrate formulation prepared by the method according to the preceding aspect.

[0130] In another aspect, the invention provides a method of controlling fungal growth in a target crop including the step of applying to the target crop a fungicidally-effective amount of an emulsifiable concentrate formulation described herein.

[0131] By "fungicidally-effective amount" is meant that dosage of the formulation of propiconazole sufficient to exert the desired fungicidal activity. As will be appreciated, this may vary depending upon, for example, the concentration of propiconazole in the formulation, the target fungal species and the type of target crop. In one embodiment, the emulsifiable concentrate formulation is applied at a rate of about 20 to about 200 mL/Ha based on volume of the emulsifiable concentrate formulation.

[0132] Formulations incorporating diluted emulsifiable concentrates according to the present invention can be used for the control of certain fungal diseases of bananas, oats, peanuts, perennial ryegrass, pineapples, stone fruit (apricots, peaches, nectarines, plums and prunes), sugarcane, wheat, turfgrasses, mushrooms, corn, wild rice, almonds, sorghum, pecans, coffee, ornamental plants, sunflower, berries and vegetables.

[0133] One of the advantages of a higher loading product formulation according to the present invention is that lesser quantities of the formulation are required to achieve the same application rate when diluted for application to the crop to be treated. A 750g/L propiconazole emulsifiable concentrate is applied at 550/750 = about 0.73 of the rate of application of a standard 550g/L propiconazole emulsifiable concentrate if the end user applies active ingredient in the same absolute amount per unit of area. Consequently, such a 750g/L propiconazole emulsifiable concentrate will pro rata use appreciably less packaging/labelling/storage/transport. There will also be less environmental impact through reduced solvent use.

[0134] Mastering a stable formulation at a loading higher than 625g/L is difficult. Significant investments in time and materials are required to develop reproducible stable high loading emulsifiable concentrate formulations.

EXAMPLES

[0135] In order that the present invention may be more readily comprehended, reference is made to the following examples, some of which are preferred embodiments of the present invention.

EXAMPLE 1

[0136] The following propiconazole emulsifiable concentrate according to the invention was made by mixing the following components.

TABLE 1.1

Component Parts by Weight (g/L) Propiconazole 95% technical 789.5 (contains 750g/l of propiconazole) Aromatic solvent (Recosol 150) 242.8 Density - 0.891 Boiling Range - 182 -205°C Flash point - 67°C Aromatic content - 99% Cation-anion composite liquid surfactant 68.8 consists of ethoxylated fatty amine, neutralized with dodecylbenzenesulhponic acid - solvent free liquid (Rhodameen RAM/7) Nonyl phenol alkoxylate Termul 200 45.9 (solvent-free solid)

Total 1.147 Density= 1.147g/L

[0137] In the above formulation propiconazole is present at 0.95x789.5=750 parts by weight and solubilising moiety is present at 242.8+68.8=310 parts by weight. The propiconazole/solubilising moiety ratio is thus 750/310=2.42.

[0138] In the above formulation propiconazole is present at 0.95x789.5=750 parts by weight and solvent is present at 242.8 parts by weight. The propiconazole/solvent ratio is 750/242.8=3.08.

EC FORMULATIONS OF PROPICONAZOLE CONTAINING 750g/L PROPICONAZOLE

EXAMPLE 2

[0139] In this example, N-methyl pyrrolidone was used as the solvent. (Compare with formulation of Example 1 see Table 1.1)

TABLE 2.1

FORMULATION

Chemicalname) Function Amount, g Loading, g/L

(±)-1-[2-(2,4-dichlorophenyl)-4- Active propyl-1,3-dioxolan-2-ylmethyl]- ingredient 3955.9 751.6 1H-1,2,4-triazole e.g., Propiconazole (95% purity) N-methyl Pyrrolidone Solvent 1403.0 280.6 Ethoxylated fatty amine used: Rhodameen RAM7 (anionic Surfactant 361.1 72.2 surfactant) Alkoxylated alkyl phenol used: Termul 200 (non-ionic surfactant) Surfactant 243.1 48.6

1.153 Total, g Density= 1.153g/L

TABLE 2.2

RESULTS OF FORMULATION

Parameter Method Required Results Remarks

Appearance Visual Brown clear liquid Brown clear Pass liquid

Validated chromatographic method Assay (Accuracy: 98-102 725 to 775g/L 751.1 g/L Pass %) Propiconazole (Linearity: R>0.99) (Precision: s/average <2%)

pH at 1% aq. CIPAC MT 75.3 - 7.34 Solution

Specific gravity CIPAC MT 3.1 - 1.192 (temperature at 20°C)

<2mL cream after Emulsion 30 min, trace of oil 0.5mL of characteristi CIPAC MT 36.1 after 30 min and cream and Pass cs complete re- traces of oil emulsion after 24h

Persistent CIPAC MT 47.2 <60mL after 1 min 12 mL n/a Foaming

Brown clear Brown clear Cold temp. liquid, liquid, stability CIPACMT75.3 homogeneous, free homogeneous, (Accelerated from phase freefrom Pass Ageing) separation in any phase format separation in any format Viscosity (temperature CIPAC MT 192 n/a at 5°C)

Viscosity (temperature CIPAC MT 192 190 cPs Pass at 20°C)

Test parameter Long Term Various as per above maintained within - n/a Performance required range after accelerated aging to approximate 2 years.

General Remarks Pass PASS or FAIL?

Description: Pass

EXAMPLE 3

[0140] In this example, Alkylphenol ether sulphate/Tallowamine ethoxylated salts was used as the cation-anion composite surfactant. (Compare with formulation of Example 1 see Table 1.1)

TABLE 3.1

Propiconazole active present at 750 g/L

FORMULATION

Chemicalname) Function Amount, g Loading, g/L (±)-1-[2-(2,4-dichlorophenyl)-4 propyl-1,3-dioxolan-2-ylmethyl]- Active 3951.2 750.7 1H-1,2,4-triazole ingredient e.g., Propiconazole (95% purity) Recosol150 Solvent 1261.3 252.3 Alkylphenol ether sulphate/ Tallowamine ethoxylated salts Surfactant 373.5 74.7 used: Toximul TANS 5 Alkoxylated alkyl phenol used: Surfactant 237.7 47.5 Termul 200 (non-ionic surfactant) 1125.2 Total, g Density= 1.125g/L

TABLE 3.2

RESULTS OF FORMULATION

Parameter Method Required Results Remarks

Appearance Visual Brown clear liquid Brown liquid Pass

Validated chromatographic method Assay (Accuracy: 98-102 725 to 775 g/L 750.7 g/L Pass %) Propiconazole (Linearity: R>0.99) (Precision: s/average <2%)

pH at CIPAC MT 75.3 7.11 1% aq. Solution

Specific gravity (temperature at CIPAC MT 3.1 - 1.164 °C)

<2mL cream after Emulsion 30 min, trace of characteristics CIPAC MT 36.1 oil after 30 min Traces of oil Pass and complete re emulsion after 24h

Persistent CIPAC MT 47.2 <60mL after 1 min 5 mL Pass Foaming

Brown clear Brown clear Cold temp. liquid, liquid, stability CIPAC MT75.3 homogeneous, free homogeneous, Pass (Accelerated from phase free from phase Ageing) separation in any separation in any format format

Viscosity (temperature at CIPAC MT 192 °C)

Viscosity (temperature at CIPAC MT 192 260 cPs Pass °C)

Test parameter Long Term maintained within Performance Variousasperabove required range after accelerated aging to approximate 2 years.

General Remarks PASS PASS or FAIL?

Description: PASS

EXAMPLE 4

[0141] In this example, Tri-styryl phenol alkoxylate was used as the non-ionic surfactant. (Compare with formulation of Example 1 see Table 1.1)

TABLE 4.1

Propiconazole active present at 750 g/L

FORMULATION

Chemicalname) Function Amount, g Loading, g/L

(±)-1-[2-(2,4-dichlorophenyl)-4 propyl-1,3-dioxolan-2-ylmethyl]- Active 3956.1 751.7 1H-1,2,4-triazole ingredient e.g., Propiconazole (95% purity) Recosol150 Solvent 1287.3 257.5 Ethoxylated fatty amine used: Rhodameen RAM7 (anionic Surfactant 369.3 73.9 surfactant) Tri-styryl phenol alkoxylate used: Termul 3150 (non-ionic Surfactant 239.2 47.8 surfactant) Total, g 1130.9 Density= 1.130g/L

TABLE 4.2

RESULTS OF FORMULATION

Parameter Method Required Results Remarks

Appearance Visual Brown clear liquid Brown clear PASS liquid Validated chromatographic method (Accuracy: 98- 725 to 775 g/L Assay 102o%) 751.7 g/L PASS (Linearity: Propiconazole R>0.99) (Precision: s/averageS52 % )

pH at CIPAC MT 75.3 - 6.82 1% aq. Solution

Specific gravity (temperature at CIPAC MT 3.1 - 1.171 °C)

<2mL cream after 30 Emulsion CIPACMT36.1 min, trace of oil 1 mL of cream PASS characteristics after30-m and and traces of oil complete re emulsion after 24h

Persistent CIPAC MT 47.2 <60mL after 1 min 5 mL n/a Foaming

Brown clear liquid, Brown clear Cold temp. homogeneous, free liquid, stability CIPAC MT75.3 from phase homogeneous, PASS (Accelerated ro a free from phase Ageing) separationinany separation in any format format

Viscosity (temperature at CIPAC MT 192 - n/a °C)

Viscosity (temperature at CIPAC MT 192 210 cPs n/a °C)

Test parameter maintained within Long Term Various as per required range after n/a Performance above accelerated aging to approximate 2 years.

General Remarks PASS PASS or FAIL?

Description: PASS

EXAMPLE 5

[0142] In this example, Isophorone was used as the solvent. (Compare with formulation of Example 1 see Table 1.1)

TABLE 5.1

Chemicalname) Function Amount, g Loading, g/L

(±)-1-[2-(2,4-dichlorophenyl)-4 propyl-1,3-dioxolan-2-ylmethyl]- Active 3951.0 750.7 1H-1,2,4-triazole ingredient e.g.,. Propiconazole (95% purity) Isophorone Solvent 1435.0 287.0 Ethoxylated fatty amine used: Rhodameen RAM7 (anionic Surfactant 345.4 69.3 surfactant) Alkoxylated alkyl phenol used: Surfactant 244.1 46.3 Termul 200 (non-ionic surfactant) 1155.6 Total, g Density= 1.155g/L Outcome PASS

TABLE 5.2 RESULTS OF FORMULATION RESULTS OF FORMULATION

Parameter Method Required Results Remarks

Appearance Visual Brown clear liquid Brownuiclear Pass

Validated chromatographic method 725 to 775 g/L Assay (Accuracy: 98-102 %) Propiconazole 750.7 g/L Pass (Linearity: R>0.99) (Precision: s/average 52%) pH at 1% aq. CIPAC MT 75.3 7.40 Solution Specific gravity ClPAC MT 3.1 1.195 (temperature at 20C) <2mL cream after 30 Emulsion ClPAC MT 36.1 min, trace of oil after Traces of P characteristics 30 min and complete cream and oil re-emulsion after 24h Persistent CIPAC MT 47.2 <60mL after 1 min 20 mL Pass Foaming Brown clear Cold temp. Brown clear liquid, liquid, stability ClPACMT75.3 homogeneous, free freefrom Pass (Accelerated from phase separation phase Ageing) in any format separationin any format Viscosity (temperature CIPAC MT 192 n/a n/a at 5C) Viscosity (temperature CIPAC MT 192 765cPS Pass at 20C) Test parameter Long Term maintained within Various as per above required range after - n/a Performance accelerated aging to approximate 2 years. General Remarks PASSor PASS FAIL?

Description: PASS

EXAMPLE 6

[0143] In this example, Recosol 200 was used as the solvent. (Compare with formulation of Example 1 see Table 1.1)

TABLE 6.1

Chemicalname) Function Amount, g Loading, g/L

(±)-1-[2-(2,4-dichlorophenyl)-4 propyl-1,3-dioxolan-2-ylmethyl]- Active 3958.9 752.2 1H-1,2,4-triazole ingredient e.g., Propiconazole (95% purity) Recosol200 Solvent 1335.3 267.1 Ethoxylated fatty amine used: Rhodameen RAM7 (anionic Surfactant 353.1 70.6 surfactant) Alkoxylated alkyl phenol used: Surfactant 246.6 49.3 Termul 200 (non-ionic surfactant) 1139.2 Total, g Density= 1.139g/L Outcome PASS

TABLE 6.2 RESULTS OF FORMULATION

RESULTS OF FORMULATION

Parameter Method Required Results Remarks

Appearance Visual Brown clear liquid Brownclear Pass liquid Validated chromatographic method 775 to 825 g/L Assay (Accuracy: 98-102 %) Propiconazole 752.2 g/L Pass (Linearity: R>0.99) (Precision: s/average 52%) pH at M7537.34 1% aq. Solution MT75.3 Specific gravity 1.176 (temperature at CIPAC MT 3.1 200) <2mL cream after 30 Emulsion CIPAC MT 36.1 min, trace of oil after Traces of oil Pass characteristics 30 min and complete re-emulsion after 24h

Persistent Foaming CIPAC MT 47.2 <60mL after 1 min 9 mL Pass

Brown clear liquid, Brown clear Cold temp. stability homogeneous, free 1quid, (Accelerated MT75.3 from phase frefomphaeose Pass Ageing) separation in any frerophs format separation in any format Viscosity MT 192 n/a (temperature at 5C) Viscosity (temperature at MT 192 525 cPs Pass 200) Test parameter Long Term maintained within Various as per above required range after - n/a Performance accelerated aging to approximate 2 years. General Remarks PASS or FAIL? PASS

Description: PASS

EXAMPLE 7

Production protocol for formulation of the invention

[0144] The formulation procedure for a 10,OOL batch, inclusive of quality control measures, was as follows, with the steps being identified numerically as 1.1, 1.2, 1.3 and so on.

[0145] 1.1 Ensure formulation vessel is empty and clean.

[0146] 1.2 Charge solvent as follows to the formulation vessel with agitator off:

1. Aromatic solvent 150 (e.g., Recosol 150) 2200kg

[0147] 1.3 Charge active ingredient as follows to the formulation vessel with continuous agitation:

2. Propiconazole 95% Tech 7895kg

[0148] 1.4 Charge the surfactants as follows, clearing residual surfactant from any pumps or process lines used with the remaining complement of solvent:

3. Alkoxylated alkylphenol (e.g., Termul 200) 459kg 4. Neutralized ethoxylated alkylamine 688kg (e.g., Rhodameen RAM/7) 5. Aromatic solvent 150 (e.g., Recosol 150) 228kg

[0149] 1.5 Continue agitating for a minimum of 30 minutes following the last ingredient's addition.

[0150] 1.6 Sample approximately IL of product, ensuring it is representative.

[0151] 1.7 Sub-sample 250mL from the original IL sample, and subject it to the following testing regime.

[0152] 1.7.1 Specific gravity (CIPAC MT3.1).

[0153] 1.7.2 pH 1% aqueous (CIPAC MT75.3).

[0154] 1.7.3 Emulsion characteristics (CIPAC MT36.1).

[0155] 1.7.4 Persistent foam (CIPAC MT47.2)

[0156] 1.7.5 Active constituent (propiconazole) content (validated method as per APVMA report: MV20120723 - Propiconazole 750 EC Fungicide - July 2012).

[0157] 1.8 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.

[0158] 1.9 If pH 1% aqueous is satisfactory, 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.

[0159] 1.10 If emulsion stability in standard hard water is satisfactory, 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 (Alkoxylated alkylphenol (e.g., Termul 200) and Neutralized ethoxylated alkylamine (e.g., Rhodameen RAM/7)). After suitable agitation time to ensure homogeneity, resample and retest. Repeat adjustment process until emulsion stability is within the bounds of the acceptable range.

[0160] 1.11 If persistent foaming characteristics are satisfactory, 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.

[0161] 1.12 If active constituent level is satisfactory, 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 aromatic solvent 150 (for a high active content) or additional propiconazole active constituent (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.

[0162] 1.13 Catalogue and store a retention sample of approximately 200g.

[0163] 1.14 Generate a certificate of analysis noting results of testing.

[0164] 1.15 Issue quality clearance giving authority to package goods.

[0165] 1.16 Package the finished goods ensuring both the batch number and manufacturing date is noted on the label.

EXAMPLE 8

FIELD TRIAL TO DEMONSTRATE BIOEQUIVALENCE OF FORMULATIONS ACCORDING TO THE INVENTION SUMMARY

[0166] The sample made according to the method of the invention (See Example 1) is designated Propiconazole 750 EC (containing 750g/L of propiconazole) in the bioequivalence study.

[0167] The sample labelled Cracker Jack 550 EC is a commercially available Imtrade product (containing 550g/L of propiconazole).

[0168] At Arthurton, South Australia, in 2014, Propiconazole 750 EC at four rates was compared with Cracker Jack 550 EC to determine bioequivalence in the control of stripe rust (Puccinia striiformis) in wheat cv. H45.

[0169] All chemical treatments were applied in 100 L/ha of spray using an LPG pressurised hand-held spray unit incorporating Agrotop AM 110-01 nozzles at crop growth stage BBCH 41.

[0170] No crop phytotoxicity was observed in any treatment at any assessment timing. The corresponding application rates of Propiconazole 750 EC and Cracker Jack 550 EC recorded statistically equivalent grain yield. A significant rate response was evident for the application rate of propiconazole, which could be correlated to increased levels of stripe rust control.

[0171] The corresponding application rates of Propiconazole 750 EC and Cracker Jack 550 EC recorded statistically equivalent stripe rust severity and incidence at all assessment timings.

[0172] Propiconazole 750 EC and Cracker Jack 550 EC were statistically equivalent in terms of crop safety and stripe rust control in wheat cv. H45.

MATERIALS AND METHODS PRODUCTS

TABLE 8.1

Active Concentration Batch Product name ingredient of active Formulation number (ai) ingredient Propiconazole propiconazole 750 g/L Emulsifiable IAS12062 750 EC Concentrate Cracker Jack propiconazole 550 g/L Emulsifiable 14137 550 EC Concentrate

TREATMENTS

TABLE 8.2

Rate Product Active Application No. Product ingredient schedule (mL/ha) (grient (g ai/ha) 1 Untreated control nil nil

2 Propiconazole 750 EC 85 63.5

3 Cracker Jack 550 EC 115 63.5

4 Propiconazole 750 EC 127.5 95.25 One foliar Cracker Jack 550 EC 172.5 95.25 application on 05/09/14 at crop 6 Propiconazole 750 EC 170 127 growth stage BBCH 41. 7 Cracker Jack550EC 230 127

8 Propiconazole 750 EC 340 254

9 Cracker Jack550EC 460 254

CHRONOLOGY OF EVENTS

TABLE 8.3

Days after Crop stage Date application Event (DAA) Scale Description

17/05/14 -111DAA BBCH Dry seed sown Crop sown 00 04/0/14 1DAAEarly boot BBCH fl sheth Pre-spray disease severity 41 flagsheath and incidence assessment extending BBCH Early boot, Application of treatments /09/14 0DAA 41 ext ein 2-9

BBCH 70% of spikes Crop phytotoxicity and 12/09/14 7DAA 57 visible disease severity and incidence assessments BBCH 80% of spikes Crop phytotoxicity and 18/09/14 13DAA 68 with anthers disease severity and incidence assessments BBCH 90% of spikes Crop phytotoxicity and /09/14 20DAA 69 with anthers disease severity and incidence assessments

/11/14 61DAA BBCH Harvested Crop harvested 99 product Grain yield assessed

RESULTS

TABLE 8.4 Crop phytotoxicity to wheat cv. H45 at 7, 13 & 20DAA, Arthurton, South Australia, 2014

Crop phytotoxicity Rate (mean % compared to No. Treatment untreated control) 7DAA 13DAA 20DAA

1 Untreated control nil 0 0 0 2 Propiconazole 750 EC 63.5 0 0 0 3 Cracker Jack 550 EC 63.5 0 0 0 4 Propiconazole 750 EC 95.25 0 0 0 Cracker Jack 550 EC 95.25 0 0 0 6 Propiconazole 750 EC 127 0 0 0 7 Cracker Jack 550 EC 127 0 0 0 8 Propiconazole 750 EC 254 0 0 0 9 Cracker Jack 550 EC 254 0 0 0 P-value 1 1 1 LSD (5% level) NSD NSD NSD Factorial analysis Application rate of propiconazole 63.5 g ai/ha 0 0 0 95.25 g ai/ha 0 0 0 127 g ai/ha 0 0 0 254 g ai/ha 0 0 0 P-value 1 1 1 LSD (5% level) NSD NSD NSD Formulation of propiconazole Propiconazole 750 EC 0 0 0 Cracker Jack 550 EC 0 0 0 P-value 1 1 1 LSD (5% level) NSD NSD NSD DAA: Days after application NSD = No significant difference due to a P-value > 0.05

TABLE 8.5 Grain yield of wheat cv. H45 at 61DAA, Arthurton, South Australia, 2014

Rate Grain yield No. Treatment Rate (mean kg/ha) 61DAA 1 Untreated control nil 5374 c 2 Propiconazole 750 EC 63.5 5801 ab 3 Cracker Jack 550 EC 63.5 5586 bc 4 Propiconazole 750 EC 95.25 5786 ab Cracker Jack 550 EC 95.25 5789 ab 6 Propiconazole 750 EC 127 5717 ab 7 Cracker Jack 550 EC 127 5731 ab 8 Propiconazole 750 EC 254 5959 a 9 Cracker Jack 550 EC 254 5941 a P-value 0.0024 LSD (5% level) 249.5 Factorial analysis Application rate of propiconazole 63.5 g ai/ha 5694 b 95.25 g ai/ha 5787 b 127 g aiha 5724 b 254 g aha 5950 a P-value 0.0047 LSD (5% level) 123 Formulation of propiconazole Propiconazole 750 EC 5816 Cracker Jack 550 EC 5762 P-value 0.606 LSD (5% level) NSD DAA: Days after application NSD = No significant difference due to a P-value > 0.05

TABLE 8.6 Stripe rust (Pucciniastriiformis) severity on leaves of wheat cv. H45 at 7DAA, Arthurton, South Australia, 2014

Stripe rust severity Rate (mean % of leaf area infected) No. Treatment (gaia) 7DAA Flag Flag-i Flag-2

1 Untreated control nil 1.23 1.40 0.38 2 Propiconazole 750 EC 63.5 0.08 0.18 0.33 3 Cracker Jack 550 EC 63.5 0.30 0.10 0.00 4 Propiconazole 750 EC 95.25 0.00 0.00 0.05 Cracker Jack 550 EC 95.25 0.13 0.50 0.25 6 Propiconazole 750 EC 127 0.08 0.00 0.05 7 Cracker Jack 550 EC 127 0.50 0.10 0.05 8 Propiconazole 750 EC 254 0.00 0.00 0.00 9 Cracker Jack 550 EC 254 0.08 0.15 0.10 P-value 0.0709 0.1106 0.2923 LSD (5% level) NSD* NSD* tA Factorial analysis Application rate of propiconazole 63.5 g ai/ha 0.19 0.14 0.16 95.25 g ai/ha 0.06 0.25 0.15 127 g ai/ha 0.29 0.05 0.05 254 g ai/ha 0.04 0.08 0.05 P-value 0.4889 0.7346 0.7785 LSD (5% level) NSD NSD NSD Formulation of propiconazole Propiconazole 750 EC 0.04 0.04 0.11 Cracker Jack 550 EC 0.25 0.21 0.10 P-value 0.2751 0.2864 0.7756 LSD (5% level) NSD NSD NSD DAA: Days after application NSD No significant difference due to a P-value > 0.05 tA = Data transformed using x = Arcsine square root percent (y) * = Data failed Bartlett's test and cannot be transformed for homogeneity

TABLE 8.7 Stripe rust (Puccinia striiformis) severity on leaves of wheat cv. H45 at 13DAA, Arthurton, South Australia, 2014

Stripe rust severity Raite (mean % of leaf area infected) No. Treatment Rt 13DAA (g ailha) Flag Flag-1 Flag-2

1 Untreated control nil 0.05 1.20 a 1.20 2 Propiconazole 750 EC 63.5 0.00 0.18 b 0.10 3 Cracker Jack 550 EC 63.5 0.03 0.03 b 0.00 4 Propiconazole 750 EC 95.25 0.00 0.08 b 0.00 Cracker Jack 550 EC 95.25 0.05 0.08 b 0.05 6 Propiconazole 750 EC 127 0.03 0.00 b 0.00 7 Cracker Jack 550 EC 127 0.03 0.08 b 0.10 8 Propiconazole 750 EC 254 0.10 0.05 b 0.08 9 Cracker Jack 550 EC 254 0.00 0.03 b 0.00 P-value 0.5439 0.0001 0.0008 LSD (5% level) NSD tA 0.498* Factorial analysis Application rate of propiconazole 63.5 g ai/ha 0.01 0.10 0.05 95.25 g ai/ha 0.03 0.08 0.03 127 g ai/ha 0.03 0.04 0.05 254 g ai/ha 0.05 0.04 0.04 P-value 0.7749 0.5225 0.9178 LSD (5% level) NSD NSD NSD Formulation of propiconazole Propiconazole 750 EC 0.03 0.08 0.04 Cracker Jack 550 EC 0.03 0.05 0.04 P-value 0.7177 0.5774 0.8675 LSD (5% level) NSD NSD NSD Means followed by the same letter are not significantly different (P = 0.05, LSD) DAA: Days after application NSD = No significant difference due to a P-value > 0.05 tA = Data transformed using x = Arcsine square root percent (y) * = Data failed Bartlett's test and cannot be transformed for homogeneity

TABLE 8.8 Stripe rust (Pucciniastriiformis) severity on leaves of wheat cv. H45 at 20DAA, Arthurton, South Australia, 2014

Stripe rust severity Rate (mean % of leaf area infected) No. Treatment (gaia) 20DAA Flag Flag-1 Flag-2 Flag-3

1 Untreated control nil 8.93 9.80 5.03 2.83 2 Propiconazole 750 EC 63.5 0.03 0.03 0.08 0.40 3 Cracker Jack 550 EC 63.5 0.00 0.03 0.20 0.08 4 Propiconazole 750 EC 95.25 0.03 0.05 0.18 0.00 Cracker Jack 550 EC 95.25 0.00 0.03 0.28 0.10 6 Propiconazole 750 EC 127 0.00 0.00 0.13 0.08 7 Cracker Jack 550 EC 127 0.00 0.03 0.05 0.18 8 Propiconazole 750 EC 254 0.00 0.05 0.03 0.05 9 Cracker Jack 550 EC 254 0.00 0.03 0.03 0.15 P-value 0.0001 0.0001 0.0001 0.0001 LSD (5% level) 1.585* 2.799* 1.029* 0.714* Factorial analysis Application rate of propiconazole 63.5 g ai/ha 0.01 0.03 0.14 0.24 95.25 g ai/ha 0.01 0.04 0.23 0.05 127 g ai/ha 0.00 0.01 0.09 0.13 254 g ai/ha 0.00 0.04 0.03 0.10 P-value 0.631 0.797 0.3043 0.5257 LSD (5% level) NSD NSD NSD NSD Formulation of propiconazole Propiconazole 750 EC 0.01 0.03 0.10 0.13 Cracker Jack 550 EC 0.00 0.03 0.14 0.13 P-value 0.1817 0.7177 0.6201 0.8729 LSD (5% level) NSD NSD NSD NSD DAA: Days after application NSD = No significant difference due to a P-value > 0.05 * = Data failed Bartlett's test and cannot be transformed for homogeneity

TABLE 8.9 Stripe rust (Pucciniastriiformis) incidence on leaves of wheat cv. H45 at -1DAA, Arthurton, South Australia, 2014

Stripe rust incidence Rate (mean % of leaves infected) No. Treatment (gaiha) 1DAA Flag Flag-i Flag-2

1 Untreated control nil 0 3 0

TABLE 8.10 Stripe rust (Pucciniastriiformis)incidence on leaves of wheat cv. H45 at 7DAA, Arthurton, South Australia, 2014

Stripe rust incidence Rate (mean % of leaves infected) No. Treatment (gaia) 7DAA Flag Flag-i Flag-2

1 Untreated control nil 20 20 13 2 Propiconazole 750 EC 63.5 5 5 10 3 Cracker Jack 550 EC 63.5 13 5 0 4 Propiconazole 750 EC 95.25 0 0 5 Cracker Jack 550 EC 95.25 10 5 3 6 Propiconazole 750 EC 127 3 0 3 7 Cracker Jack 550 EC 127 10 5 5 8 Propiconazole 750 EC 254 0 0 0 9 Cracker Jack 550 EC 254 5 8 8 P-value 0.1791 0.0815 0.1901 LSD (5% level) NSD NSD NSD Factorial analysis Application rate of propiconazole 63.5 g ai/ha 9 5 5 95.25 g ai/ha 5 3 4 127 g a/ha 6 3 4 254g a/ha 3 4 4 P-value 0.6085 0.8554 0.9514 LSD (5% level) NSD NSD NSD Formulation of propiconazole Propiconazole 750 EC 2 1 4 Cracker Jack 550 EC 9 6 4 P-value 0.1727 0.0689 0.6376 LSD (5% level) NSD NSD NSD DAA: Days after application NSD No significant difference due to a P-value > 0.05

TABLE8.11 Stripe rust (Pucciniastriiformis) incidence on leaves of wheat cv. H45 at 13DAA, Arthurton, South Australia, 2014

Stripe rust incidence Rate (mean % of leaves infected) No. Treatment (gaia) 13DAA Flag Flag-i Flag-2

1 Untreated control nil 3 43 a 45 a 2 Propiconazole 750 EC 63.5 0 13 b 10 b 3 Cracker Jack 550 EC 63.5 3 3 bc 0 b 4 Propiconazole 750 EC 95.25 0 8 bc 0 b Cracker Jack 550 EC 95.25 5 8 bc 5 b 6 Propiconazole 750 EC 127 3 0 c 0 b 7 Cracker Jack 550 EC 127 3 8 bc 8 b 8 Propiconazole 750 EC 254 5 5 bc 5 b 9 Cracker Jack 550 EC 254 0 3 bc 0 b P-value 0.6342 0.0001 0.0001 LSD (5% level) NSD 11.9 14.83 Factorial analysis Application rate of propiconazole 63.5 g ai/ha 1 8 5 95.25 g ai/ha 3 8 3 127 g ai/ha 3 4 4 254 g ai/ha 3 4 3 P-value 0.9573 0.5978 0.8302 LSD (5% level) NSD NSD NSD Formulation of propiconazole Propiconazole 750 EC 2 6 4 Cracker Jack 550 EC 3 5 3 P-value 0.391 0.7027 0.824 LSD (5% level) NSD NSD NSD Means followed by the same letter are not significantly different (P = 0.05, LSD) DAA: Days after application NSD = No significant difference due to a P-value > 0.05

TABLE 8.12 Stripe rust (Pucciniastriiformis) incidence on leaves of wheat cv. H45 at 20DAA, Arthurton, South Australia, 2014

Stripe rust incidence (mean % of leaves infected) No. Treatment Ratea) 20DAA Flag Flag-1 Flag-2 Flag-3

1 Untreated control nil 88 a 88 a 93 a 65 a 2 Propiconazole 750 EC 63.5 3 b 3 b 8 be 18 b 3 Cracker Jack 550 EC 63.5 0 b 3 b 13 b 5 be 4 Propiconazole 750 EC 95.25 3 b 5 b 10 bc 0 c Cracker Jack 550 EC 95.25 0 b 3 b 5 be 8 be 6 Propiconazole 750 EC 127 0 b 0 b 3 c 5 be 7 Cracker Jack 550 EC 127 0 b 3 b 5 bc 5 bc 8 Propiconazole 750 EC 254 0 b 3 b 3 c 5 be 9 Cracker Jack 550 EC 254 0 b 3 b 3 c 5 be P-value 0.0001 0.0001 0.0001 0.0001 LSD (5% level) tA tA 9.65 16.63 Factorial analysis Application rate of propiconazole 63.5 g ai/ha 1 3 10 11 95.25 g ai/ha 1 4 8 4 127 g ai/ha 0 1 4 5 254 g ai/ha 0 3 3 5 P-value 0.631 0.879 0.3012 0.5125 LSD (5% level) NSD NSD NSD NSD Formulation of propiconazole Propiconazole 750 EC 1 3 6 7 Cracker Jack 550 EC 0 3 6 6 P-value 0.1817 0.8243 0.824 0.1817 LSD (5% level) NSD NSD NSD NSD Means followed by the same letter are not significantly different (P = 0.05, LSD) DAA: Days after application NSD = No significant difference due to a P-value > 0.05 tA = Data transformed using x = Arcsine square root percent (y)

DISCUSSION

[0173] At Arthurton, South Australia, in 2014, Propiconazole 750 EC at four rates was compared with Cracker Jack 550 EC to determine bioequivalence in the control of stripe rust (Puccinia striiformis) in wheat cv. H45.

[0174] No crop phytotoxicity was observed in any treatment at any assessment timing (Table 1). All treatments except for Cracker Jack at the low rate of 63.5 g ai/ha recorded significantly higher grain yield higher compared to the untreated control (Table 2). This yield response could be attributed to the control of stripe rust disease.

[0175] All application rates of Propiconazole recorded statistically equivalent grain yield when compared to the corresponding rates of Cracker Jack. Applying propiconazole at 254 g ai/ha resulted in significantly higher grain yield compared to 63.5, 95.25 and 127 g ai/ha application rates.

[0176] Initial assessments found negligible levels of stripe rust in the trial site prior to application (Table 3). The disease evolved slowly initially, but by 20 days after application (DAA) stripe rust was of high incidence and moderate severity in the untreated control.

[0177] The corresponding application rates of Propiconazole and Cracker Jack recorded statistically equivalent stripe rust severity and incidence in assessments at 7, 13 and 20DAA, while the factorial analysis comparing Propiconazole formulation found no significant difference between the two formulations at any assessment timing.

[0178] According to the factorial analysis comparing application rate, there was no significant rate response observed at any assessment timing.

However, there was a numerical response to rate of application, with lower disease incidence appearing in higher rates of application.

CONCLUSIONS ON BIOEQUIVALENCE

[0179] No crop phytotoxicity was observed in any treatment at any assessment timing.

[0180] The corresponding application rates of Propiconazole 750 EC and Cracker Jack 550 EC recorded statistically equivalent grain yield.

[0181] A significant rate response was evident for the application rate of propiconazole, which could be correlated to increased levels of stripe rust control.

[0182] The corresponding application rates of Propiconazole 750 EC and Cracker Jack 550 EC recorded statistically equivalent stripe rust severity and incidence in assessments at all assessment timings.

[0183] Propiconazole 750 EC and Cracker Jack 550 EC were statistically equivalent in terms of crop safety and stripe rust control in wheat cv. H45.

APPENDICES

TABLE 8.13 Appendix i. Trial details

SITE DETAILS

Grower Ian Westbrook

Location Kulpara-Maitland Road, Arthurton, South Australia

GPS co-ordinates -34.185615, 137.821501

Soil type Loam over limestone

Crop Wheat

Variety H45

Trial design Factorial design

Replications 4

Plot size 1.75 mx 10 m

Row spacing 250 mm

Sowing rate 85 kg/ha

Sowing date 17/05/14

Fertiliser Granulock Z 25 @ 80 kg/ha

Harvest date 05/11/14

[0153] The complete disclosures of the patents, patent documents and publications cited herein are incorporated by reference in their entirety as if each were individually incorporated. Various modifications and alterations to this invention will become apparent to those skilled in the art without departing from the scope and spirit of this invention. It should be understood that this invention is not intended to be unduly limited by the illustrative embodiments and examples set forth herein and that such examples and embodiments are presented by way of example only with the scope of the invention intended to be limited only by the claims set forth herein as follows.

[0154] Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" and "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.

[0155] The reference in this specification to any prior art publication (or information derived from it), or to any matter is known, is not, and should not be taken as an acknowledgment or admission or any form of suggestion that that prior art publication (or information derived from it) or known matter forms part of the common general knowledge in the field of endeavour to which this specification relates.

Claims (20)

1. An emulsifiable concentrate formulation comprising:

propiconazole at a concentration of at least about 800g/L;

at least one agriculturally acceptable surfactant selected from the group consisting of an alkoxylated alkylphenol, an alkoxylated tristyryl phenol, an alkyl or aryl or alkylaryl sulfonate, an alkoxylated amine, an alkoxylated alkyl amine, an alkoxylated tallow amine, an alkoxylated oleil amine, an ether sulphate and any combination thereof; and

at least one agriculturally acceptable solvent selected from the group consisting of an aromatic hydrocarbon, a lactam, a ketone and any combination thereof.

2. The formulation of Claim 1, wherein the surfactant is selected from the group consisting of an alkoxylated nonylphenol, an ethoxylated tristyryl phenol, a calcium dodecylbenzene sulfonate, an ethoxylated alkyl amine, an alkylphenol ether sulphate, an ethoxylated tallow amine, an ethoxylated oleil amine and any combination thereof.

3. The formulation of Claim 1 or Claim 2, wherein the solvent is selected from the group consisting of an aromatic hydrocarbon, a pyrrolidone, a cyclic ketone, and any combination thereof.

4. The formulation of Claim 3, wherein the agriculturally acceptable solvent is selected from the group consisting of solvent naphtha (petroleum) heavy aromatic, N-methyl pyrrolidone, isophorone, and any combination thereof.

5. The formulation of any one of the preceding claims, wherein the weight ratio of propiconazole to a non-herbicide portion of the emulsifiable concentrate formulation is at least 2.

6. The formulation of any one of the preceding claims, wherein the weight ratio of propiconazole to the solvent is at least 2.5.

7. The formulation of any one of the preceding claims, wherein the weight ratio of propiconazole to the surfactant is at least 4.

8. The formulation of any one of the preceding claims, wherein the concentration of the solvent is about 50 to about 350 g/L.

9. The formulation of Claim 8, wherein the concentration of the solvent is about 200 to about 300 g/L.

10. The formulation of any one of the preceding claims, wherein the concentration of the surfactant is about 25 to about 200 g/L.

11. The formulation of Claim 10, wherein the concentration of the surfactant is about 40 to about 150 g/L.

12. The formulation of any one of the preceding claims, wherein the surfactant is selected from the group consisting of a non-ionic surfactant, an anionic surfactant, a cationic surfactant, a zwitterionic surfactant, a cation-anion composite surfactant and any combination thereof.

13. The formulation of Claim 12, wherein surfactant comprises at least one anionic surfactant and at least one non-ionic surfactant.

14. The formulation of Claim 12, wherein the surfactant comprises at least one cation-anion composite surfactant and at least one non-ionic surfactant.

15. The formulation of any one of Claims 12 to 14, wherein the concentration of the non ionic surfactant is about 10 to about 80 g/L.

16. The formulation of Claim 12 or Claim 14, wherein the concentration of the cationic anionic composite surfactant is about 20 to about 150 g/L.

17. The formulation of Claim 12 or Claim 13, wherein the concentration of the anionic surfactant is about 20 to about 150 g/L.

18. A method of preparing an emulsifiable concentrate formulation according to any one of the preceding claims including the steps of:

(a) adding propiconazole to a vessel, wherein propiconazole is present at a concentration of at least about 800g/L of the emulsifiable concentrate formulation;

(b) adding at least one agriculturally acceptable solvent to the vessel, the at least one agriculturally acceptable surfactant selected from the group consisting of an alkoxylated alkylphenol, an alkoxylated tristyryl phenol, an alkyl or aryl or alkylaryl sulfonate, an alkoxylated amine, an alkoxylated alkyl amine, an alkoxylated tallow amine, an alkoxylated oleil amine, an ether sulphate and any combination thereof;

(c) adding at least one agriculturally acceptable surfactant to the vessel, the at least one agriculturally acceptable solvent selected from the group consisting of an aromatic hydrocarbon, a lactam, a ketone and any combination thereof; and

(d) mixing the vessel so as to facilitate uniformity of the emulsifiable concentrate formulation.

19. An emulsifiable concentrate formulation prepared by the method according to Claim 18.

20. A method of controlling fungal growth in a target crop including the step of applying to the target crop a fungicidally-effective amount of an emulsifiable concentrate formulation according to any one of Claims I to 17 and 19.