AU2017214765A1 - Emulsifiable concentrate formulation - Google Patents

Abstract

An emulsifiable concentrate formulation including as active agents prosulfocarb and triallate and also including at least one agriculturally acceptable surfactant, selected from the group consisting of an alkoxylated alcohol, an alkoxylated alkylphenol, an alkoxylated tristyryl phenol, an alkoxylated oil, and an alkyl or aryl or alkylaryl sulfonate; wherein the sum of concentrations of prosulfocarb and triallate in the emulsifiable concentrate formulation is greater than 500 g/L and more preferably greater than 700 g/L and even more preferably greater than 900 g/L is provided. Also provided are methods of making the emulsifiable concentrate formulation as well as a method of controlling weeds in a target crop by application of the emulsifiable concentrate formulation thereto.

Description

EMULSIFIABLE CONCENTRATE FORMULATION

FIELD OF THE INVENTION

This invention relates to multi-active pre-emergence herbicides formulated as emulsión concentrates. In particular this invention relates to emulsión concéntrate formulations that contain both prosulfocarb and triábate.

BACKGROUND OF THE INVENTION

Prosulfocarb (also known as S-Benzyl dipropylthiocarbamate, and as S-(phenylmethyl)dipropylcarbamothioate) is in the thiocarbamate family of herbicides and has a mode of action based on the inhibition of lipid synthesis. Prosulfocarb is root-absorbed (below the seed), and when the root system of the weed extends beyond the prosulfocarb zone, the weed can survive. Technical grade prosulfocarb material has a melting point of approximately -20°C and a solubility in water of 13 mg/L at 20°C. Uptake of prosulfocarb by a plant is assisted by soil moisture.

Triábate (also known as S-(2,3,3-trichloro-2-propenyl) bis (1-methylethyl)carbamethioate) is also in the thiocarbamate family of herbicides and also has a mode of action based on the inhibition of fat synthesis. However, triábate is absorbed by the coleoptile of the weed (above the seed), and uptake occurs via the absorption of triábate vapour. Triábate has a melting point of 2930° and a solubility in water of 4 mg/L.

The use of prosulfocarb and triábate in combination can be advantageous in agronomic scenarios where weeds exhibit mixed seed-bank physiology. Use in combination may enable better weed control when the weeds are present at a range of growth stages and this allows a farmer greater flexibility in the timing of herbicide application. The mode of action of prosulfocarb differs from that of triábate in a way that enables the herbicide combination to be more effective against resistant weeds (e.g. resistant ryegrass) than use of either prosulfocarb alone or triábate alone.

If a farmer wants to apply both prosulfocarb and triábate to a field through a multi-nozzle spray rig, that farmer may separately add a single-active emulsifiable concéntrate of prosulfocarb and a single-active emulsifiable concéntrate of triábate to the spray water tank of his spray rig (this is cabed tank mixing). Disadvantages of tank-mix methodology inelude: ♦ The requirement to transport and handle twice as many containers ♦ The requirement to safely dispose of twice as many empty containers ♦ The capacity to make a mistake in the mixing ratio (this is particularly problematic when farm labourers are not well-educated) ♦ The need for label instructions to be more complex , and to be co-ordinated between 2 sepárate containers ♦ The need to have more carrier solvents than are required in a one-pack formulation ♦ Lower emulsión quality where actives are introduced into the spray water tank via sepárate formulations as opposed to the jointly optimised emulsión of a combined actives formulation

In “Herbicide Efficacy in No-Till Farming Systems in Southern NSW 2010”, Grassroots Agronomy, Greg Condon and Kirrily Condon (GRDC funded project), there is reference to use of a tank mix of Boxer Gold (2.5 L/ha) and Avadex Xtra (1.6 L/ha). Boxer Gold is an emulsifiable concéntrate that contains 800g/L prosulfocarb in coformulation with 120g/L s-metolachlor. Avadex Xtra is an emulsifiable concéntrate with 500g/L triábate.

SUMMARY OF THE INVENTION

The present invention is directed to an emulsifiable concéntrate formulation and methods of use thereof.

In a first aspect, the invention provides an emulsifiable concéntrate formulation comprising prosulfocarb and triallate, and further comprising at least one solid, liquid or liquid-containing agriculturally acceptable surfactant selected from the group consisting of an alkoxylated alcohol, an alkoxylated alkylphenol, an alkoxylated tristyryl phenol, an alkoxylated oil, an alkyl or aryl or alkylaryl sulfonate, and any combination therein, wherein the sum of concentrations of prosulfocarb and triábate in the emulsifiable concéntrate formulation is greater than 500 g/L.

Suitably, the weight ratio of prosulfocarb to triábate is in the range of about 3:1 to about 1:1.

Suitably, the weight ratio of prosulfocarb and triábate combined to a nonherbicide portion of the emulsifiable concéntrate formulation is at least 5:1.

In one embodiment, the weight ratio of prosulfocarb and triábate combined to the agriculturally acceptable surfactant in the concéntrate is at least 6:1.

Suitably, the emulsifiable concéntrate formulation of the present aspect further comprises an agriculturally acceptable solvent. Preferably, the weight ratio of prosulfocarb and triábate combined to the agriculturally acceptable solvent is at least 10:1.

The agriculturally acceptable solvent is suitably selected from the group consisting of an ester, a ketone, a lactam, an amide, a hydrocarbon and any combination thereof. Preferably, the agriculturally acceptable solvent is selected from the group consisting of a simple ketone, an aromatic ketone, a cyclic ketone, an acétate ester, an alkyl benzoate ester, a pyrrolidone, an aromatic hydrocarbon and any combination thereof. Even more preferably, the agriculturally acceptable solvent is selected from the group consisting of acetone, acetophenone, ethyl benzoate, a heptyl acétate ester, isophorone, methyl benzoate, N-methyl pyrrolidone, propiophenone, solvent naphtha (petroleum) heavy aromatic and any combination thereof.

In one embodiment, the concéntrate ineludes about 400 to about 800 g/L prosulfocarb and about 150 to about 600 g/L triallate.

In one embodiment, the at least one agriculturally acceptable solid, liquid or liquid-containing surfactant is selected from the group consisting of an alkoxylated polypropyleneglycol, an alkoxylated nonylphenol, a castor oil ethoxylate, an ethoxylated tristyryl phenol, a calcium dodecylbenzene sulfonate and any combination thereof.

For the present aspect, the at least one agriculturally acceptable solid, liquid or liquid-containing surfactant is suitably selected from the group consisting of non-ionic surfactants, anionic surfactants, cationic surfactants, zwitterionic surfactants, cation-anion composite surfactants and any combination thereof.

Suitably, the at least one agriculturally acceptable solid, liquid or liquid-containing surfactant is present at a concentration of at least about 50 g/L.

Suitably, the at least one agriculturally acceptable solid, liquid or liquid-containing surfactant is or comprises a non-ionic surfactant selected from the group consisting of an alkoxylated alcohol, an alkoxylated alkylphenol, an alkoxylated tristyryl phenol, an alkoxylated oil and any combination thereof. Preferably, the non-ionic surfactant is selected from the group consisting of an alkoxylated polypropyleneglycol, an alkoxylated nonylphenol, a castor oil ethoxylate, an ethoxylated tristyryl phenol and any combination thereof.

In particular embodiments, the non-ionic surfactant is present at about 10 to about 100 g/L in the formulation.

In one embodiment, the at least one agriculturally acceptable solid, liquid or liquid-containing surfactant is or comprises an anionic surfactant. Preferably, the anionic surfactant is or comprises an alkyl or aryl or alkylaryl sulfonate. Even more preferably, the anionic surfactant is or comprises a calcium alkylbenzene sulfonate salt, optionally in a liquid solvent carrier.

In particular embodiments, the anionic surfactant is present in the range of about 10 to about 100 g/L.

In one 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.

The emulsifiable concéntrate formulation of the present aspect suitably comprises about 600 to about 750 g/L prosulfocarb, about 300 to about 400 g/L triallate, about 0 to about 50 g/L of an agriculturally acceptable solvent, about 20 to about 30 g/L of a non-ionic surfactant, and about 25 to about 32 g/L of an anionic surfactant.

In a second aspect, the invention provides a method of preparing a concéntrate according to the first aspect including the steps of (a) adding prosulfocarb to a vessel; (b) adding triallate to the vessel; (c) adding at least one agriculturally acceptable surfactant to the vessel; and (d) agitating the vessel so as to facilítate uniformity of the concéntrate.

Suitably, the method of the present aspect further ineludes the step of adding an agriculturally acceptable solvent to the vessel prior to step (d).

In a third aspect, the invention provides a method of controlling weeds in a target crop including the step of applying to the target crop a diluted emulsión of an emulsifiable concéntrate formulation of prosulfocarb and triallate at a rate of about 1 to about 8 L/ha based on volume of the emulsifiable concéntrate formulation.

Suitably, the emulsifiable concéntrate formulation is that of the first aspect.

As used herein, except where the context requires otherwise, the term “comprisé" and variations of the term, such as “comprising”, “comprises” and “comprised”, are not intended to exelude further elements, components, integers or steps but may inelude 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 ineludes one surfactant, one or more surfactants and a plurality of surfactants.

DETAILED DESCRIPTION

To overeóme the aforementioned deficiencies it would be desirable to provide for an emulsifiable concéntrate (EC) combining prosulfocarb and triallate. There is a tendeney 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.

In view of the above, the present invention is at least partly predicated on the surprising discovery that prosulfocarb in a liquid form can assist in solubilising triallate in a co-formulation of prosulfocarb and triallate together with an agriculturally acceptable surfactant. This is important because the level of agriculturally acceptable solubilising agents, such as surfactants and solvents, in the formulations can be significantly decreased relative to triallate single-active formulations so as to achieve a highly concentrated formulation.

Accordingly, in one broad aspect, the invention provides an emulsifiable concéntrate formulation comprising prosulfocarb and triallate, and further comprising at least one solid, liquid or liquid-containing agriculturally acceptable surfactant, wherein the sum of concentrations of prosulfocarb and triallate in the emulsifiable concéntrate formulation is greater than 500 g/L.

In a related aspect, the invention provides an emulsifiable concéntrate formulation comprising prosulfocarb and triallate, and further comprising at least one solid, liquid or liquid-containing agriculturally acceptable surfactant selected from the group consisting of an alkoxylated alcohol, an alkoxylated alkylphenol, an alkoxylated tristyryl phenol, an alkoxylated oil, an alkyl or aryl or alkylaryl sulfonate, and any combination therein, wherein the sum of concentrations of prosulfocarb and triallate in the emulsifiable concéntrate formulation is greater than 500 g/L.

The term ''agriculturally accepíable'' as used herein 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.

For the present aspect, the sum of concentrations of prosulfocarb and triallate in the emulsifiable concéntrate formulation is suitably greater than 500 g/L, preferably greater than 700 g/L, more preferably greater than 800 g/L, even more preferably greater than 900 g/L. In particular embodiments, the sum of concentrations of prosulfocarb and triallate in the emulsifiable concéntrate formulation is about 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690, 700, 710, 720, 730, 740, 750, 760, 770, 780, 790, 800, 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, 1090, 1100 g/L or any range therein.

With respect to the concéntrate of the present aspect, prosulfocarb may be present in a concentration of about 400 g/L to about 800 g/L prosulfocarb or any range therein, such as, but not limited to, about 450 g/L to about 750 g/L, about 500 g/L to about 700 g/L, or about 550 g/L to about 650 g/L. In particular embodiments, prosulfocarb is present in a concentration of about 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690, 700, 710, 720, 730, 740, 750, 760, 770, 780, 790, 800 g/L or any range therein. In certain embodiments of the present invention, prosulfocarb is present in a concentration of about 600 g/L to about 700 g/L.

Suitably, triallate is present in the emulsifiable concéntrate formulation of the invention at a concentration of about 150 g/L to about 600 g/L triallate or any range therein, such as, but not limited to, about 200 g/L to about 500 g/L, about 250 g/L to about 450 g/L, or about 300 g/L to about 350 g/L. In particular embodiments, triallate is present in a concentration of about 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, g/L or any range therein. In one preferred embodiment, triallate is present in a concentration of about 300 g/L to about 350 g/L.

Suitably, the weight ratio of prosulfocarb to triallate is in the range of about 3:1 to about 1:1. It will be appreciated that the weight ratio of prosulfocarb to triallate may be, for example, 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 or any range therein. Preferably, the weight ratio of prosulfocarb to triallate is in the range of about 2.5:1 to about 1.5:1.

Suitably, the weight ratio of the sum of prosulfocarb and triallate to a nonherbicide portion of the emulsifiable concéntrate formulation is at least 5:1 (e.g., 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1, 9.5:1, 10:1, 10.5:1, 11:1, 11.5:1, 12:1, 12.5:1, 13:1, 13.5:1, 14:1, 14.5:1, 15:1 or any range therein). It will be appreciated that the non-herbicide portion of the emulsifiable concéntrate 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 prosulfocarb and triallate combined to the non-herbicide portion of the formulation is at least 7:1, more preferably at least 8:1, and even more preferably at least 10:1.

Preferably, the weight ratio of prosulfocarb and triallate combined to the agriculturally acceptable surfactant in the concéntrate is at least 6:1 (e.g., 6:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1, 9.5:1, 10:1, 10.5:1, 11:1, 11.5:1, 12:1, 12.5:1, 13:1, 13.5:1, 14:1, 14.5:1, 15:1 or any range therein). In further embodiments, the weight ratio of prosulfocarb and triallate combined to the agriculturally acceptable surfactant in the concéntrate is at least 8:1 and even more preferably at least 10:1.

Suitably, the at least one agriculturally acceptable surfactant is present in the emulsifiable concéntrate formulation of the invention at a concentration of about 40 g/L to about 100 g/L or any range therein, such as, but not limited to, about 50 g/L to about 90 g/L, about 60 g/L to about 80 g/L, or about 55 g/L to about 75 g/L. In particular embodiments, the at least one agriculturally acceptable surfactant is present in a concentration of about 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, 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 g/L or any range therein. In one preferred embodiment, the at least one agriculturally acceptable surfactant is present in a concentration of about 50 g/L to about 60 g/L.

Accordingly, in particular embodiments, the at least one agriculturally acceptable surfactant is present at a concentration of at least about 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, 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 g/L or any range therein.

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.

Suitably, the at least one agriculturally acceptable solid, liquid or liquid-containing surfactant is selected from the group consisting of an alkoxylated alcohol, an ethoxylated tristyryl phenol, a castor oil ethoxylate, an alkoxylated nonylphenol, a calcium dodecylbenzene sulfonate and any combination thereof. Preferably, the at least one agriculturally acceptable solid, liquid or liquid-containing surfactant is selected from the group consisting of an alkoxylated polypropyleneglycol (e.g., Termul 203), an alkyl polyoxyalkylene ether, an ethylene oxide-propylene oxide block co-polymer (e.g., Termul 203), an alkoxylated nonylphenol (e.g., Termul 200), a castor oil ethoxylate, such as a castor oil-54-ΕΟ (e.g., Termul 1285), an ethoxylated tristyryl phenol, such as a tristyryl-16-EO (e.g., Termul 3150), a calcium dodecylbenzene sulfonate (e.g., Ninate 60E, Kemmat HF60, Rhodacal 70), and any combination thereof.

In particular embodiments, the at least one agriculturally acceptable solid, liquid or liquid-containing surfactant is not a nonylphenol-20-ΕΟ (e.g., Teric N20), a nonylphenol-30-ΕΟ (e.g., Teric N30) or a EO/PO block copolymer nonylphenol ethoxylate (e.g., Teric PE64 and Teric PE68).

In particular embodiments, the at least one agriculturally acceptable solid, liquid or liquid-containing surfactant is or comprises a non-ionic surfactant selected from the group consisting of an alkoxylated alcohol, an alkoxylated alkylphenol, an alkoxylated tristyryl phenol, an alkoxylated oil and any combination thereof. Preferably, the non-ionic surfactant is selected from the group consisting of an alkoxylated polypropyleneglycol (e.g., Termul 203), an alkoxylated nonylphenol (e.g., Termul 200), a castor oil ethoxylate, such as a castor oil-54-ΕΟ (e.g., Termul 1285), an ethoxylated tristyryl phenol, such as a tristyryl-16-EO (e.g., Termul 3150) and any combination thereof.

In particular embodiments, the non-ionic surfactant is present at about 10 to about 100 g/L in the formulation, or any range therein, such as, but not limited to, about 20 g/L to about 80 g/L, about 25 g/L to about 35 g/L, or about 50 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, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, 15, 15.5, 16, 16.5, 17, 17.5, 18, 18.5, 19, 19.5, 20, 20.5, 21, 21.5, 22, 22.5, 23, 23.5, 24, 24.5, 25, 25.5, 26, 26.5, 27, 27.5, 28, 28.5, 29, 29.5, 30, 30.5, 31, 31.5, 32, 32.5, 33, 33.5, 34, 34.5 35, 35.5, 36, 36.5, 37, 37.5, 38, 38.5, 39, 39.5, 40, 40.5, 41, 41.5, 42, 42.5, 43, 43.5, 44, 44.5, 45, 45.5, 46, 46.5, 47, 47.5, 48, 48.5, 49, 49.5, 50, 50.5, 51, 51.5, 52, 52.5, 53, 53.5, 54, 54.5, 55, 55.5, 56, 56.5, 57, 57.5, 58, 58.5, 59, 59.5, 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 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 30 g/L and more preferably about 25 g/L to about 28 g/L. In other embodiments, the non-ionic surfactant is present in a concentration of about 40 g/L to about 60 g/L and more preferably about 52 g/L to about 58 g/L.

Suitably, the at least one agriculturally acceptable solid, liquid or liquid-containing surfactant is or comprises an anionic surfactant. Preferably, the anionic surfactant is or comprises an alkyl or aryl or alkylaryl sulfonate. Even more preferably, the anionic surfactant is or comprises a calcium alkylbenzene sulfonate salt, optionally in a liquid solvent carrier. Suitably, the alkyl moiety of the calcium alkylbenzene sulfonate salt, which may be straight or branched, is C8-C14 alkyl. Preferably the alkyl moiety is C10-02 alkyl.

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. By way of example, for those triáis listed in Table 2, 48.6 g/L of Ninate 60E is equivalent to only 29.2 g/L of surfactant, which when combined with 26.3 g/L of non-ionic surfactant (e.g., Termul 200 or equivalent) equals 55.5 g/L of surfactant in these embodiments.

For the formulation of the present invention, the anionic surfactant may be present in a concentration of about 10 to about 100 g/L in the formulation, or any range therein, such as, but not limited to, about 20 g/L to about 80 g/L, about 25 g/L to about 35 g/L, or about 50 g/L to about 60 g/L. In particular embodiments of the present invention, the anionic surfactant is present in a concentration of about 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, 15, 15.5, 16, 16.5, 17, 17.5, 18, 18.5, 19, 19.5, 20, 20.5, 21, 21.5, 22, 22.5, 23, 23.5, 24, 24.5, 25, 25.5, 26, 26.5, 27, 27.5, 28, 28.5, 29, 29.5, 30, 30.5, 31, 31.5, 32, 32.5, 33, 33.5, 34, 34.5 35, 35.5, 36, 36.5, 37, 37.5, 38, 38.5, 39, 39.5, 40, 40.5, 41, 41.5, 42, 42.5, 43, 43.5, 44, 44.5, 45, 45.5, 46, 46.5, 47, 47.5, 48, 48.5, 49, 49.5, 50, 50.5, 51, 51.5, 52, 52.5, 53, 53.5, 54, 54.5, 55, 55.5, 56, 56.5, 57, 57.5, 58, 58.5, 59, 59.5, 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 g/L or any range therein. In particular embodiments, the anionic surfactant is present in a concentration of about 20 g/L to about 30 g/L and more preferably about 25 g/L to about 28 g/L.. In other embodiments, the anionic surfactant is present in a concentration of about 40 g/L to about 60 g/L and more preferably about 52 g/L to about 58 g/L.

Suitably, the emulsifiable concéntrate formulation of the present further comprises an agriculturally acceptable solvent. Preferably, the weight ratio of prosulfocarb and triallate combined to the agriculturally acceptable solvent is at least 6:1, preferably at least 10:1, and more preferably at least 15:1.

The agriculturally acceptable solvent may be any as are known in the art, such as aliphatic paraffmic oils, aromatic solvents, C6-C16 aromatic solvents, chlorinated hydrocarbons, alcohols, ketones, ethers, esters, vegetable oils, methylated vegetable oils, petroleum fractions, sugar esters of fatty acids, alkane compounds, aryl compounds, alkylaryl compounds, heterocyclic compounds, lactams, amides, xylene, toluene, pyrrolidones, substituted pyrrolidones, glycol ethers, and end-capped glycol ethers.

In exemplary embodiments, the agriculturally acceptable solvent is selected from the group consisting of an ester, a ketone, a lactam, an amide, a hydrocarbon and any combination thereof. Preferably, the agriculturally acceptable solvent is selected from the group consisting of a simple ketone, an aromatic ketone, a cyclic ketone, an acétate ester, an alkyl benzoate ester, a pyrrolidone, an aromatic hydrocarbon and any combination thereof. Even more preferably, the agriculturally acceptable solvent is selected from the group consisting of acetone, acetophenone, ethyl benzoate, a heptyl acétate ester, isophorone, methyl benzoate, N-methyl pyrrolidone, propiophenone, solvent naphtha (petroleum) heavy aromatic and any combination thereof.

Referring to the ratios for the emulsifiable concéntrate formulation described herein, such as the ratio of a herbicide component (i.e., prosulfocarb plus triallate) to a non-herbicide portion (e.g., surfactant and/or solvent), the ratio of the herbicide component to a solvent, and the ratio of the herbicide component (prosulfocarb plus triallate) to a surfactant, are important quality parameters for an EC formulation as the ratios affect: (a) the quantity of solvent released to the environment as a consequence of applying a given amount of herbicide to a cultivation zone; (b) the amount of high-quality packing material that is utilised in carrying a given amount of herbicide to a cultivation zone; (c) he amount of used packaging material that needs to be recycled or otherwise disposed of after applying a given amount of herbicide to a cultivation zone; (d) the contact toxicity of the EC formulation; and (e) the flammability of the EC formulation.

In a related aspect, the invention provides a method of preparing an emulsifiable concéntrate formulation according to the aforementioned aspect including the steps of: (a) adding prosulfocarb to a vessel; (b) adding triallate to the vessel; (c) adding at least one agriculturally acceptable surfactant to the vessel; and (d) mixing the vessel so as to facilítate uniformity of the emulsifiable concéntrate formulation.

Suitably, the method of the present aspect further ineludes the step of adding an agriculturally acceptable solvent, such as that hereinbefore described, to the vessel prior to step (d).

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 prosulfocarb, triallate, surfactant and optionally solvent may be mixed by any means known in the art.

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 polypropyleneglycol, an alkoxylated nonylphenol, a castor oil ethoxylate, an ethoxylated tristyryl phenol, a calcium dodecylbenzene sulfonate and any combination thereof.

Suitably, the method of the present aspect is performed at about 30°C or above so as to facilítate melting of the triallate.

It will be appreciated that the triallate, prosulfocarb, surfactant and optionally solvent may be added to the vessel in any order. By way of example, prosulfocarb may be added to the vessel after the addition of triallate.

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

The present emulsifiable concéntrate formulations provide for a number of advantages in both formulation and use. One particularly advantageous feature is that the formulations are storage stable in ultra-low temperature storage conditions. This is important in cold-temperature markets such as Cañada as well as for the common practice of low temperature longer term storage of such formulations. By way of example, the embodiment described in table 1.1 was placed in a freezer at -17 °C for 2 weeks. On removal from the freezer, the formulation was found not to have crystallised. By contrast a prior art formulation of triallate was found to have extensively crystallised under these conditions.

In a further aspect, the invention provides a method of controlling weeds in a target crop including the step of applying to the target crop a diluted emulsión of an emulsifiable concéntrate formulation of prosulfocarb and triallate at a rate of about 1 to about 8 L/ha based on volume of the emulsifiable concéntrate.

Suitably, the emulsifiable concéntrate formulation is that of the first aspect.

Given the above, the application rate (based on volume of the emulsifiable concéntrate) may be about 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7.0, 7.5, 8 L/ha and any range therein. Preferably, the application rate is in the range of about 2 L/ha to about 5 L/ha, and even more preferably about 3 L/ha to about 4 L/ha.

The various features and embodiments of the present invention, referred to in individual sections above apply, as appropriate, to other sections, mutatis mutandis. Consequently features specified in one section may be combined with features specified in other sections as appropriate.

The following examples are provided by way of illustration only and are in no way limiting upon the scope of the invention.

EXAMPLES EXAMPLE1

The following prosulfocarb/triallate emulsifiable concéntrate formulation according to the invention was made by mixing the components in table 1.1 in the amounts shown therein.

TABLE 1

In the above formulation, prosulfocarb is present at 0.985x671.4= 661 parts by 5 weight and the triallate is present at 333 parts by weight, and solubilising moiety is present at 3.8 (Recosol 200)+ 0.4x47.7(solvent component of Ninate 60E) = 22.9 parts by weight. The ratio of (prosulfocarb + triallate) to solubilising moiety is 994/22.9 = 43.4. The ratio of (prosulfocarb+triallate) to solvent is 994/3.8 = 262. 10 Example la

Method of Manufacture

Prosulfocarb 666 + Triallate 333 EC Herbicide

Formulation of a nominally 10000L batch of product, inclusive of quality control measures, is as foliows: 1.1. Ensure formulation vessel is empty and clean 1.2. Charge active ingredient as follows to the formulation vessel with ongoing agitation:

1.3. Charge the surfactants as follows, clearing residual surfactant from any pumps or process lines used with the remaining complement of solvent:

1.4. Continué agitating for a mínimum of 30 minutes following the last ingredient’s addition 1.5. Sample approximately 1L of product, ensuring it is representative 1.6. Sub-sample 250mL from the original 1L sample, and subject it to the following testing regime. 1.6.1. Specific gravity (CIPAC MT3.1) 1.6.2. pH 1% aqueous (CIPAC MT75.3) 1.6.3. Emulsión characteristics (CIPAC MT36.1) 1.6.4. Persistent foam (CIPAC MT47.2) 1.6.5. Active constituent (Prosulfocarb) contení (validated method) 1.6.6. Active constituent (Triallate) contení (validated method) 1.7. If specific gravity is within the bounds of the acceptable range listed in the specification, record the valué and proceed to the next test. If specific gravity is outside of the bounds of the acceptable range listed in the specification, agítate the formulation charge until specific gravity is constant. 1.8. If pH 1% aqueous is satifactory, record results and proceed to the next test. 1.9. If emulsión stability in standard hard water is satifactory, record results and proceed to the next test. If emulsión stability is outside the bounds of the acceptable range listed in the specification, adjust the contents of surfactants (Alkyl polyoxyalkylene ether (eg. Termul 203) and/or Alkylbenzenesulfonic acid, calcium salt in 2-ethylhexanol (eg. Ninate 60E)) as necessary. After suitable agitation time to ensure homogeneity, resample and retest. Repeat adjustment process until emulsión stability is within the bounds of the acceptable range. 1.10. If persistent foaming characteristics are satifactory, record results and proceed to the next test. 1.11. 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 aromatic 200 solvent (for high active contení) or additional prosulfocarb and/or triallate active constituent (for low active contení). 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. 1.12. Catalogue and store a retention sample of approximately 200g 1.13. Generate a certifícate of analysis noting results of testing 1.14. Issue quality clearance giving authority to package goods 1.15. Package the fmished goods ensuring both the batch number and manufacturing date is noted on the label. EXAMPLE 2

Triáis by variation of surfactant (Non-ionic: eg. Termul 200, Termul 1285, Termul 3150) (An-ionic: eg. Kemmat HF60, Rhodacal 70) 1. The original surfactants that were used for the Prosulfocarb 666 g/L Triallate 333g/L Emulsifiable concéntrate is a combination of an anionic surfactant - Calcium Dodecylbenzene Sulphonate (eg. Ninate 60E) and a non-ionic surfactant - alcohol alkoxylate (eg. Termul 203) with a surfactant concentration ratio of 65:35. Solvent used is solvent naphtha (petroleum), heavy aromatic (eg. Recosol 200). 2. Triáis by varying the surfactants (non-ionic and anionics) were done by substituting the surfactant pairings with the original surfactants used in the formulation. • Triáis 2.1 to 2.3 are for the substitution of the non-ionic surfactants with alternatives while the anionic surfactant (Ninate 60 E) is kept constant. The non-ionic surfactants inelude alcohol alkoxylates (Termul 203) ethoxylated tristyryl phenol (eg. Termul 3150), castor oil ethoxylate (eg. Termul 1285) and alkoxylated alkyl phenol (eg. Termul 200) gave favourable results in terms of coid temperature stability, emulsión characteristics and viscosity. • Triáis 2.4 to 2.5 are for the substitution of anionic surfactants with alternatives and the non-ionic surfactant (Termul 203) is kept constant. The Calcium dodecylbenzene sulfonates, linear (eg. Kemmat HF60) and branched (eg. Rhodacal 70), produced favorable results in terms of emulsión characteristics, coid temperature stability and viscosity.

TABLE 2: VARIATION OF SURFACTANTS

Legend: E - Emulsión characteristics done at 5% aq. CTS - Coid temp stability at 2deg. C P- Pass F- Fail

Trial # 2.1

Prosulfocarb active present at 666 g/L Triallate active present at 333 g/L 5 Trial details: Triáis by variation of non-ionic surfactants

Non-ionic surfactant/ Anionic/Solvent used: Termul 200/ Ninate 60E/ Recosol 200

FORMULA TION

Trial # 2.2 5

Prosulfocarb active present at 666 g/L

T'iMollofT^ncnrit ot rr/T

Trial details: Triáis by variation of surfactant

Non-ionic surfactant/ Anionic/Solvent used: Termull285 / Ninate 60E/ R200 5

FORMULA TION

Trial # 2.3

5 Prosulfocarb active present at 666 g/L

Triallate active present at 333 g/L

Trial details: Triáis by variation of surfactant

Non-ionic surfactant/ Anionic/Solvent used: T3150 / Ninate 60E/ R200 5 _FORMULATION____

Trial # 2.4

Prosulfocarb active present at 666 g/L 5 Triallate active present at 333 g/L

Trial details: Triáis by variation of anionic surfactants

Non-ionic surfactant/ Anionic/Solvent used: T203/Kemmat HF60/ Recosol 200 10 FORMULATION_

Trial # 2.5

Prosulfocarb active present at 666 g/L 5 Triallate active present at 333 g/L

Trial details: Triáis by variation of anionic surfactants

Non-ionic surfactant/ Anionic/Solvent used: T203 /Rhodacal 70 / Recosol 200 ΓΠΡΜΤΤΤ ΑΤΤΠΝ

EXAMPLE 3

Triáis by variation of solvent used. (eg. Acetone, Methyl benzoate, Propiophenone, Isophorone, Acetophenone, Ethyl benzoate, Recosol 150, Exxate 700, NMP) 1. The original surfactants that were used for the Prosulfocarb 666 g/L Triallate 333g/L emulsifiable concéntrate is a combination of an anionic surfactant - Calcium Dodecylbenzene Sulphonate (eg. Ninate 60E) and a non-ionic surfactant - alcohol alkoxylate (eg. Termul 203) with a surfactant concentration ratio of 65:35. Solvent used is solvent naphtha (petroleum), heavy aromatic (eg. Recosol 200). 2. Triáis by varying the solvent were done. All triáis gave favourable results in terms of coid temperature stability, emulsión characteristics and viscosity.

TABLE 3: VARIATION OF SOLVENT

Legend:

E - Emulsión characteristics done at 5 % aq. CTS - Coid temp stability at 2°C P- Pass F- Fail

Triai #3.1

Prosuifoearb active preseni «t 666 g/L

I'riíhlSata active prescut. si 333 g/L

Trial deíails: Triáis by vanaíion of seívent

Noh-ííhííc ssríactí:í¡i./ Amionic/Solveni «sed: Ternnij 263/N inste 6ÜE/ Acetóme

FQRMULATION

Triad # 3.2.

Prosnííoearl» active prescní. at g/L

Trialiate active preseat at. 333 ”/i

Trial fietails: Trinis by variation of sotvent

Non-ionic snríaeíaní/ Anionic/SolveiHÍ tised: Termal 2Θ3/ Ninate 60E/ Acetophenoae

mKMÍií.ATiON

Tria! # 3.3

Prosuifocarb active present ai 666 g/L

Trialiate active preseet at. 333 ”/!

Trial fíei.ails: Triáis by variation of sotvent

Non-ionic snrtactaní/ Aaionic/Solveiet aseó: Termal 2Θ3/ Ninate 60E/ F.tlíyi Benxoate FORMliLATiON_

Triad # 3.4

5 Prosaifocarb active present ai 666 g/L Trialiaíe active presene, at 333 g/L TPr-i.sB rfí±t»iÍBc» Tr-ioíc B-tsr 57<ίϊ·ί«3<ΪΛϊϊ jyF cjiív,¿*v-<f

Νβη-iomr siH'íariíim./ Aíiionic/Solvmí used: Termn! 203/ Niaate 60EZ E.xxate 700 lORMULATIOW_

Triad # 3.5

PiOsiiífoíarl» active presení. at f>í>í> g/L

Trialiatc active present at 333 g/L

Trial fietails: Triáis by variatijüi of sotvent

Non-ioaic snríaeíaní/ Aaionic/Solvent tised: Teraiui 2Θ3/ Ninate 60E/ isopherene FORMiJíATiON_,_,_,_,_,

Trial # 3.6

Prosíiífocarb active presení. at 6í>fs g/L

Triábate active presen! at 333 g/T

Trsal deíaíls: Triáis by variatien of soívení

Non-ionic sarfijcíaut/ Anienic/Solvení ased: Termal 203/ Nótate 60E'Meíltyi Benzaate FORMTÍ.tVTiON_

Trial # 3.7

Prosuifoearb active presea! «t 666 g/1.

Trialiate active prescat at 333 g./L

Trial details: Triáis by variation of sofvent

Nen-ienir snrfactaní/ Anionie/Solvent osed: Termal 203/Mínate 60E/N-methyi pyrroiidone

Triai # 3.8

Frostiifocarb active prescaí ai 666 g/L

I'rialSata active prescut. si 333 g/L

Trial deísils: Triáis by variatíon ofsofvent

Noh-ííhííc ssriactam./ Auionie/Solveuí usad: Tennti! 203/Ninsie 60EZ Prepiopbeuene lORMULATIOW_

Triad # 3.9 5 Prosaifocarb active present ai 666 g/L Teialiaíe active prestid. ai 333 g/í..

Tria! deeails: Triáis by variatioü of snivent 10 Nen-iomc snrfactanf/ Ánioose/Solvtnf. tiseti: Termai 203/ Nájate 60E/ Reteso! 150 , FORMULAT1ON_,_,_,_,_,

EXAMPLE 4

Triáis by variation of active loading. (eg. No solvent) 1. The original surfactants that were used for the Diablo dúo emulsifiable concéntrate is a combination of an anionic surfactant - Calcium Dodecylbenzene Sulphonate (eg. Ninate 60E) and a non-ionic surfactant -Block Co- polymer (eg. Termul 203) with a surfactant concentration ratio of 65:35. Solvent used is solvent naphtha (petroleum), heavy aromatic (eg. Recosol 200). 2. Triáis by varying the active loading were done. All triáis gave favourable results in terms of coid temperature stability, emulsión characteristics and viscosity.

TABLE 4: VARIATION OF ACTIVE LOADING

Legend: E - Emulsión characteristics done at 5 % aq.

CTS - Coid tenw stabilitv at 2dee. C

P- Pass F- Fail 'Iríai # 4.1

Trini tíeiails: Trinis by varialion of active ieading to elimínale solveat ase.

Increasing Prosuífoearb ieading I» 675g/L te elimínate sotvent use, Triaiiate ni 333g/L.

Non-ionic surfaeíaní/ Anionic/Solveni. ased: Termal 203/ Ninate 60E/ Κ2ΘΘ FORMliLATiON_

ΐ ría} # 4.2.

Trini tíetails: Trinis by varialion of active ieading to elimínale solveat ase.

Increasing Triatlate loatling to 352g/l. to diminate sdvent use. Prosnlfoearb at 655g/L.

Non-ionic snrfneíaní/ Anionic/Solveni. aseó: Termal 203/ Ninate 60E/ Κ2ΘΘ FORMULATiON_

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.

Throughout this specification and claims which follow, unless the context requires otherwise, the word “comprise”, and variations such as “comprises” and “comprising”, will be understood to imply the inclusión of a stated integer or step or group of integers or steps but not the exclusión of any other integer or step or group of integers or steps.

The reference to any prior art in this specification is not, and should not be taken as, an acknowledgement or any form or suggestion that the prior art forms part of the common general knowledge in Australia.

Claims (24)

1. An emulsifiable concéntrate formulation comprising prosulfocarb and triallate, and further comprising at least one solid, liquid or liquid-containing agriculturally acceptable surfactant selected from the group consisting of an alkoxylated alcohol, an alkoxylated alkylphenol, an alkoxylated tristyryl phenol, an alkoxylated oil, an alkyl or aryl or alkylaryl sulfonate, and any combination therein, wherein the sum of concentrations of prosulfocarb and triallate in the emulsifiable concéntrate formulation is greater than 500 g/L.

2. The concéntrate according to claim 1, wherein the weight ratio of prosulfocarb to triallate is in the range 3:1 to 1:1.

3. The concéntrate according to claim 1 or claim 2, wherein the weight ratio of prosulfocarb and triallate combined to a non-herbicide portion of the emulsifiable concéntrate formulation is at least 5:1.

4. The concéntrate according to any one of the preceding claims, wherein the weight ratio of prosulfocarb and triallate combined to the agriculturally acceptable surfactant in the concéntrate is at least 6:1.

5. The concéntrate according to any one of the preceding claims, wherein the concéntrate ineludes about 400 to about 800 g/L prosulfocarb and about 150 to about 600 g/L triallate.

6. The concéntrate according to any one of the preceding claims, wherein the at least one agriculturally acceptable solid, liquid or liquid-containing surfactant is present at a concentration of at least about 50 g/L.

7. The concéntrate according to any one of the preceding claims wherein the at least one agriculturally acceptable solid, liquid or liquid-containing surfactant is selected frnm the urnnn cnnsistinu nf a nnn-innic surfactant an aninnic surfactant, a cationic surfactant, a zwitterionic surfactant, a cation-anion composite surfactant and any combination thereof.

8. The concéntrate according to any one of the preceding claims wherein the at least one agriculturally acceptable solid, liquid or liquid-containing surfactant comprises a non-ionic surfactant selected from the group consisting of an alkoxylated alcohol, an alkoxylated alkylphenol, an alkoxylated tristyryl phenol, an alkoxylated oil and any combination thereof.

9. The concéntrate according to claim 8, wherein the non-ionic surfactant is selected from the group consisting of an alkoxylated polypropyleneglycol, an alkoxylated nonylphenol, a castor oil ethoxylate, an ethoxylated tristyryl phenol, and any combination thereof.

10. The concéntrate according to any one of claims 7 to 9, wherein the non-ionic surfactant is present at about 10 to about 50 g/L in the formulation.

11. The concéntrate according to any one of the preceding claims wherein the at least one agriculturally acceptable solid, liquid or liquid-containing surfactant comprises an anionic surfactant that is or comprises an alkyl or aryl or alkylaryl sulfonate.

12. The concéntrate of claim 11, wherein the anionic surfactant is or comprises a calcium alkylbenzene sulfonate salt, optionally in a liquid solvent carrier.

13. The concéntrate according to any one of claim 7, 11 or 12 wherein the anionic surfactant is present in the range of about 10 g/L to about 100 g/L.

14. The concéntrate according to any one of the preceding claims wherein the at least one agriculturally acceptable solid, liquid or liquid-containing surfactant is selected from the group consisting of an alkoxylated polypropyleneglycol, an alkoxylated nonylphenol, a castor oil ethoxylate, an ethoxylated tristyryl phenol, a calcium dodecylbenzene sulfonate and any combination thereof.

15. The concéntrate according to any one of the preceding claims, further comprising an agriculturally acceptable solvent and wherein the weight ratio of prosulfocarb and triallate combined to the agriculturally acceptable solvent is at least 10:1.

16. The concéntrate according to claim 15 wherein the agriculturally acceptable solvent is selected from the group consisting of an ester, a ketone, a lactam, an amide, a hydrocarbon and any combination thereof.

17. The concéntrate according to claim 16, wherein the agriculturally acceptable solvent is selected from the group consisting of a simple ketone, an aromatic ketone, a cyclic ketone, an acétate ester, an alkyl benzoate ester, a pyrrolidone, an aromatic hydrocarbon and any combination thereof.

18. The concéntrate according to claim 17, wherein the agriculturally acceptable solvent is selected from the group consisting of acetone, acetophenone, ethyl benzoate, a heptyl acétate ester, isophorone, methyl benzoate, N-methyl pyrrolidone, propiophenone, solvent naphtha (petroleum) heavy aromatic and any combination thereof.

19. The concéntrate according to any one of the preceding claims comprising at least two agriculturally acceptable surfactants and wherein the at least two agriculturally acceptable surfactants inelude at least one anionic surfactant and at least one non-ionic surfactant.

20. The concéntrate according to any one of the preceding claims comprising about 600 to about 750 g/L prosulfocarb, about 300 to about 400 g/L triallate, about 0 to about 50 g/L of an agriculturally acceptable solvent, about 20 to about 30 g/L of a non-ionic surfactant, and about 25 to about 32 g/L of an anionic surfactant.

21. A method of preparing a emulsifiable concéntrate formulation according to any one of the preceding claims including the steps of (a) adding prosulfocarb to a vessel; (b) adding triallate to the vessel; (c) adding at least one agriculturally acceptable surfactant to the vessel; and (d) agitating the vessel so as to facilítate uniformity of the concéntrate.

22. The method of claim 21, further comprising the step of adding an agriculturally acceptable solvent to the vessel prior to step (d).

23. A method of controlling weeds in a target crop including the step of applying to the target crop a diluted emulsifiable concéntrate formulation of prosulfocarb and triallate at a rate of about 1 to about 8 L/ha based on volume of the emulsifiable concéntrate.

24. The method of claim 23, wherein the emulsifiable concéntrate formulation is that of any one of claims 1 to 20.