AU2018203399B2 - Propyzamide formulations - Google Patents

Abstract

A water-dispersible granular formulation containing propyzamide, wherein the propyzamide is loaded to at least 600 g/kg based upon the total formulation, and wherein the formulation further includes a surface active agent.

Description

PROPYZAMIDE FORMULATIONS FIELD OF THE INVENTION

[0001] The present invention relates to granular formulations of the herbicide propyzamide. In particular, this invention relates to water-dispersible granular formulations of propyzamide that contain a high level of propyzamide as active agent and to methods of preparing said formulations.

BACKGROUND OF THE INVENTION

[0002] The herbicide propyzamide, belongs to the benzamide category of herbicides. Propyzamide has the nomenclature 3, 5-dichloro-N-(1, 1-dimethylprop-2-ynyl) benzamide, and has also been referred to as "pronamide". Propyzamide is a group D herbicide, with a mode of action based on inhibition of microtubule assembly. The water solubility ofpropyzamide in 15 mg/L at 25°C, and the melting point is 155°C.

[0003] Propyzamide is the active agent in Kerb herbicide, sold by Dow AgroSciences and has also been sold under the trade name Clanex. In Australia, water dispersible granular formulations of propyzamide containing 500 g/kg propyzamide have been sold by 4Farmers under the trade name 4Farmers Propyzamide 500 WG, and by Imtrade under the trade name Edge 500 WG herbicide. Water-dispersible granular formulations of500 g/kg propyzamide have also been sold by Titan Ag Pty Ltd under the trade name Titan Propyzamide 500 WG.

Granulation

[0004] Patent literature such as Kurita and Misumi (EP 1382244), entitled "Granular Compositions and Process for Producing Same", published in Japanese on 7 November 2002 as WO 2002/087324 and in English on 21 April 2004 as EP 1382244, teaches methods of use and compositions for a pesticide-containing wettable granule or granular wettable powder. Such wettable granules are said to diminish problems associated with dosing, dusting and bulkiness of a non-granulated wettable powder, and to diminish problems associated with high viscosity in a flowable (suspension concentrate) formulation of a finely divided active agent. Water-dispersible granular formulations are designed to disintegrate in water and to form a fine dispersion in the water for subsequent application to areas to be treated by spraying through nozzles.

[0005] In particular Kurita and Misumi teaches that the granule may be prepared by mixing a pesticidal active ingredient, a binder, and, if necessary other ingredients such as surfactants, followed by granulation of these ingredients into granules.

[0006] Kurita and Misumi also teaches that the granulation method may involve extrusion granulation, spray drying granulation, fluidised bed granulation, tumbling granulation (e.g., pan granulation), compression granulation, or coating granulation. Kneading granulation is said to be useful for making a granular wettable powder. This involves kneading of fine powder components into a dough (for example, with the addition of water to the powder prior to, or during, kneading). Surfactant, carrier and binder can be added during kneading. After dough formation, an extrusion process can be used to form the granules, which are subsequently dried. Granulation by kneading and extrusion is said to have the merit that installation and operating costs are relatively low. However, a disadvantage is that that the nature of the kneaded product is substantially influenced by the content and character of the pesticidal active ingredient. The higher the pesticidal active ingredient content, the more difficult it is to form the granules. This factor is considered to be a significant problem in the art by Kurita and Misumi.

[0007] Kurita and Misumi teaches that highly pure quartz powder may be added to such a kneaded material prior to extrusion granulation. Preferably the highly pure quartz powder is added in an amount from 15 - 95 wt%.

Surfactants

[0008] Kurita and Misumi teaches further that a surfactant or combination of surfactants may be included in a kneaded material prior to extrusion granulation. The content of such a surfactant or surfactants is preferably from 0.1 - 15% by weight of the granules. Suitable non-ionic surfactants are said to include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polyoxypropylene ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, polyoxyethylene polyoxypropylene block copolymers, sorbitan alkyl esters or higher fatty acid alkanolamides. Such nonionic surfactants may be used alone or in combination as a mixture of two or more of them. Suitable cationic surfactants are said to include alkylamine salts or quaternary ammonium salts. Such cationic surfactants may be used alone or in combination as a mixture oftwo or more ofthem. Further, suitable anionic surfactants may include naphthalenesulfonic acid polycondensate, alkenylsulfonate, naphthalenesulfonate, formalin condensate of a naphthalenesulfonate, formalin condensate of an alkylnaphthalenesulfonate, lignin sulfonate, alkylallylsulfonate, allylallyl sulfonate sulfate, polystyrene sulfonate, polycarboxylate, polyoxyethylenealkyl ether sulfate, polyoxyethylenealkylallyl ether sulfate, alkylsulfosuccinate, alkyl sulfate, alkyl ether sulfonate, or a higher fatty acid alkali salt. Such anionic surfactants may be used alone or in combination as a mixture of two or more of them.

Binders

[0009] Kurita and Misumi also teaches that binders may be included in a kneaded material prior to extrusion. The binders may include carboxymethylcellulose, polyvinyl alcohol, polyvinylpyrrolidone, dextrin, starch or a-modified starch, a physical property improving agent such as sodium tripolyphosphate, an arginate or a polyacrylate and, if necessary, other adjuvants such as a water soluble polymer, a solvent, an absorptive fine powder, a binder, a pulverization assistant, a decomposition-preventing agent, a colorant, a defoaming agent, an effect-improving agent, a perfume or a builder.

Carriers

[0010] Kurita and Misumi also teaches that carriers (other than highly pure quartz powder) may be included in a kneaded material prior to extrusion. The carrier may be a mineral carrier, a water-soluble carrier or a vegetable carrier. A suitable mineral carrier may, for example, be diatomaceous earth, talc, clay, calcium carbonate, acid clay, attapulgite, zeolite, sericite, sepiolite or calcium silicate. A suitable water-soluble carrier may, for example, be ammonium sulfate, urea, dextrin, lactose, fructose, sucrose glucose, sodium chloride, Glaubers salt, sodium carbonate, sodium bicarbonate, maleic acid, citric acid, fumaric acid, malic acid or polyethylene glycol having an average molecular weight of from 6000 to 20000. A suitable vegetable carrier may, for example, be wheat flour, wood powder, starch, bran, soy flour or a pulverized product of fiber plant. The content of such a carrier in the composition of the present invention usually may be from 0.1 to 90 wt%, preferably fi-om 0.5 to 75 wt%.

[0011] One typical method for making water-dispersible granular formulations involves combining pesticidal active ingredient, a binder, a physical property-improving agent, and a component-stabilizer, etc., and if necessary, pulverizing by e.g. an impact pulverizer, whereupon a mineral powder is mixed, water is added, and the mixture is kneaded and then granulated usually by an extrusion granulator employing a screen for a particle size of from 0.1 to 5 mm, preferably from 0.2 to 2 mm, and the granulated product is dried and sieved by a suitable screen for a predetermined grain size, to obtain the composition of Kurita and Misumi.

[0012] Further, Kurita and Misumi teaches that it is also possible that a proper amount of water, a pesticidal active ingredient, a surfactant and if necessary, other components such as a carrier, are added in necessary amounts, followed by pulverization by means of a wet type pulverizer such as a ball mill, a Dyno-mill or a sand grinder. To the resultant aqueous suspension, other components such as a surfactant, a carrier, etc., may be mixed in a suitable amount, as the case requires, obtaining a kneaded product which can be granulated by an extrusion granulator.

[0013] Based upon the teaching of Kurita and Misumi it can be seen that, in attempting to meet the need to include carriers, binders, surfactants, disintegrants and so forth in a granular wettable powder, this frequently results in the commercially viable product being made with a diminished weight of active pesticidal agent.

[0014] Propyzamide active agent has been commercially available in water dispersible granular formulation form for a considerable period of time in Australia. For all this time the loading of active agent in the product granules has been 50% by weight ofthe water-dispersible granular formulation or less. The composition of commercially available propyzamide water-dispersible granules is typically as follows:

[0015] Propyzamide 500 g/kg formulation:

CAS Identification Component %w/w

CAS# 23950-58-5 Propyzamide tech 52.0000 CAS# 107-21-1 Polyethylene glycol 2.0000 CAS# 1332-58-7 Kaolin 42.0000

CAS# 8061-51-6 Sodium lignosulphonate 2.0000 (e.g., Polyfon H) CAS# 9036-19-5 Octylphenol polyethoxy ethanol 2.0000 Total 100.0000

[0016] Commercially available water-dispersible granules typically are in the size range from about 30 microns up to 5,000 microns. In such typical prior art formulations, kaolin acts as an inert filler, and the sodium lignosulphonate and octylphenol polyethoxy ethanol are surface-active agents. Sodium lignosulphonate is a dispersant which may have some function as a granule binder. Octylphenol polyethoxy ethanol (sometimes sold under the trade name Triton X 1OOTM) is a nonionic surfactant which is an effective wetting agent. The surface active agents facilitate disintegration ofthe water-dispersible granules to a fine and relatively stable aqueous dispersion when the granules are added to the water in a spray tank prior to spray application. The kaolin has no herbicidal properties, and no surface-active effects.

[0017] It is desirable to provide a water-dispersible granular formulation of propyzamide with a loading of propyzamide at greater than 500 g/kg. The benefits of a more highly loaded water-dispersible granular formulation would include:

1. A reduced amount ofpackaging material would be necessary to carry a given amount of active ingredient to a cultivation zone.

2. The costs of disposing of used packaging material would be less.

3. A reduced weight of goods would need to be carried by a farm worker in applying a given amount of propyzamide to a cultivation zone.

4. The cost of freight (volume and weight basis) in transporting the propyzamide formulation from factory to field would be reduced.

5. A higher loading propyzamide formulation would enable a manufacturer to demonstrate superior formulation expertise to farmers.

[0018] In this specification and in the claims, the term "highly loaded" is to be taken to refer to the concentration level of active agent ofpropyzamide herbicide in a water-dispersible granular formulation on a weight by weight basis (g/kg) in the amount from at least 600 g/kg.

SUMMARY OF THE INVENTION

[0019] Accordingly, according to one aspect ofthe present invention there is provided a water-dispersible granular formulation containing propyzamide, wherein the propyzamide is loaded to at least 600 g/kg based upon the total formulation weight.

[0020] Accordingly, in another aspect of the present invention there is provided a water-dispersible granular formulation containing propyzamide, wherein the propyzamide is highly loaded based upon the total formulation weight.

[0021] According to another aspect of the present invention there is provided a water-dispersible granular formulation containing at least 600 g/kg ofpropyzamide, at least 30 g/kg of one or more surface active agents with the remainder, if any, ofthe water dispersible granular formulation being a fmely divided inert filler.

[0022] Most preferably there is a minimal amount of, or no, fmely divided inert filler in the water-dispersible granular formulation.

[0023] According to a further aspect ofthe present invention there is provided a method of manufacturing a water-dispersible granular propyzamide formulation including the steps of:

(a) blending fine propyzamide particles in the presence of(i) a first surface active agent wherein the first surface active agent is a dispersant, (ii) a second surface active agent, wherein the second surface active agent is a wetting agent, and (iii) optionally, an inert filler, to homogeneity;

(b) extruding the homogenous propyzamide blend to form moist granules; and

(c) passing the extruded moist granules through a collecting sieve; and

(d) drying the collected moist granules to a temperature up to about 80 0 C.

[0024] Preferably said first surface active agent and said second surface active agent have a combined concentration in the final form of the water-dispersible granular formulation of at least 30 g/kg.

[0025] Preferably the first surface active agent is a lignosulphonate salt or sodium lignosulphonate.

[0026] It is preferred that the aforesaid step of blending is effected in the presence of a water spray.

[0027] According to another aspect ofthe present invention there is provided a method of manufacturing a water-dispersible granular propyzamide formulation including the steps of:

(a) blending fine propyzamide particles in the presence of(i) a first surface active agent wherein the first surface active agent is a

dispersant, and (ii) a second surface active agent, wherein the second surface active agent is a wetting agent, to homogeneity;

(b) extruding the homogenous propyzamide blend to form moist granules; and

(c) passing the extruded moist granules through a collecting sieve; and

(d) drying the collected moist granules to a temperature up to about 80 0 C.

DETAILED DESCRIPTION OF THE INVENTION

[0028] Preferably, the propyzamide in the water-dispersible granular formulation is loaded to at least 600 g/kg based upon the total formulation.

[0029] Even though the water-dispersible granular formulation active herbicide agent is loaded to at least 600 g/kg, the water-dispersible granular formulation according to the present invention can be highly loaded with propyzamide up to 900 g/kg.

[0030] The propyzamide to be used in the preparation of water-dispersible granular formulation is in the form of finely divided particles.

[0031] The water-dispersible granular formulation, optionally, includes an inert filler which has no herbicidal properties. The inert filler is in the form of a finely divided material and constitutes no greater than 300 g/kg based upon the total water-dispersible granular formulation. Preferably, the inert filler constitutes no greater than 200 g/kg based upon the total water-dispersible granular formulation. More preferably, that amount is less than 100 g/kg, and even more preferably, that amount is less than 50 g/kg based on the total water-dispersible granular formulation.

[0032] The water-dispersible granular formulation includes at least one, or at least two, or at least three surface active agents. The at least one surface active agent is a dispersant. It may have the ancillary function as a granular binder. One such example of a dispersant is a lignosulphonate salt such as sodium lignosulphonate.

[0033] The second surface active agent, if present, is a wetting agent and may be an anionic surfactant.

[0034] The dispersant, being the lignosulphonate salt or sodium lignosulphonate, and the wetting agent have a combined amount in the water-dispersible granular formulation of at least 30 g/kg based upon the total weight of the formulation. The amount of lignosulphonate salt or sodium lignosulphonate may also range between 25 g/kg to 50 g/kg based upon the total weight of the formulation.

[0035] Useful wetting agents are naphthalene sulphonate condensate salt or its sodium salt. The amount ofnaphthalene sulphonate condensate salt or its sodium salt in the water-dispersible granular formulation can range between 8 g/kg to 30 g/kg based upon the weight of the total formulation, although the amount ranging between 12 g/kg to 18 g/kg is the more preferred range.

[0036] The water-dispersible granular formula also may include a third surface active agent which is also an anionic surfactant. This second anionic surfactant may be an alkyl naphthalene sulphonate blend or its sodium salt.

[0037] The amount of alkyl naphthalene sulphonate blends or its sodium salt in the water-dispersible granular formulation range between 10 g/kg to 30 g/kg, although the preferred range lies between 15 g/kg to 25 g/kg based upon the total weight ofthe formulation.

[0038] The inert filler, in the form of finely divided material, when present, is present in an amount desirably of no greater than 250 g/kg, based upon the total weight of the formulation.

[0039] In order to manufacture the wettable granular propyzamide formulation, a preferred method involves the following steps.

[0040] First, a defined quantity of finely divided propyzamide particles are loaded into a normal industrial sized commercial blender and then blended to homogeneity in the presence of a water spray or something similar, in combination with all of the other components being: (i) a lignosulphonate salt or sodium lignosulphonate; (ii) a naphthalene sulphonate condensate salt or its sodium salt; (iii) an alkyl naphthalene sulphonate blend or its sodium salt; and, optionally, (iv) the finely divided inert filler.

[0041] Then the resultant homogenous propyzamide blend is then transferred to an extruder, which is a usual industrial type extruder, and the ensuring extrusion process forms moist granules of the propyzamide blend.

[0042] The third step ofthe method of manufacture is to pass the extruded moist wet granules through a sieve, which is, preferably, a 1 m-n to 5 mm industrial type sieve. Once the moist granules pass through the sieve they are then dried to make the desired water-dispersible granular formulation. Temperatures in the order ofup to about 80°C, even though lesser temperatures may be used, are used to dry the moist granules.

[0043] After the completion of the above described process, the water-dispersible granular formulation will be in the form of dried granules and will have a moisture content of less than about 1% by weight, based upon the total weight of the formulation.

[0044] The dried granules are designed to disintegrate in water in a spray tank, and to form a fine dispersion in the water, for subsequent application by spraying through nozzles.

[0045] According to another aspect ofthe present invention there is provided a method of controlling weeds including the addition of wettable granular propyzamide formulation, wherein the propyzamide is highly loaded based on the total formulation, to spray water in a spray tank and spraying the resultant spray liquor on to a site containing weeds.

[0046] According to a further aspect of the present invention there is provided a water-dispersible granular formulation comprising: propyzamide, wherein the propyzamide is loaded to at least 600 g/kg based upon the total formulation; and a surface active agent.

[0047] In certain embodiments, the surface active agent is a single surface active agent. That is, only one surface active agent is present in the formulation.

[0048] According to another aspect of the present invention there is provided a water dispersible granular formulation comprising, consisting or consisting essentially of propyzamide, wherein the propyzamide is loaded to at least 600 g/kg based upon the total formulation; a single surface active agent; and, optionally, a binder.

[0049] Suitably, the surface active agent is present in an amount of at least 30 g/kg. Accordingly, the surface active agent of the present invention may be present in an amount of between about 30 g/kg and about 150 g/kg, about 35 g/kg and about 120 g/kg, about 40 g/kg and about 100 g/kg, or any range therein. In particular embodiments of the present invention, the surface active agent is present in an amount of about 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, 65,66,67,68,69,70,71,72,73,74, 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/kg or any range therein. In certain embodiments of the present invention, the surface active agent is present in an amount of between about 35 g/kg and about 100 g/kg. In one preferred embodiment, the surface active agent is present in an amount of between about 40 g/kg and about 80 g/kg.

[0050] The first surface active agent is suitably an anionic surfactant. Preferably, the first surface active agent is selected from the group consisting of an alkyl naphthalene sulphonate salt blend or condensate and an acid resin copolymer.In one embodiment, the acid resin copolymer is or comprises a copolymer of styrene and sodium methacrylate.

[0051] In embodiments wherein the binder is present, the binder is suitably present in an amount no greater than 300 g/kg. Accordingly, the binder of the present invention may be present in an amount of between about 1 g/kg and about 300 g/kg, about 10 g/kg and about 100 g/kg, about 20 g/kg and about 50 g/kg, or any range therein. In particular embodiments of the present invention, the binder is present in an amount of about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19,20,21,22,23,24,25,26,27,28,29,30,31,32,33,34,35, 36,37,38,39,40,41,42,43,44,45,46,47,48,49,50,55,60,65,70,75,80,85,90,95, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 220, 240, 260, 280, 300 g/kg or any range therein. In certain embodiments of the present invention, the binder is present in an amount of between about 5 g/kg and about 50 g/kg. In one preferred embodiment, the binder is present in an amount of between about 10 g/kg and about 30 g/kg.

[0052] In one embodiment, the granular formulation has a moisture content of less than about 1% by weight.

[0053] According to another aspect of the present invention there is provided a water dispersible granular formulation comprising, consisting or consisting essentially of a propyzamide and a single surface active agent, wherein the propyzamide is highly loaded based upon the total formulation.

[0054] According to another aspect of the present invention there is provided a method of controlling weeds, including the addition of the water-dispersible granular propyzamide formulation ofthe two aforementioned aspects to spray water in a spray tank and spraying the resultant spray liquor onto a site containing weeds.

[0055] The advantages of highly loaded wettable granular propyzamide formulations include: reduced packaging requirements, reduced freight costs, reduced amounts of non-herbicidally active ingredients relative to the propyzamide in the formulations leading to reduced weight and volumes to be transported, and, where inert filler is not incorporated in the highly loaded formulations, the minimising or elimination ofproblems arising from the presence of inert filler particles.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS AND EXAMPLES OF THE INVENTION

[0056] In order that the present invention may be more readily comprehended, one or more preferred embodiments are described hereinafter.

Example 1

[0057] A water-dispersible granular formulation according to the present invention was made by incorporating the following components.

Components Parts by Weight

1. Propyzamide 98% 918.4kg

2. Sodium salt ofnaphthalene sulphonate condensate 15.1kg (e.g., Morwet D 425, or Galoryl DT 505)

3. Sodium lignosulphonate 38.4kg (e.g., Polyfon H).

4. Sodium alkyl naphthalene sulphonate blend 19.4kg (e.g., Morwet EFW)

[0058] In Example 1, the formulation procedure for a 1000 kg batch, inclusive of quality control measures, was as follows, with the steps being numerically as 1.1, 1.2, 1.3, and so on.

[0059] 1.1 Ensure the blender, which is provided with water sprayers, is empty and clean.

[0060] 1.2 Charge the blender with the components via a hopper.

[0061] 1.3 Seal the blender and switch on.

[0062] 1.4 Activate the sprayers to distribute water throughout the dry mix. Set the water flow-rate to Ilt per minute, and spray until sufficient water is present to allow a consistent mix to develop. Operate the blender for a minimum of one further hour to ensure the mix is homogeneous.

[0063] 1.5 Transfer the mix to the extruder and switch the drying receiver on. Extrude the mixture in the form of granules into the receiver and air dry at a temperature of no greater than 80°C to a moisture content of approximately 1% weight based on the weight of the formulation. Where the moisture content significantly exceeds 1% weight to weight of the formulation, recycle the granules through the drying receiver (at the end of the run) until the moisture content target is achieved.

[0064] 1.6 Sample approximately 1kg of product, ensuring it is representative.

[0065] 1.7 Sub-sample approximately 250g from the original 1kg sample and subject it to the following testing regime.

1.7.1 Active constituent (Propyzamide) content (using validated method).

1.7.2 pH of a 1% aqueous solution (CIPAC MT75.3).

1.7.3 Wet sieve test (CIPAC MT185).

1.7.4 Wettability (CIPAC MT53.3).

1.7.5 Persistent foaming (CIPAC MT 47.2).

[0066] 1.8 If active constituent level is satisfactory, record results and proceed to step 1.10 described below.

[0067] 1.9 If active constituent level is outside the bounds of the acceptable range listed in the specification, adjust the level accordingly by recycling granules through the blending process (Returning to step 1.4 described above) along with additional excipients, being sodium alkyl naphthalene sulphonate, sodium lignosulphonate and naphthalene sulphonate blend in the weight to weight ratio 15:38:19 (to adjust for a high active content) or along with additional propyzamide (to adjust for a low active content).

[0068] 1.10 If the sample fail to meet a specification for any of the other parameters, quarantine the batch for further investigation and possible rework. Otherwise proceed to step 1.11 described below.

[0069] 1.11 Catalogue and store a retention sample of approximately 200g.

[0070] 1.12 Generate a certificate of analysis noting results of testing.

Tests to Confirm the Suitability of the Formulation of Example 1

[0071] For the test methods identified by the prefix CIPAC, refer to International Pesticides Analytical Council (CIPAC) published methodology.

Test Test Method Required Observed Parameter Outcome Outcome Required, Required, (Advised Preferably More preferred Preferably formulation)

White to White to Appearance Visual beige, beige, homogeneous, homogeneous, fine granule fine granule

Validated chromatographic method 875 to (Accuracy: 98- 925 g/kg 909 g/kg Assay 102%) propyzamide propyzamide (Linearity: R > 0.99)

(Precision: s/average < 2%)

pH (1%) CIPAC MT 75.3 7 to 10 8.5 -

CIPAC MT185 <2%w/w over 0.05% <1%w/w 0%w/w Wet sieve test 75pvm over 75pm over 75[pm

Spontaneity CIPAC MT174 Between 60 93.- of dispersion and 105%

Suspensibility CIPAC MT184 Between 60 96.4% - and 105%

<1 minute Wettability CIPAC MT53 (without Pass - swirling)

Persistent CIPAC MT47 <60mL after 1 12mL <30mL (1 <15mL (1 foam min minute) minute)

<1%, otherwise Dust content CIPAC MT171 inhalation 0.001% - toxicity data required

Sample flows Flowability CIPAC MT172 through Pass - aperture after <5 liftings

Attrition CIPAC >98% 99.9% resistance MT178.2

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

Bioefficacy Studies

[0072] A number of trials were carried out to assess the weed control efficacy of a highly loaded propyzamide water-dispersible granular formulation with that of a conventionally loaded propyzamide water-dispersible granular formulation when applied to sites containing grass weeds at the same active ingredient rate. The Reports ofthose tests are set out below. It was found that there was no significant difference in the level of weed control between the formulations.

DRAWINGS

[0073] The drawings comprise bar graphs showing the effects of application of the aforesaid formulations.

[0074] Figure 1 is a bar graph showing the effect on annual ryegrass plants at 74 days after application of formulations;

[0075] Figure 2 is a bar graph showing the effect on annual ryegrass panicles at 153 days after application of formulations; and

[0076] Figure 3 is a bar graph showing the effect on annual ryegrass panicles at 137 days after application of formulations.

Example BE 1

[0077] The reference formulation ofpropyzamide was Imtrade Edge 500WG. This commercially available formulation contained 500 g ai/kg Propyzamide. The current registration profile for this commercially available formulation includes use in various legume pastures including clover, medic and Lucerne as well as Lettuce crops, turf and lawns. It controls a range of annual grass weed species including annual ryegrass (L.rigidum). The trial work in this example was undertaken to examine absolute control and bioequivalence of Imtrade Edge 500 WG Herbicide and the new formulation of propyzamide (900 g/kg active agent) which is designated Imtrade Edge 900 WG (see example 1 for formulation details). The example relates to the use ofImtrade Edge 900 WG in canola for the control of annual ryegrass (Lolium rigidum).

Aims

[0078] To prove that Imtrade Edge 500 WG Herbicide and the new formulation of Imtrade Edge 900 WG Herbicide provide control of annual ryegrass at use rates of 500 and IOOg ai per hectare.

[0079] To prove that both formulations provide equivalent level of control of annual ryegrass when applied at equivalent rates (g ai/ha).

Main Conclusions

[0080] Both formulations of Edge provided a high level of annual ryegrass control (>85%) which was significantly different from the untreated control. There was no significant difference in the weed control between the two formulations of the Propyzamide when applied at the same rate (g ai) per hectare.

Treatments

[0081] Both products were applied at 2 rates; 500 and 1000 g ai per hectare.

[0082] Table 1 sets out the treatment types and application rate mL product per hectare and g ai per hectare.

Table 1

Treatment

Nil

Edge 500WG 1 kg (500g ai)

Edge 900WG 0.555 kg(500g ai)

H dge 500WG 2 kg/ha (1000g ai)

7dge 900WG 1.1lkg(1000g ai)

Experimental Details

[0083] The trial was a randomized block design comprising 4 replicates. The Edge treatments were applied prior to sowing and the canola was seeded using farmer scale seeding equipment. The trial was seeded using knife points and press wheels with no disturbance other than the seeding operation. Full application details are set out in Tables 2 and 3.

Table 2 - Trial Design

Trial Location: Walebing

State: WA

Study Design: Randomised Block

Reps: 4

Plot Width: 2.5

Plot Length: lom

Plot number: 20

Variety: Thunder Canola

Seeding date: 11 May 2011

Tillage system: Knife Points press wheels

Seed depth: 2.5 cm

Seeding rate: 5 kg/ha

Row spacing: 25 cm

Seedbed moisture: Dry at seeding, rainfall 5 DAS

Seed Bed condition: Friable

Stubble load: Low - Medium

Soil type: Sandy Loam soil

Previous Crop: Wheat

Table 3 - Application Details

Application:

12.45 -1.15 4/05/11 Date and time

Temperature 24 °C Relative humidity(%) 29%

Cloud cover (%) Nil

Wind 4.6 km/h NW Constant (speed,direct,consist)

Soil moisture status Dry top 10cm

Proximity of rain Nil

Inversion Risk Nil

Application Equipment:

Nozzle type / Size Al 001

Nozzle Spacing 50cm

Spray Height 50cm

Spray Pressure 2 bar

Speed (km/hr) 6.7 Km/hr

Spray Vol (L/ha) 70L/ha

[0084] Plant counts were taken using a 1/10m 2 quadrat and annual ryegrass was counted 74 days after treatment. Annual ryegrass panicle counts were taken 153 days after treatment. Results were analysed using Analysis of Variance and treatment means were separated at the 95% probability level (P 0.05) using Fishers least significant difference.

Results

[0085] There was no visual effect of any treatment on the canola crop. The application of Propyzamide significantly reduced annual ryegrass numbers in the crop. There was a significant reduction in annual ryegrass in all treatments irrespective of application rate or the formulation type of Edge applied. When applied at equivalent g ai/ha, both formulations controlled weeds to an equivalent level. As well as significant reduction in annual ryegrass number, surviving plants appeared stunted and less competitive than those in the untreated plot based on visual observation. When carried through to seed head formation, annual ryegrass panicle counts reflected the trends of the plant counts undertaken earlier in the season. There was a significant reduction in panicle counts in all treatments compared to the untreated control. There was no significant difference between rates applied on a g ai/ ha basis. There was no significant difference between panicle counts when comparing the different formulations when applied at the same g ai/ ha.

[0086] Figure 1 shows the effect on annual ryegrass numbers per square metre in response to the application oflmtrade Edge 500 WG Herbicide and Imtrade Edge 900 WG Herbicide, 74 days after application.

[0087] Table 4 sets out the average annual ryegrass plants per square metre per treatment per replicate 74 DAA.

Table 4

2 Annual ryegrass plant counts/m

Treatment Rep I Rep 2 Rep 3 rep 4 Average

Nil 42 124 98 96 90 a

Edge 50OWGlkg (500gai) 4 12 8 30 13.5 b

Edge 900WG 0.555kg (500gai) 0 10 18 8 9b

Edge 500WG 2kg (1000gai) 4 8 6 18 9b

Edge 900WG 1.11kg (1000gai) 2 2 0 10 3.5 b

Treatment means in the same columns followed by the same numbers are not statistically different.

[0088] Figure 2 shows the effect on annual ryegrass panicles per square metre in response to the application oflintrade Edge 500 WG Herbicide and Imtrade Edge 900 WG Herbicide, 153 days after application.

[0089] Table 5 sets out the annual ryegrass panicles per square metre per treatment per replicate 153 DAA.

Table 5

Annual ryegrass panicle counts/m2

Treatment Rep I Rep 2 Rep 3 rep 4 Average

Nil 330 144 302 512 322 a

Edge 50OWG lkg (500gai) 34 8 68 64 43.5 b

Edge 900WG 0.555kg (500gai) 12 22 32 58 31 b

Edge 500WG 2kg (1000gai) 4 30 32 40 26.5 b

Edge 900WG 1.11kg (1000gai) 10 12 4 22 12 b

Treatment means in the same columns followed by the same numbers are not statistically different.

Discussion

[0090] The use rates (g ai/ha) reflects the range of current registered rates of Imtrade Edge 500WG herbicide for control of grass weeds in other use patterns including legume pastures and Lucerne. There was a significant reduction in annual ryegrass numbers and annual ryegrass panicle counts at all rates and with both the 500g and 900 g ai formulations. There was no significant difference in herbicide efficacy between the products at comparable g ai / ha application and this highlights the bioequivalence ofthe two formulations.

Example BE 2

[0091] The reference formulation of propyzamide was lmtrade Edge 500WG. This commercially available formulation contained 500 g ai/kg Propyzamide. The current registration profile for this commercially available formulation includes use in various legume pastures including clover, medic and Lucerne as well as Lettuce crops, turf and lawns. It controls a range of annual grass weed species including annual ryegrass (L.rigidum). The trial work in this example was undertaken to examine absolute control and bioequivalence of Imtrade Edge 500 WG Herbicide and the new formulation of propyzamide (900 g/kg active agent) which is designated Imtrade Edge 900 WG (see example 1 for formulation details). The example relates to the use of Imtrade Edge 900 WG in legume-based pasture control of annual ryegrass (Lolium rigidum).

Aims

[0092] To prove that Imtrade Edge 500 WG Herbicide and the new formulation of Imtrade Edge 900 WG Herbicide provide control of annual ryegrass in pasture at use rates of 500 and 1000 g ai per hectare.

[0093] To prove that both formulations provide equivalent level of control of grass weeds, in particular annual ryegrass, when applied at equivalent rates (g ai/ha).

Main Conclusions

[0094] Both formulations of Edge provided a level of grass weed control, which was significantly different to the untreated control. This was assessed by reduction of panicle counts of the annual ryegrass. There was no significant difference in the weed control between the two formulations of the Propyzamide when applied at the same rate (g ai) per hectare based on annual ryegrass panicle counts.

Treatments

[0095] Both products were applied at 2 rates; 500 and 1000 g ai per hectare.

[0096] Table 6 sets out the treatment types and application rate mL product per hectare and g ai per hectare.

Table 6

Treatment

Nil

Edge 500 WG 1kg (500g ai)

Edge 900 WG 0.555kg (500g ai)

Edge 500 WG 2kg/ha (10OOg ai)

Edge 900 WG 1.11kg (1OOOg ai)

Experimental Details

[0097] The trial was a non-replicated large plot trial consisting of 50m x 25m plots for each treatment. The Edge treatments were applied across seeded pasture plots using a hand boom. The annual ryegrass (L.rigidum) was not seeded and had established from the residual seed bank from previous seasons across the seeded legume species. The annual ryegrass weeds were varying sizes ranging from 2 leaf to well tillered stage, with approximately 50% of the plants having multiple tillers. The legume pastures was well established at spraying. The site was seeded approximately 5 weeks prior to spraying the trial. Full application details are set out in Tables 7 and 8.

Table 7 - Trial Design

Trial Location: Kojonup

State: WA

Study Design: Large single block non replicated

Plot Width: 2.5

Plot Length: 50m

Plot number: 5

Variety: Seeded legume species

Seedbed moisture: Moist at spraying

Stubble load: Low

Soil type: Sandy Loam with gravel soil

Previous Crop: Imidazolinone Tolerant Canola

Table 8 - Application Details

Application:

Date and time 21/6/2011 12.30pm

Temperature 14.5

Relative humidity(%) 57%

Cloud cover (%) 95%

Wind (speed,direct,consist) 3.7km/hrW

Soil moisture status moist

Delta T 4

Proximity of rain Nil

Inversion Risk Nil

Application Equipment:

Nozzle type / Size Al 001

Nozzle Spacing 50cm

Spray Height 50cm

Spray Pressure 2 bar

Speed (km/hr) 6.7 Km/hr

Spray Vol (L/ha) 70L/ha

[0098] Annual ryegrass panicle counts were taken 110 days after treatment. All data from this trial was analysed using a confidence interval of 95% unless otherwise specified. Means were compared using paired t-test and single factor Analysis of Variance. All mention of significant differences contained within this report refer to statistically significant differences.

Results

[0099] There was no visual effect of any treatment on the legume pasture species.

Annual Ryegrass Biomass Reduction

[0100] The application of Propyzamide resulted in a visual reduction the biomass of the annual ryegrass in the sward. Annual ryegrass plants were discoloured and stunted when compared with the untreated, which grew well throughout the season. The treated areas exhibited symptoms of root pruning as would be expected from this herbicide mode of action.

Annual Ryegrass Panicle Counts

[0101] When carried through to seed head formation, annual ryegrass panicle counts reflected the trends observed in biomass observations of earlier in the season. There was a significant reduction in panicle number in all treatments compared to the untreated control. There was a significant difference between rates applied on a g ai/ ha basis with higher rates resulting in greater reduction in the panicle numbers. There was no significant difference between panicle counts when comparing the different formulations when applied at the same g ai/ ha. At each rate of application, Edge 900 WG provided the same level control of annualryegrass as Edge 500 WG as measured by panicle counts.

[0102] Figure 3 shows the effect on annual ryegrass panicles per square metre in response to the application of Imtrade Edge 500 WG Herbicide and Imtrade Edge 900 WG Herbicide 137 days after application.

[0103] Table 9 sets out the average annual ryegrass panicles per square metre per treatment.

Table 9

Average Ryerass Treatment panicle /m

Nil 546.8 a

Edge 500 1kg (500g ai) 87.6 b

Edge 900 0.555kg ( 500g ai) 83.6 b

Edge 500 2kg (10OOg ai) 21.6 c

Edge 900 1.11kg ( 10OOg ai) 16.4 c

Treatment means in the same columns followed by the same numbers are not statistically different.

Discussion

[0104] The use rates (g ai/ha) reflects the range of current registered rates of Imitrade Edge 500 WG Herbicide for control of grass weeds in legume pastures and Lucerne. The application timing ofthe herbicide fell outside the ideal timing, with many of the ryegrass plants tillered, resulting in more established plants which are more difficult to control with a root absorbed herbicide. This is reflected in the significant difference in rate response across the trial of the recommended range for this use pattern. The Imtrade Edge 500 WG Herbicide label also states "Rain or irrigation is necessary to thoroughly wet the top 3-4cm of soil. This is similar to 25mm rain". At this site, at the time of application the soil was moist and a soaking rain of approximately 28mm occurred within 4 days of application. This may or may not have washed the herbicide into the top 3-4cm and the next significant rainfall event was approximately 22mm some 4 days later. Despite the size of the annual ryegrass at spraying, where approximately 50% ofplants were tillering, there was an extremely visual biomass reduction for all treatments. There was a significant reduction in annual ryegrass panicles at all rates with both the 500g and 900 g ai formulations. There was no significant difference in annual ryegrass panicle numbers between the Imtrade Edge 500 WG and Imtrade Edge 900 WG product when applied at comparable rates of grams active ingredient per hectare. As a result of the plant biomass observations and subsequent annual ryegrass panicle counts, Imtrade Edge 900 WG Herbicide should be considered at least equivalent in efficacy when compared to Imtrade Edge 500 WG Herbicide.

Example 2

[0105] The aim of the present example was to prove that formulations comprising 900g/kg propyzamide could be formulated using just a single surfactant. Accordingly, a range of water dispersable granular formulations comprising 900g/kg propyzamide together with a single surfactant were made and tested according to those methods provided in Example 1.

[0106] It would be appreciated that many commercially available surfactants are available as polydisperse mixtures rather than as homogeneous preparations of only one surfactant. Accordingly, and for the purposes of the present invention, any such commercially available surfactant is treated as a single surfactant rather than as a mixture. Further, a single surfactant may also refer to one or more of a plurality of species contained within a designated class of surfactant. For example, if the designated class of surfactant is alkyl naphthalene sulphonate, wherein the alkyl group has 8 to 12 carbons, a surfactant containing octyl naphthalene sulphonates or nonyl naphthalene sulphonates is considered herein to constitute a single surfactant.

[0107] Table 10 below provides a summary of the water dispersable granular formulations containing 900g/kg propyzamide and a single surfactant.

Table 10 - Summary

Trial 1: Variation of formulation recipe at 900 g/kg Result Wet sieve Using Morwet D425 Trial 1.1 - with binder PASS 0.05% Trial 1.2 - without binder PASS 0.01%

Using Morwet EFW Trial 1.3 - with binder PASS 0.20% Trial 1.4 - without binder PASS 0.01%

Using Tersperse 2700 Trial 1.5 - without binder PASS 0.04%

Results

[0108]. Tables 11 to 15 below demonstrate the results obtained from testing the various formulations at 900g/kg propyzamide loading and containing different surfactants.

Table 11 - Propyzamide formulation including Morwet D425 surfactant and a binder Trial 1.1 - Using Morwet D425 - WG recipe with binder Component Amount added Propyzamide tech, 98% IAS15178 4590

Sodium naphthalene sulphonate 260 formaldehyde condensate (eg, Morwet D425) Starch, soluble 100

Water 50

Total amount 5000 Note: Additional water was added to the mix to aid in granule formation into WG format Results: Parameter Specs Results Appearance: - White to off white granules Assay (GC) <875 - 925 g/kg> 909 g/kg pHl%: - 8.74 CIPAC MT 75.3 Wet sieve < 2% 0.05% CIPAC MT185 Dispersibility 60- 105% 98.62% CIPAC MT 174 Suspensibility 60- 105% 79.46% CIPAC MT168 Attrition >98% 99.80% Resistance CIPAC 178.2 Dustiness <1.0% 0.002% CIPAC MT171 Persistent foaming <60mL after 1min 24 mL CIPAC MT47 Wettability Complete wetting in Complete wetting in 5 sec CIPAC MT 53 1 min Long tube < O.1mL 0.00 mL suspension (In-house method) Remarks: PASS

Table 12 - Propyzamide formulation including Morwet D425 surfactant and no binder Trial 1.2 - Using Morwet D425 - WG recipe without binder Component Amount added, g Propyzamide tech, 98% IAS15178 4590 Sodium naphthalene sulphonate 360 formaldehyde condensate (eg, Morwet D425) Starch, soluble 0 Water 50

Total amount 5000 Note: Additional water was added to the mix to aid in granule formation into WG format Results: Parameter Specs Results Appearance: - White to off white granules Assay (GC) <875 - 925 g/kg> 911 g/kg pHl%: - 8.82 CIPAC MT 75.3 Wet sieve < 2% 0.01% CIPAC MT185 Dispersibility 60-105% 98.11 %

CIPAC MT 174 Suspensibility 60-105% 80.080% CIPAC MT168 Attrition >98% 99.60% Resistance CIPAC 178.2 Dustiness <1.0% 0.001 %

CIPAC MT171 Persistent foaming <60nL after 1min 20 mL CIPAC MT47 Wettability Complete wetting in Complete wetting in 5 sec CIPAC MT 53 1 min Long tube < O.1mL 0.00 mL suspension (In-house method) Remarks: PASS

Table 13 - Propyzamide formulation including Morwet EFW surfactant and a binder Trial 1.3 - Using Morwet EFW - WG recipe with binder Component Amount added Propyzamide tech, 98% IAS15178 4590

Sodium alkyl naphthalene sulfonate 260 blend. (eg, Morwet EFW) Starch, soluble 100

Water 50

Total amount 5000 Note: Additional water was added to the mix to aid in granule formation into WG format Results: Parameter Specs Results Appearance: - White to off white granules Assay (GC) <875 - 925 g/kg> 903 g/kg pHl%: - 7.56 CIPAC MT 75.3 Wet sieve <2% 0.20% CIPAC MT185 Dispersibility 60- 105% 90.76% CIPAC MT 174 Suspensibility 60- 105% 76.22% CIPAC MT168 Attrition >98% 99.80% Resistance CIPAC 178.2 Dustiness <1.0% 0.002% CIPAC MT171 Persistent foaming <60mL after 1min 10 mL CIPAC MT47 Wettability Complete wetting in Complete wetting in 5 sec CIPAC MT 53 1 min Long tube < O.1mL 0.00 mL suspension (In-house method) Remarks: PASS

Table 14 - Propyzamide formulation including Morwet EFW surfactant and no binder Trial 1.4 - Using Morwet EFW - WG recipe without binder Component Amount added, g Propyzamide tech, 98% IAS15178 4590 Sodium alkyl naphthalene sulfonate 360 blend. (eg, Morwet EFW) Starch, soluble 0 Water 50

Total amount 5000 Note: Additional water was added to the mix to aid in granule formation into WG format Results: Parameter Specs Results Appearance: - White to off white granules Assay (GC) <875 - 925 g/kg> 898 g/kg pH1%: - 7.90 CIPAC MT 75.3 Wet sieve < 2% 0.01% CIPAC MT185 Dispersibility 60-105% 92.17% CIPAC MT 174 Suspensibility 60-105% 74.160% CIPAC MT168 Attrition >98% 99.53 %

Resistance CIPAC 178.2 Dustiness <1.0% 0.001 %

CIPAC MT171 Persistent foaming <60nL after 1min 10 mL CIPAC MT47 Wettability Complete wetting in Complete wetting in 5 sec CIPAC MT 53 1 min Long tube < O.1mL 0.00 mL suspension (In-house method) Remarks: PASS

Table 15 - Propyzamide formulation including Tersperse 2700 surfactant and no binder Trial 1.5 - Using Tersperse 2700 - WG recipe without binder Component Amount added, g Propyzamide tech, 98% IAS15178 4590 Polymeric anionic surfactant. 362 (eg, Tersperse 2700) Starch, soluble 0 Water 50

Total amount 5002 Note: Additional water was added to the mix to aid in granule formation into WG format Results: Parameter Specs Results Appearance: - white granules Assay (GC) <875 - 925 g/kg> 912 g/kg pHl%: - 9.01 CIPAC MT 75.3 Wet sieve < 2% 0.04% CIPAC MT185 Dispersibility 60- 105% 98.54 %

CIPAC MT 174 Suspensibility 60-105% 87.68% CIPAC MT168 Attrition >98% 99.80% Resistance CIPAC 178.2 Dustiness <1.0% 0.001 %

CIPAC MT171 Persistent foaming < 60mL after 1min 25 mL CIPAC MT47 Wettability Complete wetting in Complete wetting in <1min CIPAC MT 53 1 min Long tube < O.1mL 0.00 mL suspension (In-house method) Remarks: PASS

Conclusions:

[0109] All of the above water dispersible formulations comprising 900g/kg propyzamide with a single surfactant with or without a binder were successful in creating a passable wettable granular propyzamide formulation suitable for use as a herbicide.

[0110] The complete disclosures of any 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 persons 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 ofthe invention intended to be limited only by the claims set forth herein as follows.

[0111] Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise" and variations such as "comprises" or "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.

[0112] The reference in this specification to any prior publication (or information derived from it) or to any matter which is known, is not, and should not be taken as an acknowledgment or admission or any form of suggestion that the prior 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.

[0113] The present application is a divisional of Australian Patent Application No. 2016210595, which is further a divisional of Australian Patent Application No. 2013248217, the disclosures of which are incorporated by reference herein in its entirety.

Claims (10)

1. A water-dispersible granular formulation comprising: propyzamide, wherein the propyzarnide is loaded to at least 825 g/kg based upon the total fonnulation; and a surface active agent, wherein the surface active agent is or comprises: (a) a wetting agent; and/or (b) a dispersing agent, wherein the dispersing agent is or comprises a naphthalene sulphonate and/or an acid resin copolymer.

2. The water-dispersible granular formulation of Claim 1, wherein the surface active agent is present in an amount of at least 30 g/kg.

3. The water-dispersible granular formulation of Claim 2, wherein the surface active agent is present in an amount ranging between 40 g/kg to 80 g/kg.

4. The water-dispersible granular formulation according to any one of the preceding claims, wherein the surface active agent is an anionic surfactant.

5. The water-dispersible granular formulation according to any one of the preceding claims, wherein the surface active agent is selected from the group consisting of an alkyl naphthalene sulphonate salt blend or condensate and an acid resin copolymer.

6. The water-dispersible granular formulation of any one of the preceding claims, wherein the acid resin copolymer is or comprises a copolymer of styrene and sodium methacrylate.

7. The water-dispersible granular formulation according to any one of the preceding claims, further comprising a binder.

8. The water-dispersible granular fonnulation of Claim 7, wherein the binder is present in an amount no greater than 150 g/kg.

3507222v1

9. The water-dispersible granular fonnulation according to any one of the preceding claims, wherein the granular formulation has a moisture content of less than about 1% by weight.

10. A method of controlling weeds, including the addition of the water dispersible granular propyzamide formulation of any one of Claims I to 9 to spray water in a spray tank and spraying the resultant spray liquor on to a site containing weeds.

3507222v1

Oct 2018 24May 2013248217 15 2018203399 2013

This data, for application number 2013248217, is current as of 2016-07-31 21:00 AEST

Oct 2018 24May 2013248217 15 2018203399 2013

This data, for application number 2013248217, is current as of 2016-07-31 21:00 AEST

Oct 2018 24May 2013248217 15 2018203399 2013

This data, for application number 2013248217, is current as of 2016-07-31 21:00 AEST