AU2014101026A4 - Phenylurea Formulation - Google Patents

Abstract

- 43 A water-dispersible granular formulation containing linuron, wherein the linuron is loaded to at least 650 g/kg based upon the total formulation, and wherein the formulation further includes a first surface active agent being a dispersant, a second surface active agent being a wetting agent, and, optionally, an inert filler.

Description

PHENYLUREA FORMULATION FIELD OF THE INVENTION [0001] The present invention relates to granules of the herbicide linuron. In particular, the invention relates to water-dispersible granule formulations of linuron that contain a high level of linuron as active agent, and to methods of preparing said formulations. BACKGROUND OF THE INVENTION [0002] Linuron belongs to the family of urea herbicides and has a mode of action that involves inhibition of photosynthesis. It is a group C herbicide. Linuron is the active agent in formulations sold in Australia under the trade names Afalon, Aphalon, Cephalon, DuPont 326, herbicide 326, Loex, Lorox, methoxydiuron, Sinuron, Garnitan, Laroks, Linorox, Linurex, Premalin, Sarclex, Arresin, AShlade, HOE 2810, Atlas linuron. [0003] Linuron water-dispersible granules containing 50% or less loading of linuron have been sold in Australia under the trade names as follows: Linuron WDG Herbicide (Griffin), and Linuron DF 500 g/kg (AgNova technologies). 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 -2 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%.

-3 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 of two or more of them. Further, suitable anionic surfactants may include naphthalenesulfonic acid polycondensate, alkenylsulfonate, naphthalenesulfonate, formalin condensate of a naphthalenesulfonate, formalin condensate of an alkylnaphthalenesulfonate, lignin sulfonate, alkylallylsulfonate, alkylallyl 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 -4 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 from 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.

-5 [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] Linuron active agent has been commercially available in water dispersible granule 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 of granules or less. [0015] It is desirable to provide a water-dispersable granule of linuron with a loading significantly higher than 500 g/kg. The benefits of a more highly loaded granular wettable powder formulation would include: [0016] 1. A reduced amount of packing material would be necessary to carry a given amount of active ingredient to a cultivation zone. [0017] 2. The cost of disposing of used packaging material would be less. [0018] 3. A reduced weight of goods would need to be carried by a farm worker in applying a given amount of linuron to a cultivation zone.

-6 [00 19] 4. The cost of freight (volume and weight basis) in transporting the linuron formulation from factory to field would be reduced. [0020] 5. A higher loading linuron formulation would enable a manufacturer to demonstrate superior formulation expertise to farmers. [0021] In this specification and claims, the term "highly loaded" is to be taken to refer to the concentration level of active agent in a water dispersible granule form in a formulation on a weight by weight basis (g/kg) in the amount from at least 650 g/kg. SUMMARY OF THE INVENTION [0022] Accordingly, according to one aspect of the present invention there is provided a water-dispersible granule formulation containing linuron, wherein linuron is highly loaded. [0023] Accordingly, according to another aspect of the present invention there is provided a water-dispersible granule formulation containing linuron, wherein linuron is loaded to at least 700 g/kg based on the total formulation weight. [0024] Accordingly, according to another aspect of the present invention there is provided a water-dispersible granule formulation containing at least 700 g/kg of linuron, at least 60 g/kg of one or more surface active agents with the remainder, if any, of the water-dispersible granule formulation being finely divided inert filler. [0025] Most preferably, there is a minimal amount of finely divided filler in the water-dispersible granule formulation.

-7 [0026] According to a further aspect of the present invention there is provided a method of manufacturing a water-dispersible granular linuron formulation including the steps of: [0027] (a) blending fine linuron particles in the presence of one or more surface active agents, preferably, (i) a first surface active agent wherein the first surface active agent functions as a dispersant, (ii) a second surface active agent, wherein the second surface active agent functions as a wetting agent, and (iii) optionally, an inert filler, to homogeneity; [0028] (b) extruding the homogenous linuron blend to form moist granules; and [0029] (c) passing the extruded moist granules through a collecting sieve; and [0030] (d) drying the collected moist granules to a temperature of no greater than 80'C. [0031] Preferably the first surface active agent and the second surface active agent have a combined concentration in the final form of the water dispersible granule formulation of at least 60 g/kg. [0032] Preferably the first surface active agent is a salt of naphthalene sulfonate formaldehyde condensate or sodium naphthalene sulfonate formaldehyde condensate. [0033] It is preferred that the aforesaid step of blending is effected in the presence of a water spray.

-8 DETAILED DESCRIPTION OF THE INVENTION [0034] Preferably the linuron in the water-dispersable granular formulation is loaded to at least about 650 g/kg based on the total weight of the formulation. [0035] Preferably the linuron in the water-dispersable granular formulation is loaded to at least about 700 g/kg based on the total weight of the formulation. [0036] Preferably the linuron in the water-dispersable granular formulation is loaded to at least about 800 g/kg based on the total weight of the formulation. [0037] The linuron to be used in the preparation of water-dispersible granules is in the form of finely divided particles. [0038] The water-dispersible granule formulation may include inert filler that has no herbicidal properties. The inert filler is in the form of a finely divided material and constitutes no more than 250 g/kg based on the total weight of the formulation. [0039] The water-dispersible granule formulation includes at least one, optionally at least two, or optionally at least three surface active agents. The at least one surface active agent functions as a dispersant. It may have ancillary function as a granular binder. One such example of a dispersant is a naphthalene sulfonate formaldehyde condensate such as sodium naphthalene sulfonate formaldehyde. [0040] The second surface active agent, if present, functions as a wetting agent and may be an anionic surfactant.

-9 [0041] The dispersant, being a naphthalene sulfonate formaldehyde condensate such as sodium naphthalene sulfonate formaldehyde, and the wetting agent have a combined amount in the water-dispersible granule formulation of at least 60 g/kg based on the total weight of the formulation. The amount of naphthalene sulfonate formaldehyde condensate such as sodium naphthalene sulfonate formaldehyde may also range from 30 g/kg to 130 g/kg based on the total weight of the formulation. [0042] Useful wetting agents are naphthalene sulfonate salts such as sodium naphthalene sulfonate. The amount of naphthalene sulfonate salts such as sodium naphthalene sulfonate can range between 10 to 60 g/kg based on the total weight of the formulation, though the amount ranging between 25 to 40 g/kg is the more preferred range. [0043] The water-dispersible granule formulation may also include a third type of surface active agent which may also be an anionic surfactant. This third surface active agent may be an alkyl sulphate salt such as sodium dodecyl (lauryl) sulphate. [0044] The amount of alkyl sulphate salt such as sodium dodecyl (lauryl) sulphate may range between 10 to 40 g/kg, although the preferred range lies between 15-30 g/kg based on the weight of the total formulation. [0045] The inert filler in the form of finely divided material, when present, is present in an amount of no greater than 250 g/kg, and preferably no greater than 80 g/kg. [0046] In order to manufacture the water-dispersible granular linuron formulation, a preferred method involves the following steps. [0047] First, a defined quantity of finely divided linuron particles are loaded into a normal industrial sized commercial blender and then blended to - 10 homogeneity in the presence of a water spray or something similar, in combination with all of the other components being: (i) a naphthalene sulfonate formaldehyde concentrate salt; (ii) naphthalene sulphonate salt; (iii) an alkyl sulfate salt; and, optionally, (iv) the finely divided inert filler. [0048] Then the resultant homogenous linuron blend is then transferred to an extruder, which is a usual industrial type extruder, and the ensuring extrusion process forms moist granules of the linuron blend. [0049] The third step of the method of manufacture is to pass the extruded moist wet granules through a sieve, which is, preferably, a 1 mm 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 of up to about 80'C, even though lesser temperatures may be used, are used to dry the moist granules. [0050] After the completion of the above described process, the water dispersible granular formulation will be in the form of dried granules with a moisture content of the order of 1% by weight, based upon the total weight of the formulation. [0051] 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. [0052] According to another aspect of the present invention there is provided a method of controlling weeds including the addition of wettable granular linuron formulation, wherein the linuron 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 soil or weeds.

- 11 [0053] The advantages of highly loaded wettable granular linuron formulations include: reduced packaging requirements, reduced freight costs, reduced amounts of non-herbicidally active ingredients relative to the linuron 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 of problems arising from the presence of inert filler particles. DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS AND EXAMPLES OF THE INVENTION [0054] In order that the present invention may be more readily comprehended, one or more preferred embodiments are described hereinafter. EXAMPLE 1 [0055] A water-dispersible granule formulation according to the present invention (at 800 g/kg linuron) was made by incorporating the following components: Component Purchased from Parts by (incl. trade name) weight (g/kg) Linuron 97% technical Linuron (CAS# 330-55-2) 824.7 Manufacturer unknown Sodium napthalene Proprietary Name = Morwet 80.0 sulphonate D425 (CAS# Proprietary) formaldehyde condensate (e.g. Manufactured by Akzo Nobel Morwet D425) Purchased from Akzo Nobel Sodium napthalene Proprietary Name = Morwet 30.0 sulphonate (e.g. EFW (CAS# Proprietary) Morwet EFW) Manufactured by Akzo Nobel Purchased from Akzo Nobel - 12 Dodecyl (lauryl) Dodecyl sulphate, sodium salt (CAS# 20.0 sulphate, sodium salt 151-21-3) Manufacturer unknown Kaolin clay Kaolin (CAS# 1332-58-7) 45.3 Manufacturer unknown [0056] In Example 1, the formulation procedure for a batch, inclusive of quality control measures, was as follows, with the steps being identified numerically as 1.1, 1.2, 1.3, and so on. [0057] 1.1 Ensure the blender, which is provided with water sprayers, is empty and clean. [0058] 1.2 Charge the blender with the components via a hopper. [0059] 1.3 Seal the blender and switch on. [0060] 1.4 Activate the sprayers to distribute water throughout the dry mix. Introduce sufficient spray water to develop a consistent mix. Operate the blender for a minimum of one further hour to ensure the mix is homogeneous. [0061] 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. [0062] 1.6 Sample approximately 1 kg of product, ensuring it is representative.

- 13 [0063] The water-dispersible granules of example 1 were characterised on the basis of the following parameters. Test Test Method Required Observed Required, Required, Parameter Preferably More (Advised Preferably r preferred Preferably formulation) Appearance Visual White to Off-white, brown, homogeneous,

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homogeneous, granule granule Assay Validated 775 to 825 chromatographic g/kg linuron method (Accuracy: 98 102%) 818 g/kg linuron (Linearity: R > 0.99) (Precision: s/average < 2%) pH (1%) CIPAC MT 75.3 7 to 11 8.9 - <2% w/w over <1% w/w <0.5% Wet sieve test CIPAC MT 185 75 ptm 0.17% over w/w over 75 ptm 75 ptm Spontaneity CIPAC MT174 Between 60 94.4% - of dispersion and 105% Suspensibility CIPAC MT 184 Between 60 96.6% and 105%0 9.0 <1 minute Wettability CIPAC MT53 (without Pass - swirling) Persistent CIPAC MT47 <60 mL after 24 mL <30 mL (1 foam 1 mmn minute) <1%, otherwise Dust content CIPAC MT171 inhalation 0.004% <0.1% toxicity data required - 14 Sample flows Flowability CIPAC MT172 through Pass aperture after Ps <5 liftings Attrition CIPAC >98% 100.0% resistance MT178.2 Long Term Various as per Test parameter Complies Performance above maintained within required range after - accelerated aging to approximate 2 years. [0064] 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, or along with additional linuron (to adjust for a low active content). [0065] 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 as follows: [0066] Catalogue and store a retention sample of approximately 200 g, and generate a certificate of analysis noting results of testing. Tests to Confirm the Suitability of the Formulation of Example 1 [0067] For the test methods identified by the prefix CIPAC, refer to International Pesticides Analytical Council (CIPAC) published methodology.

- 15 BIOEFFICACY STUDIES [0068] A number of trials were carried out to assess the weed control efficacy of a highly loaded linuron water-dispersible granular formulation with that of a conventionally loaded linuron water-dispersible granular formulation when applied to sites containing grass weeds at the same active ingredient rate. The Reports of those trials are set out below. It was found that there was no significant difference in the level of weed control between the formulations. [0069] The reference formulation of linuron was Lorox Linuron DF Herbicide, a dry flowable powder formulation containing 500 g ai/Kg linuron as supplied by Tessenderlo Kerlgy, Inc. This formulation is described as being for selective weed control in carrots, coriander, parsnips, cereals, onions, potatoes, soy beans, sweet corn and maize. The test formulation was identified as Imtrade Linuron 800 WG or as Imtrade Linuron, a water dispersible granule formulation containing 800 g ai/Kg linuron as supplied by the applicant (see Example 1 for formulation details). The trial work in this example was undertaken to examine the bio-equivalency of Lorox Linuron DF Herbicide and the new formulation on common hard-to-kill broad leaf weeds in wheat and barley crops. Treatments [0070] Table 1 sets out the treatment types and application rate of g ai per hectare. Table 1 Tmt Treatment description concentration Rate Units 1 Untreated check 2 Imtrade Linuron 800WG 800 g/kg linuron 312 g/ha - 16 3 Lorox Linuron DF 500 g/kg linuron 500 g/ha Herbicide 4 Imtrade Linuron 800WG 800 g/kg linuron 531 g/ha 5 Lorox Linuron DF 500 g/kg linuron 850 g/ha Herbicide 6 Imtrade Linuron 800WG 800 g/kg linuron 1062 g/ha 7 Lorox Linuron DF 500 g/kg linuron 1700 g/ha Herbicide Experimental Details [0071] The trial was a randomised block design comprising three replicates. Full details are set out in Tables 2, 3, 4, 5 and 6. Experimental Design Table 2 Study Design Complete Randomised Block Replications 3 Plot length 20 x 30 cm pots Site Details Table 3 Location Adelaide, Waite Campus Cocoa peat potting mix produced by mixing 540 L of coco Soil Description peat, 220 L of water and 60 L of sand prior to steaming for 1 hour.

- 17 Crop and Sowing Details Table 4 Timing 1: 1" May: Early Post emergent crop Date Sown th Timing 2: 15 April: Late post emergent crop Varieties Wheat (Mace), Barley (Westminister) Seeding Rate 20 plants/seedlings per tray At Sowing The following additives were then mixed to the pasteurised mix; 180 Nutrition g Dolomite lime; 600 g Agricultural lime; 240 g Hydrated lime; 180 g Gypsum; 180 g superphosphate; 450 g iron sulphate; 30 g iron chelate; 180 g Micromax trace elements; 450 g Calcium nitrate and 1800 g of Osmocote mini 3-4 m (16-3-9+te). Incorporate By Sowing (IBS) of weeds Weeds: sown 5 mm deep. Herbicide sprayed onto soil surface then covered with 5 mm soil to simulate IBS. Tillage type Weeds: post-emergence treatments. Seedlings planted into trays. Crops: sown 20 mm deep. Post-emergence treatments applied at the relevant timing. Crop and weed seeds sown into moist seedbed. The watering for the duration (watering equivalent to 90 mm per month) of the trial (30 Moisture days) was equivalent to 90 mm of rainfall. This is very close to the average rainfall that is received in Clare, SA (average rainfall for June 80 mm, July 73 mm) - 18 Experimental Application Methods: Pre-emergence and Post-emergence Table 5 Crop and Weed Growth Stage all timings detailed in the below table. at Application Wheat var. Mace Crops Barley var. Westminister Wild radish (Raphanus raphanistrum) Target weeds Wild Turnip (Brassica tournefortii) Indian Hedge Mustard (Sisymbrium orientale) Crop Sowing Density 20 seeds per tray Weed Sowing Density 20 seeds per tray Timing 1: 1" May: Early Post emergent crop, pre emergence weeds treatment Date Timing 2: 1" May: Early post emergent crop and weed treatment Timing 3: 15 th April: Late post emergent crop and weed treatment Spray Time 9 am -10 am 15th April: 16'C Temperature I May: 14C Soil Moisture moist to surface Application equipment Spray Chamber Speed 4 km/hr Pressure 2 bar Spray Volume 100 L/ha - 19 Nozzles Tee-Jett 110-01 Number of Nozzles 2 Spacing 50 cm Propellant Compressed Air Rates and Timings Table 6 Treatment Application Application timing rate (g/ha) 1. Untreated -- - 2. Imtrade Linuron 800 312 g Apply pre weed emergence, WG post crop 2-4 leaf stage 3. Lorox Linuron DF 500 g Herbicide 4. Untreated Apply when weeds are > 5 cm in height/width and crop 5. Imtrade Linuron 800 312 g is 2-4 leaf stage WG 6. Lorox Linuron DF 500 g Herbicide 7. Untreated Apply when weeds are 5-15 cm in height/width and 8. Imtrade Linuron 800 531 g crop is 4 leaf - early tiller WG 9. Lorox Linuron DF 850 g Herbicide 10. Imtrade Linuron 800 1062 g WG 11. Lorox Linuron DF 1700 g Herbicide [0072] Survival was calculated by dividing the number of seeds germinating in the treated trays compared to germination in the untreated - 20 checks. A score of 100% indicates complete germination and a score of 0% indicates zero germination (complete control). A subjective score was given based on the level of biomass reduction compared to the untreated checks. A score of 100% indicates complete control and a score of 0% indicates zero herbicide effect. Notations Used: DAA = Days After Application; UTC = Untreated Check; DWT = Dry Weight; GS = Growth Stage; IBS = Incorporated By Sowing; HD = Herbicide damage; ANA= Analysis not applicable. [0073] Calculated means were separated with use of LSD at P = 0.05. Transformation of data did not improve homogeneity of variance, thus, ANOVA was performed on non-transformed percentage herbicide damage and survival. Data on variance was visually inspected by plotting residuals to confirm homogeneity of variance before statistical analysis. Genstat software (Version 15.0, VSN International, Hemel, Hempstead, United Kingdom; VSN 2013) was used for statistical analysis. Early Post Emergent Crop [0074] Table 7 sets out percentage herbicide damage (%) at 11, 21 and 30 DAA of Mace wheat. Imtrade Linuron and Lorox Linuron were applied when the crop was at the 2-leaf stage. In this Table and the following Tables: ns = no significant interaction at P>0.05; numbers with different letters are significantly different (P<0.05); ANA refers to analysis not applicable because data is not significantly different.

- 21 Table 7 Tmt Treatment description 11 DAA 21 DAA 30 DAA 1 Untreated Check 0 a 0 a 0 2 Imtrade Linuron @ 312 8 A 6 g/ha 20 b 3 Lorox Linuron @ 500 g/ha 20 b 16 b 2 P value 0.003 0.012 0.274 L.S.D. (P=0.05) 11 9.4 ns [0075] Table 8 sets out Percent herbicide damage (%) at 11, 21 and 30 DAA of Westminister barley. Imtrade Linuron and Lorox Linuron were applied when the crop was at the 2-leaf stage. Table 8 Tmt Treatment description 11 DAA 21 DAA 30 DAA 1 Untreated Check 0 a 0 a 0 a 2 Imtrade Linuron @ 312 11 A 4 g/ha 18 b 3 Lorox Linuron @ 500 g/ha 32 c 19 b 12 b P value <0.001 0.042 0.006 L.S.D. (P=0.05) 8.5 14.4 6.2 Late Post Emergent Crop and Weed Treatment [0076] Table 9 sets out percent herbicide damage (%) at 11, 21 and 30 DAA of Mace wheat. Imtrade Linuron and Lorox Linuron were applied when the crop was at the 2-tiller stage.

- 22 Table 9 Tmt Treatment description 11 DAA 21 DAA 30 DAA 7 Untreated Check 0 a 0 0 8 Imtrade Linuron @ 531 g/ha 17 b 0 0 9 Lorox Linuron @ 850 g/ha 5 a 0 3 10 Imtrade Linuron @ 1062 g/ha 23 c 0 0 11 Lorox Linuron @ 1700 g/ha 18 bc 0 3 P value <0.001 ANA 0.633 L.S.D. (P=0.05) 6.2 ns [0077] Table 10 sets out percent herbicide damage (%) at 11, 21 and 30 DAA of Westminister barley. Imtrade Linuron and Lorox Linuron were applied when the crop was at the 2-tiller stage. Table 10 Tmt Treatment description 11 DAA 21 DAA 30 DAA 7 Untreated Check 0 a 0 a 0 8 Imtrade Linuron @ 531 g/ha 3 a 7 c 0 9 Lorox Linuron @ 850 g/ha 2 a 3 b 0 10 Imtrade Linuron @ 1062 g/ha 13 b 20 e 0 11 Lorox Linuron @ 1700 g/ha 3 a 15 d 0 P value 0.005 <0.001 ANA L.S.D. (P=0.05) 5.7 3.2 Pre-emergence Weeds Treatment [0078] Table 11 sets out percent herbicide damage (%) at 11, 21 and 30 DAA of Wild Radish. Imtrade Linuron and Lorox Linuron were applied pre emergent.

- 23 Table 11 Tmt Treatment description 11 DAA 21 DAA 30 DAA 1 Untreated Check 0 a 0 a 0 a 2 Imtrade Linuron @ 312 g/ha 53 b 57b 13 b 3 Lorox Linuron @ 500 g/ha 50 b 47 b 23 b P value 0.002 0.031 0.014 L.S.D. (P=0.05) 17.7 39 12.0 [0079] Table 12 sets out percent survival (%) at 11, 21 and 30 DAA of Wild Radish. Imtrade Linuron and Lorox Linuron were applied pre-emergent. Table 12 Tmt Treatment description 11 DAA 21 DAA 30 DAA 1 Untreated Check 100 a 100 a 100 a 2 Imtrade Linuron @ 312 g/ha 62 b 35 b 35 b 3 Lorox Linuron @ 500 g/ha 53 b 37b 37b P value 0.027 0.007 0.007 L.S.D. (P=0.05) 31 32 32 [0080] Table 13 sets out percentage percent herbicide damage (%) at 11, 21 and 30 DAA of Wild Turnip. Imtrade Linuron and Lorox Linuron were applied pre-emergent.

- 24 Table 13 Tmt Treatment description 11 DAA 21 DAA 30 DAA 1 Untreated Check 0 0 0 2 Imtrade Linuron @ 312 g/ha 99 c 100 100 3 Lorox Linuron @ 500 g/ha 96 b 100 100 P value <0.001 ANA ANA L.S.D. (P=0.05) 1.5 [0081] Table 14 sets out percent survival (%) at 11, 21 and 30 DAA of Wild Turnip. Imtrade Linuron and Lorox Linuron were applied pre-emergent. Table 14 Tmt Treatment description 11 DAA 21 DAA 30 DAA 1 Untreated Check 100 100 100 2 Imtrade Linuron @ 312 g/ha 81 0 0 3 Lorox Linuron @ 500 g/ha 88 0 0 P value 0.174 ANA ANA L.S.D. (P=0.05) ns [0082] Table 15 sets out percent herbicide damage (%) 11, 21 and 30 DAA of Indian Hedge Mustard. Imtrade Linuron and Lorox Linuron were applied pre-emergent.

- 25 Table 15 Tmt Treatment description 11 DAA 21 DAA 30 DAA 1 Untreated Check 0 0 0 2 Imtrade Linuron @ 312 g/ha 100 100 100 3 Lorox Linuron @ 500 g/ha 100 100 100 P value ANA ANA ANA L.S.D. (P=0.05) [0083] Table 16 sets out percent survival (%) 11, 21 and 30 DAA of Indian Hedge Mustard. Imtrade Linuron and Lorox Linuron were applied pre emergent. Table 16 Tmt Treatment description 11 DAA 21 DAA 30 DAA 1 Untreated Check 100 100 100 2 Imtrade Linuron @ 312 g/ha 0 0 0 3 Lorox Linuron @ 500 g/ha 0 0 0 P value ANA ANA ANA L.S.D. (P=0.05) Early Post Emergent Weed Treatment [0084] Table 17 sets out percent herbicide damage (%) at 7, 14, 21 and 30 DAA of Wild Radish. Imtrade Linuron and Lorox Linuron were applied when the weeds were at the 5-10 cm height.

- 26 Table 17 Tmt Treatment description 7 DAA 14 DAA 21 DAA 30 DAA 4 Untreated Check 0 a 0 a 0 a 0 a 5 Imtrade Linuron @ 312 96 b 63 b g/ha 57b 77 b 6 Lorox Linuron @ 500 g/ha 57b 90 c 73 b 87 b P value 0.001 <0.001 <0.001 <0.006 L.S.D. (P=0.05) 17.7 10.0 24 35 [0085] Table 18 sets out percent herbicide damage (%) at 7, 14, 21 and 30 DAA of Wild Turnip. Imtrade Linuron and Lorox Linuron were applied when the weeds were at the 5-10 cm height. Table 18 Tmt Treatment description 7 DAA 14 DAA 21 DAA 30 DAA 4 Untreated Check 0 a 0 a 0 0 5 Imtrade Linuron @ 312 100 100 g/ha 73 b 93 b 6 Lorox Linuron @ 500 g/ha 83 b 100 b 100 100 P value <0.001 <0.001 ANA ANA L.S.D. (P=0.05) 15.1 1.5 [0086] Table 19 sets out percent herbicide damage (%) at 7, 14, 21 and 30 DAA of Indian Hedge Mustard. Imtrade Linuron and Lorox Linuron were applied when the weeds were at the 5-10 cm height.

- 27 Table 19 Tmt Treatment description 7 DAA 14 DAA 21 DAA 30 DAA 4 Untreated Check 0 a 0 0 0 5 Imtrade Linuron @ 312 g/ha 80 b 100 100 100 6 Lorox Linuron @ 500 g/ha 90 b 100 100 100 P value <0.001 ANA ANA ANA L.S.D. (P=0.05) 13.1 Late Post Emergent Weed Treatment [0087] Table 20 sets out percent herbicide damage (%) at 11, 21 and 30 DAA of Wild Radish. Imtrade Linuron and Lorox Linuron were applied when the weeds were at the 5-15 cm height/width. Table 20 Tmt Treatment description 11 DAA 21 DAA 30 DAA 7 Untreated Check 0 a 0 a 0 a 8 Imtrade Linuron @ 531 g/ha 40 be 57 b 87 b 9 Lorox Linuron @ 850 g/ha 27 b 63 b 95 c 10 Imtrade Linuron @ 1062 g/ha 73 d 99 c 100 c 11 Lorox Linuron @ 1700 g/ha 53 c 90 c 97 c P value <0.001 <0.001 <0.001 L.S.D. (P=0.05) 18 17 5 [0088] Table 21 sets out percent herbicide damage (%) at 11, 21 and 30 DAA of Wild Turnip. Imtrade Linuron and Lorox Linuron were applied when the weeds were at the 5-15 cm height/width.

-28 Table 21 Tmt Treatment description 11 DAA 21 DAA 30 DAA 7 Untreated Check 0 a 0 0 8 Imtrade Linuron @ 531 g/ha 57b 100 100 9 Lorox Linuron @ 850 g/ha 50b 100 100 10 Imtrade Linuron @ 1062 g/ha 80 c 100 100 11 Lorox Linuron @ 1700 g/ha 80 c 100 100 P value <0.001 ANA ANA L.S.D. (P=0.05) 9.7 [0089] Table 22 sets out percent herbicide damage (%) at 11, 21 and 30 DAA of Indian Hedge Mustard. Imtrade Linuron and Lorox Linuron were applied when the weeds were at the 5-15 cm height/width. Table 22 Tmt Treatment description 11 DAA 21 DAA 30 DAA 7 Untreated Check 0 a 0 0 8 Imtrade Linuron @ 531 g/ha 80 c 100 100 9 Lorox Linuron @ 850 g/ha 70 b 100 100 10 Imtrade Linuron @ 1062 g/ha 83 c 100 100 11 Lorox Linuron @ 1700 g/ha 80 c 100 100 P value <0.001 ANA ANA L.S.D. (P=0.05) 8.8 T- uc N)c T-u r 00 t0

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0 0 ~ 0 - - __ - 0 ~ - - __ - (jl 0 - ~Q W t-~ C ~ ~Jt ~Jt ~ t-~ C 0 I k) -~ - (JJ q~ 0 ~ 4~ ~0 ~ ~Q W W 4~ W ~ ~0 .0 .0 .0 .0 .0 ~0 CC ~ ~ CC CC ~ .0 .0 .0 ~ 0 .0 .0 .0 - - .0 .0 .0 ~0 .0 .0 ~ ~0 ~ -~ 0 ~0 ~0 ~0 ~0 ~0 ~0 CC 4~ ~ CC CC 0 o _ _ -t 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 -t 0 ~0 ~0 ~0 .0 ~0 ~0 ~0 ~ CC ~0 ~0 - 0 ~ ~ ~0 ~ - 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 - 35 Discussion [0095] A pot trial was conducted to investigate bioequivalency of IMTRADE LINURON 800WG compared to LOROX LINURON DF HERBICIDE when used in wheat and barley at equivalent g.ai rates, targeting key broadleaf weeds at various stages of growth. Crop Safety Early-post emergent crop [0096] IMTRADE LINURON did not cause significant damage (8%) in wheat at 21 DAA whereas LOROX LINURON DF HERBICIDE did (16%). However, at 30 DAA the damage caused by either product was not significantly different from the untreated. [0097] In barley, LOROX LINURON caused more damage (32%) than IMTRADE LINURON (18%) at 11 DAA. IMTRADE LINURON was safer than LOROX LINURON at 21 and 30 DAA in barley. Late-post emergent crop treatment [0098] Early damage (11 DAA) was observed on wheat with IMTRADE LINURON that was statistically significant when compared to LOROX LINURON at equivalent g.ai/ha. At the higher rates of each product (2x field rate) significant damage at 11 DAA was observed compared to the untreated control, but no significance between products was observed. At subsequent timings (21 DAA and 30 DAA), the wheat crop fully recovered, growing out of the early post application damage from both products at all rates. [0099] At the 2x application rate of IMTRADE LINURON (531 g/ha), a significant difference was observed in crop damage out to 21 days when - 36 compared to equivalent g.ai/ha of LOROX LINURON. By the 30 DAA timing, all treatments and rates were statistically similar, with the crop growing out of the post application damage observed at the earlier assessment timings. Weed Efficacy Pre-emergent weeds treatment [0100] IMTRADE LINURON, when used as a pre-emergent treatment, provided equivalent control to that obtained by LOROX LINURON on Wild Radish emergence. Approximately 50% herbicidal damage was caused with 53-62% and 35-37% survival at 11 and 21 DAA, respectively. No differences in survival were observed between 21 and 30 DAA. The plants present at 21 DAA of both products recovered exhibiting reduced levels of biomass reduction that were not statistically different from each other. [0101] No significant reduction in survival of wild turnip was observed at 11 DAA with either product. The plants were however strongly inhibited in size, with IMTRADE LINURON causing statistically greater herbicide damage at 11 DAA. At the 21 and 30 DAA timings, total control was observed with both products. [0102] Indian hedge mustard was totally inhibited by both products at 11 DAA with no plants observed at any subsequent timing. Early-post emergent weed treatment [0103] Both products caused equivalent damage to young wild radish 7 DAA. At 14 DAA, statistically greater damage was caused by LOROX LINURON when compared to the equivalent g.ai/ha application of IMTRADE LINURON, whereas at 21 DAA the damage caused by both products was not - 37 significantly different. A slight recovery of about 10% reduction in biomass was observed by wild radish at 30 DAA by both products. [0104] Strong inhibition of wild turnip was caused by both herbicides from 7 DAA. There was no statistically significant difference in the control of wild turnip at any timing between IMTRADE LINURON and LOROX LINURON. Complete control was observed at the latter timings with both products. [0105] The damage caused by both herbicides on Indian hedge was not statistically significant, with both IMTRADE LINURON and LOROX LINURON providing complete control post 7 DAA. Late-post emergent weed treatment [0106] IMTRADE LINURON provided equivalent or better control than LOROX LINURON on wild radish at 11 DAA. Overall damage increased at 21 DAA, with no significant difference noted at equivalent g.ai/ha of both products. At 30 DAA IMTRADE LINURON exhibited significantly lower control of wild radish when applied at the 1x rate, but was statistically equivalent at 2x application rates. [0107] No statistical differences were noted between either IMTRADE LINURON or LOROX LINURON at any equivalent rate or timing for the control of Wild Turnip. Complete control was observed with both products post 14 DAA. [0108] LOROX LINURON caused significantly less damage than IMTRADE LINURON on Indian hedge mustard at 11 DAA. Complete control was observed with both products at subsequent timings.

- 38 Conclusion [0109] Crop Safety: At equivalent active ingredient application levels, a similar level of safety with IMTRADE LINURON 800WG compared to LOROX LINURON DF HERBICIDE was observed in wheat and barley. [0110] Weed Efficacy: The efficacy of IMTRADE LINURON 800WG treatments on wild radish, wild turnip and Indian hedge mustard applied as pre emergence, early- or late- post-emergent treatments at equivalent active ingredient application levels were equivalent to LOROX LINURON DF HERBICIDE. [0111] 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 of the invention intended to be limited only by the claims set forth herein as follows. [0112] 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. [0113] 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 - 39 matter forms part of the common general knowledge in the field of endeavour to which this specification relates.

Claims (21)

1. A water-dispersible granular formulation containing linuron, wherein the linuron is loaded to at least 650 g/kg based upon the total formulation, and wherein the formulation further includes: (a) a first surface active agent wherein the first surface active agent is a dispersant; (b) a second surface active agent, wherein the second surface active agent is a wetting agent; and, optionally, (c) an inert filler.

2. The water-dispersible granular formulation according to claim 1, wherein the first surface active agent and a second surface active agent have a combined amount of at least 60 g/kg.

3. The water-dispersible granular formulation according to claim 1 or claim 2 wherein, the first surface active agent includes a salt of naphthalene sulfonate formaldehyde condensate or sodium naphthalene sulfonate formaldehyde condensate.

4. The water-dispersible granular formulation according to claims 1 to 3, wherein the first surface active agent is in the amount ranging between 30 g/kg to 130 g/kg.

5. The water-dispersible granular formulation according to any one of claims 1 to 4, wherein the second surface active agent includes an anionic surface active agent.

6. The water-dispersible granular formulation according to any one of claims 1 to 5, wherein the second surface active agent includes a naphthalene sulphonate salt or sodium naphthalene sulphonate . - 41

7. The water-dispersible granular formulation according to claim 6, wherein the naphthalene sulphonate salt or sodium naphthalene sulphonate is in the amount ranging between 10 g/kg to 60 g/kg.

8. The water-dispersible granular formulation according to either claim 6 or claim 7, wherein the naphthalene sulphonate salt or sodium naphthalene sulphonate is in the amount ranging between 25 g/kg to 40 g/kg.

9. The water-dispersible granular formulation according to any one of claims 1 to 8, which further includes a third surface active agent, wherein the third surface active agent includes an anionic surfactant.

10. The water-dispersible granular formulation according to claim 9, wherein the third surface active agent includes alkyl sulphate salt or sodium dodecyl (lauryl) sulfate.

11. The water-dispersible granular formulation according to claim 10, wherein the alkyl sulphate salt or sodium dodecyl (lauryl) sulphate is in the amount ranging between 10 g/kg to 40 g/kg.

12. The water-dispersible granular formulation according to any one of claims 1 to claim 11, wherein the inert filler, when present, is no greater than 250 g/kg.

13. The water-dispersible granular formulation according to any one of claims 1 to 12, wherein the inert filler, when present, is in the form of finely divided material.

14. The water-dispersible granular formulation according to any one of claims 1 to 13, wherein the granular formulation has moisture content of less than about 1% by weight. - 42

15. A water-dispersible granular formulation containing linuron, wherein the linuron is highly loaded based upon the total formulation.

16. A water dispersible granule formulation containing 824.7 g/kg linuron 97%, 80 g/kg sodium naphthalene sulphonate formaldehyde condensate, 30.0 g/kg sodium naphthalene sulphonate, 20.0 g/kg dodecycl (lauryl) sulphate, sodium salt, and 45.3 g/kg kaolin clay, all weights being grams per kilogram of total formulation.

17. A method of manufacturing a water-dispersible granular linuron formulation comprising the steps of: (a) blending fine linuron particles and at least one surface active agent being a dispersant, and at least one other surface active agent, being a wetting agent, to form a linuron blend; (b) extruding the homogenous linuron blend to form moist granules; (c) passing the extruded moist granules through a collecting sieve; and (d) drying the collected moist granules to a temperature up to about 80'C.

18. The method according to claim 17, wherein the step of blending linuron particles is carried out in the presence of any one or more of the following additional components: finely divided inert filler; and a third surface active agent.

19. The method according to either claim 17 or claim 18, wherein the step of blending is carried out in the presence of a water spray.

20. The method according to any one of claims 17 to 19, wherein the collecting sieve is 1 mm to 5 mm.

21. A method of controlling weeds, including the addition of highly loaded water-dispersible granular linuron formulation to spray water in a spray tank and spraying the resultant spray liquor onto soil or onto a site containing weeds.