AU2020244434A1 - Granular Pesticide Composition for Turf and Forestry and Method - Google Patents

Abstract

A broadcast granule composition comprising a granule core and coatings about the core the coatings comprising (i) a coating layer of powder comprising pesticide about the core; and (ii) a coating of sticker about the powder coating layer.

Description

Granular Pesticide Composition for Turf and Forestry and Method

Technical Field

Field

[0001] This invention relates to a granular composition of pesticides for use in forestry and turf care and to preparation of the composition. In particular the invention relates to a broadcast granule composition that is a granular composition to be applied to soil and/or vegetation by directly spreading onto the soil and/or vegetation.

Background of Invention

[0002] Pesticides for use in forestry and turf management may be used in granular form by absorbing a solution or dispersion of pesticide onto a granule core. The use of solvents or liquid carriers for coating a granule core with pesticide presents a number of problems. The use of solvent typically leads to an increase in cost or process complexity. Solvent or liquid carrier may weaken the surface of the core moiety, leading to dust formation in transport and storage of the coated core moiety, or to granule compression in storage. The solvent may compromise the appearance of the final coated product in a consumer package.

[0003] Organic solvents often present a manufacturing or consumer hazard and generally require removal by heating. The required safety precautions and disposal requirement for such solvents also impose a significant cost on the manufacturer. The generation of fine-powder containing pesticide during manufacture, storage and handling of pesticide granules may also present a hazard because of the flammability of some pesticides. The use of granulation methods involving agitation during or after granule formation may lead to dust formation exacerbating the hazards and potential flammability problem.

Summary of Invention

[0004] In one aspect the invention provides a broadcast granule composition comprising a granule core and coatings about the core the coatings comprising

(i) a coating layer of comprising pesticide powder about the core; and

(ii) a coating of sticker about the pesticide powder coating layer.

[0005] In a further aspect the invention provides a method of preparing the broadcast granules, comprising:

(i) contacting a granule core with a powder comprising pesticide with agitation to deposit a coating of pesticide powder about the granule core;

(ii) contacting the powder coated granule core with a heated sticker with agitation to overcoat the pesticide coated core with the heated sticker.

[0006] The invention is concerned with a granular composition of pesticide for use particularly in forestry and turf management. Pesticides for use in the composition include specific herbicides and insecticides for use in turf and forestry applications.

[0007] Forestry herbicides may be selected from the group consisting of: imazopyr, metsulfuron-methyl, sulfometuron, sulfometuron-methyl, triclopyr, aminopyralid, dicamba, fosamine, hexazinone, picloran and 2,4D.

[0008] Forestry insecticides may be selected from the group consisting of: azodiractin, acelepryn, abamectin, acetamiprid, acephile, bifenthrin, borate, carbaryl, chlorfenapyr, cyantraniliprole, cyfluthrin, deltamethrin, dimethoate, dinotefuran, amamectin benzoate, fenoxycarb, fipronil, floxicamid, fluvalinate, imidacloprid, lambda cyhalothrin, malathion, neem oils, inceticidal oils, pyrethroid, pymetrazine, pyrethrin, pyridalyl, Spinosad, spinetoram, spiromesifen, tolfenpyrad, trichlorfor.

[0009] Turf herbicides may be selected from the group consisting of: terpene alcohols and saponified fatty acids, bromoxynil, MCPA, dicamba, prosulfuron, iodosulfuron, rimsulfuron, diclofop-methyl, dithiopyr, MCPA dimethylamine salt, Dicamba dimethylamine salt, quinclorac, DSMA, oryzalin, MCPA potassium salt, clopyralid potassium, diflufenican, metolachlor, metribuzin, MSMA, trifloxisulfuron sodium, bispyribac-sodium, pine oil, pendimethalin, propyzamide, florasulam, fluoroxpyr, halosulfuron-methyl. Carfentrazone, MCPA-sodium, carfentrazone-ethyl, diflufenican and clopyralid olamine, MCPA acid, indaziflam, foramsulfuron, dicamba acid, MCPA isooctyl ester, bromoxynil octanoate, siduron, prodiamine, s metolachlor, isoxaben, florasulan and amicarbazone.

[0010] Turf insecticides may be selected from the group consisting of: chlorantraniliprole, abamectin, clofentezine, exotazole,, diafenthiuron, fluopram, imidacloprid, fipronil, diazinon, indoxacarb, bifenthrin, cyantraniliprole, chlorantraniliprole chlorpyrifos, and beta-cyfluthrin.

[0011] Turf pesticides and/or forestry pesticides may be used in powder form where they are high melting point solids (e.g. greater than 700C) or where they are liquid or lower melting point solids they may be absorbed onto a suitable solid powder carrier. Suitable solid powder carriers are typically of high porosity such as porous silica (e.g. aluminium silicate, mesoporous silica gel, granulated fused silica).

[0012] The application of sticker about the pesticide powder coated granule core allows a uniform coating of powder to be immobilised on the surface of the granule core. Overcoating of the sticker provides a protective coating which reduces dust formation without build-up of a mass of sticker and pesticide powder on the walls of the mixing vessel used for agitation of the granules. This can not readily be achieved by methods with the alternative order of addition which involve adding a sticking agent to the core, and then adding a powder mixture to the sticky core.

[0013] The invention further provides a method of controlling pests in forestry or turf management comprising applying the above described broadcast granules to the locus of pests.

Detailed Description

[0014] Throughout the description and the claims of this specification the word "comprise" and variations of the word, such as "comprising" and "comprises" is not intended to exclude other additives, components, integers or steps.

[0015] The granular herbicide containing pesticide is suitable to be applied to soil and/or vegetation by directly spreading the granule composition onto the soil and/or vegetation at a suitable dosage rate. The dry granule composition can generally be applied with a dry spreader or by hand to a target area, such as an area of turf and when exposed to water by way of, for example, rain or irrigation, the pesticide herbicide may migrate from the granular composition to the soil surface.

[0016] The terms turf and lawn are used herein to be essentially equivalent and interchangeable. Common types of grasses used in lawns around Australia include Kikuyu grass, Buffalo grass, Couch grass, Zoysia grass and Tall Fescue.

[0017] We have found that the process of the invention comprising blending the dry-coated core with a sticking agent to provide an adhered coating of sticking agent about the powder coated core provides a significant improvement when compared with a corresponding process of first adding sticker to the core and then adding the powder mixture to the sticky core. Without wishing to be bound by theory, it is believed that the formation of the primary blend in the instant invention may involve an electrostatic affinity between the surface of the granule core and the surface of the pesticide powder, leading to a substantially uniform dry-coated layer of carrier powder around the core. The electrostatic forces provide a relatively uniform layer of powder comprising pesticide which becomes locked in place on application of the sticking agent.

[0018] Without wishing to be bound by theory, it is further believed that when the core of the invention is dry-coated with powder comprising pesticide powder, the interstitial spaces between the powder particles of the dry coating have capillary character which efficiently soaks up post-added sticking agent into the region proximal to the surface of the core. This efficient deposition of sticking agent onto the granule rather than the walls of the vessel used for agitation does not occur when the sticking agent is applied to the core before the carrier powder is added.

[0019] The viscosity of the sticker may be chosen to optimise the performance in adhering to the pesticide powder coated granule core and providing a free-flowing granular composition with an effective barrier to dust formation.

[0020] The sticker may have a ratio of kinematic viscosity at 400 C to the kinematic viscosity 100C of at least 8. The sticker, in one set of embodiments has a ratio of kinematic viscosity at 40 0C to the kinematic viscosity 100°C of at least 11, preferably at least 14, more preferably at least 14 such as at least 17, at least 20, at least 23, at least 26, at least 28, or at least 30. Typically, the sticking agent has a ratio of kinematic viscosity at 40 0C to the kinematic viscosity 100C is no more than 50 such as no more than 40 or no more than 35.

[0021] The specific kinematic viscosity of the sticker will depend on the desired temperature for mixing with the powder coated granule core and the conditions under which the granular composition is to be stored and used. In one set of embodiments the sticker has a kinematic viscosity of the sticker at 400C of more than 150 centistokes. The sticker may have a kinematic viscosity at 400C of more than 1500 centistokes, preferably more than 5,000, 10,000, 15,000, 20,000 centistokes. The broadcast granule may have a kinematic viscosity at 400C of no more than 40,000, preferably no more than 30,000, such as no more than 20,000 centistokes.

[0022] The kinematic viscosity of the sticker at 100°C is typically more than 8 centistokes preferably more than 50 centistokes, more preferably more than 100, such as more than150, more than 200, more than 300, more than 400, or more than 500 centistokes. The kinematic viscosity of the sticker at 100C is, in one set of embodiments, no more than 1500, preferably no more than 1200, such as no more than 1000, no more than 900, no more than 800, no more than 700, no more than 600, or no more than 500 centistokes.

[0023] For example, in one set of embodiments (i) the kinematic viscosity at 400C of no more than 50,000 centistokes, and (ii) a kinematic viscosity at 100°C of no more than 2,000 centistokes.

[0024] The broadcast granule composition comprises a powder coating of the granule core. The concentration of pesticide in the granule will depend on the end use application of the granular herbicide, the size of the granule core and the desired treatment rate. In a preferred set of embodiments, particularly for end use in control of weeds in turf, the concentration of pesticide in the granular composition is at least 0.05%, preferably at least 0.1%, more preferably at least 0.3%, still more preferably at least 0.5 % on a weight/weight basis. Typically, the concentration of pesticide in the granular composition is no more than 10%, preferably no more than 5%, such as no more than 3% or no more than 2 %, on a weight/weight basis.

[0025] The concentration of sticker in the granule composition may depend on the specific physical and chemical properties of the sticker and the conditions selected for manufacture and use. Typically, the concentration of the sticker in the granular composition is at least 0.1%, preferably at least 0.2%, such as at least 0.3%, at least

0.4%, on a weight/weight basis. The sticker is typically present in amounts of up to 4%, preferably up to 3% such as up to 2% or up to 1%on a weight/weight basis of the granular composition.

[0026] The granular composition comprises a granule core which provides a carrier for the pesticide powder. The core may be selected from a wide range of materials which may be inert or may and preferably is selected from plant nutrients, soil conditioning agents, fertilisers, pesticidal actives and plant growth regulators.

[0027] The core may comprise materials such as clays, aluminosilicates, talc or mixtures. In one set of embodiments the granule core comprises one or more plant nutrients preferably selected from the group consisting of carbon, nitrogen, phosphorous, potassium, potassium, sulfur, calcium, magnesium, boron, chlorine, copper, iron, manganese, molybdenum, nickel and zinc.

[0028] The broadcast granule composition may comprise one or more carrier materials selected from clay, calcium carbonate, ammonium nitrate, ammonium sulfate, ammoniated superphosphate, ammonium chloride, monoammonium phosphate, diammonium phosphate, ammonium nitrate, calcium cyanamide, calcium nitrate, urea guanidine, guanidine nitrate, nitro guanidine, superphosphate, triple superphosphate, potassium nitrate, potash, potassium chloride, potassium sulfate, potassium metaphosphate, urea, urea phosphate silicon dioxide, gums, insoluble metal oxides, minerals, bentonite, perlite, talc, kaolin, aluminum silicate, diatomaceous earth, attapulgite, barium sulfate, mica, calcium carbonate, precipitated silicates, aluminum silicate, zeolites and mixtures or combinations thereof.

[0029] The core of the broadcast granule composition may comprise one or more chelating agents that bind plant nutrients. Examples of chelating agents include for example EDTA, amine-polycarboxylates, glucuronates and the like.

[0030] The core of the broadcast granule composition may be prepared by a range of methods known in the art for granule formation. These may include crushing to the required size, attrition or agglomeration of smaller particles and prilling. It is preferred that the granule core is a prilled or granulated composition.

[0031] Core fertiliser granules may be of a controlled release type known in the industry. In a further embodiment the cores may comprise a mixture of coated and uncoated fertiliser granules.

[0032] In one embodiment the core moiety comprises a fertiliser that may comprise a single nutrient or a composite of various nutrients. Nutrients used in the invention may include ammonium nitrate, ammonium sulfate, ammoniated superphosphate, ammonium chloride, monoammonium phosphate, diammonium phosphate, calcium nitrate, calcium carbonate, urea guanidine, guanidine nitrate, nitroguanidine, superphosphate, triple superphosphate, potassium nitrate, potash, potassium chloride, potassium sulfate, potassium metaphosphate, urea, urea phosphate, or mixtures or combinations.

[0033] In one embodiment the core moieties may comprise fertiliser that has at least one of nitrogen (N), phosphorous (P) or potassium (K). These elements may be combined in different ratios. For example in one aspect, the NPK ratios may be 13 13-13 or 27-0-0, or 12-50-0 of 21-7-15, or 15-15-15, 10-11-18 or 16-6-8. Other NPK ratios will be evident to those skilled in the art.

[0034] In a particularly preferred embodiment the core moieties comprise a soil amendment agent which comprises no more than 10% by weight of N, P, or K values, preferably no more than 5%, such as no more than 3%, no more than 2% or no more than 1% by weight.

[0035] In one preferment the soil amendment agent is in the form of a prill wherein the prill comprises finely divided soil amendment agent such as calcium carbonate.

[0036] The use of a prilled granule core comprising soil amendment agent may be preferable to the use of a core fertiliser moiety because soil amendment agents can be added over a wider range of application doses than fertiliser agents, and this provides superior flexibility with respect to the application rate of pesticide in the form of a pesticide-coated prill.

[0037] In one preference the agitated granules (immediately prior to the addition of sticker) are agitated in a rotating pan or container such as a cement mixer, however preferably the granules are agitated using a screw impeller within a static vessel (such as exists in a Nauta mixer).

[0038] In a preferred embodiment of the invention the ganule core comprises calcium carbonate, preferably in an amount of at least 30% w/w, more preferably at least 50% w/w, such as at least 70% w/w or at least 80% w/w of the granule core composition. The more preferred granule core is a prilled calcium carbonate composition comprising at least 50% w/w, such as at least 70% w/w or at least 80% w/w calcium carbonate.

[0039] The sticker may be a material of uniform molecular weight or a material that comprises components with a plurality of molecular weights, and the key attribute of the sticker is the high differential in kinematic viscosity between 400C (cold) and 100C (warm).

[0040] In one preferment the sticker comprises no more than 20% by weight of solvents or water, preferably no more than 10%.

[0041] Examples of stickers include random, block or mixed random/block polymers or oligomers including polymers and oligomers comprising based on olefins such as polyethylene, oxidised polyethylene, propylene, polyisobutylene, styrene containing moieties, polyester moieties, polyether moieties (including polyoxyethylene, polyoxypropylene and polyoxybutylene moieties), vinyl resin moieties such as polyvinylacetate, polyvinyl alcohol, polyvinyl pyrrolidone, acrylic moieties, cellulose derivatives, polyamides, polyamines, polyimides, polycarbonates, polysufones, polysulfides, polysaccharides and blends of two or more thereof. The above stickers may be derivatised e.g. with chloride moieties, hydroxy moieties, carboxy moieties, ether moieties or ester moieties.

[0042] Stickers may comprise polyesters such as polycaprolactone, waxes, natural resins, fats and oils and modified products of these. Examples of waxes include beeswax, Japan wax, paraffin and the like.

[0043] An even more preferred type of sticking agent has a number-average molecular weight of 400-1400, such as about 950-1400.

[0044] The coating of sticker comprises at least one selected from the group consisting of stearamide; polyolefins such as polyethylene, oxidized polyethylene, polypropylene, polyisobutylene, styrene-based polymer; polyolefin (block) copolymers; polyesters; polyesters (block) copolymers; polyethers, such as polyethylene oxide, polypropylene oxide; polyether (block) copolymer; vinyl resin such as polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyvinyl pyrrolidone, polyvinyl acetal, polyvinyl methyl acetamide; acrylic polymers; cellulose derivatives such as cellulose acetate; polyamides; polyamines; polyimides; polycarbonates; polysulfones; polysulfides; polysaccharides and blends of two or more thereof.

[0045] In one embodiment of the invention, the process of the invention involves heating the thermoplastic polymer or viscous material to reduce the viscosity on contact of the sticking agent with the pesticide powder that dry-coats the core. The temperature to which the sticking agent is heated will depend on the specific sticking agent and the properties optimal for providing a coating of the sticking agent on the pesticide powder that dry-coats the core. In one embodiment the sticking agent is heated to a temperature in the range of 400C to 1300C such as 400C to 800C or 500C to 800C. The sticking agent may be heated to a temperature sufficient to provide a Kinematic viscosity of no more 30,000 cSt such as from 1 cSt to 30,000 cSt or from 1 cSt to 10,000 cSt such as 1 cSt to 5000 cSt or 1 cSt to 2000 cSt.

[0046] The coating of sticker preferably comprises polybutene having a Kinematic viscosity of at least 200 centistokes (cSt) at 400C. The coating of sticking agent may comprise polybutene may have and a Kinematic viscosity of at least 300, centistokes (cSt) at 400C.

[0047] In one set of embodiments the broadcast granule composition comprises polybutene sticker having a Kinematic viscosity of no more than 10,000 cSt at 100°C preferably no more than 5,000 cSt at 1000C

[0048] In a particularly preferred embodiment the broadcast granule composition comprises a polybutene sticker of molecular weight (Mn) from 400 to 3000.

[0049] The more preferred sticking agent is polybutene and in particular polybutene of molecular weight (Mn) from 400 to 3000. Examples of specific grades of polybutene and their physical properties are provided in Table 1.

[0050] Table 1

Item Unit PB450 PB680 PB950 PB1300 PB1400 PB2400

Molecular weight Mn 450 680 950 1300 1400 2450 Kinematic Viscosity 400C cSt 190 1,700 7,200 22,000 27,000 206,000 1OOOC cSt 14 80 230 645 810 4,700 Flash Point (COC) OC 160 175 210 220 230 260 Pour Point OC -31 -14 0 3 5 17 Density @25°C g/cm3 0.854 0.874 0.890 0.896 0.899 0.906 Color APHA 15 15 15 15 15 15 Density @250C wt% 0.7 0.64 0.18 0.11 0.10 0.05 Loss on Heating mgKOH/g 0.01 0.01 0.01 0.01 0.01 0.01 Water Content Ppm 30 30 30 30 30 30

[0051] The pesticide powder may be applied to the granule core in admixture with a carrier powder. In this embodiment it is preferred that the weight ratio of pesticide powder to carrier powder is at least 1:30 such as at least 1:10 or at least 1:5.

[0052] The carrier powder, when present, may be selected from materials used in the core of the granular composition. In one set of embodiments the carrier comprises at least one selected from the group consisting of silicon dioxide, gums, insoluble metal oxides, minerals, bentonite, perlite, talc, kaolin, aluminum silicate, diatomaceous earth, attapulgite, barium sulfate, mica, calcium carbonate, precipitated silicates, aluminum silicate and zeolites.

[0053] The turf herbicides that can for example be selected from the group consisting of terpene alcohols and saponified fatty acids, bromoxynil, MCPA, dicamba, prosulfuron, iodosulfuron, rimsulfuron, diclofop-methyl, dithiopyr, MCPA dimethylamine salt, Dicamba dimethylamine salt, quinclorac, DSMA, oryzalin, MCPA potassium salt, clopyralid potassium, diflufenican, metolachlor, metribuzin,MSMA, trifloxisulfuron sodium, bispyribac-sodium, pine oil, pendimethalin, propyzamide, florasulam, fluoroxpyr, halosulfuron-methyl. Carfentrazone, MCPA-sodium, carfentrazone-ethyl, diflufenican, clopyralid olamine, MCPA acid, indaziflam, foramsulfuron, dicamba acid, MCPA isooctyl ester, bromoxynil octanoate, siduron, isoxaben, florasulan, s-metalochlor, prodiamine, amicarbazone and mixtures of two or more thereof.

[0054] Turf insecticides that can, for example be selected from the group consisting of chlorantraniliprole, abamectin, clofentezine, exotazole, diafenthiuron, fluopram, imidacloprid, fipronil, diazinon, indoxacarb, bifenthrin, cyantraniliprole, chlorpyrifos, beta-cyfluthrin and mixtures of two or more thereof.

[0055] Turf herbicides or turf insecticides are present in powder form. Where they are high melting point solids (e.g. greater than 700C) the powder may consist of the pesticide in finely divided form. Where they are liquid or lower melting point solids the powder may be in the form of the pesticide absorbed onto a suitable solid powder carrier. Suitable solid powder carriers are typically of high porosity such as porous silica (e.g. aluminium silicate, mesoporous silica gel, granulated fused silica).

[0056] The diameter of the pesticide broadcast granules of the composition is not narrowly critical but is typically no more than 5mm, preferably no more than 4mm such as no more than 3mm. Typically the granule core diameter is at least 0.5mm, preferably at least 1mm, such as at least 2mm.

[0057] The pesticide powder component of the broadcast granule composition is typically of particle size no more than 150 microns, preferably no more than 100 microns, such as no more than 50 microns or no more than 20 microns. Where other powder components are used as part of the powder component comprising pesticide they will typically also be of this size.

[0058] In one aspect of the invention the broadcast granule composition:

the granule core has an average diameter 1mm to 5mm; and

the pesticide powder has an average diameter of no more than 100 microns such as 5 to 100 microns.

[0059] One of the advantages of the broadcast granular herbicide of the invention is the ability to avoid the use of significant amounts of volatile organic solvent.

Typically, the composition comprises no more than 4% w/w of the granule of volatile organic solvent.

[0060] In one aspect the invention provides a method of preparing the above described broadcast granules, comprising:

(i) contacting a granule core with a powder comprising pesticide with agitation to deposit a coating of pesticide powder about the granule core;

(ii) contacting the powder coated granule core with a heated sticker with agitation to overcoat the pesticide coated core with the heated sticker.

[0061] The method may comprise contacting a granule core with a powder comprising pesticide with agitation in a rotating mixing vessel selected from a drum or pan or a mixing vessel provided with an agitator such as a rotating screw. In one embodiment the agitation of the granule core composition is provided by in a rotating drum such as a cement mixer. The rotation speed of the drum is preferably slower than 1 revolution per 2 seconds, more preferably slower than 1 revolution per 5 seconds.

[0062] It is preferred that the core granule composition is agitated in a controlled and gentle manner during contact with the pesticide powder as such conditions facilitate effective coating onto the core. The pesticide powder is preferably added gradually to the agitated granule core and the agitation carried out at a slow rate. For example, the granule core may be agitated at a rate slow enough to adhere a substantially uniform coating of at least 80% of the pesticide is to the surface of the granule core, more preferably at least 90%, such as at least 95%, at least 96%, at least 97%, at least 98%, or at least 99% by weight.

[0063] In one set of embodiments the powder comprising pesticide is added to the agitated core over a time period of at least 5 minutes, preferably at least 10 minutes such as at least 15, at least 20 or at least 25 minutes.

[0064] In another embodiment the agitation of the granule core is provided in a vessel with a rotating screw impeller.

[0065] The rotation speed of the screw impeller is typically no more than one rotation per 2 seconds, preferably no more than 1 rotation per 5 seconds.

[0066] In a particularly preferred embodiment, the sticker is combined with the granule core with the sticker at a temperature of from 400C to 1300C, preferably 500C to 800C, prior to contact with the granule core.

[0067] In the invention, it is surprising that providing a first coating of fine-powder pesticide to the cores, and then then adding sticker as an overcoat (preferably in a gentle agitation environment) leads to no more loss of sticker to the walls of the vessel.

[0068] Without wishing to be bound by theory it is believed that the pre-existing powder coating provides a highly absorbent coating in which the interstitial spaces of the powder coating can take up sticker in a much more efficient way than competing adhesion to the smooth walls of the vessel (or screw impeller).

[0069] Without wishing to be bound by theory it is believed that the fine-powder pesticide in the first coating about the core is held in place by electrostatic forces.

[0070] Other benefits of the Invention include:

the ability to avoid volatile solvents and the loss of volatiles to atmosphere in manufacturing or in storage, transport and use;

the low energy requirement for preparation of the granular pesticide composition;

the uniformity of product and ability to minimise the quantity of off-spec material;

diminished dust formation during storage and handling;

reduced number of application campaigns to achieve turf management objective saving time, fuel and water. One application is required to deliver herbicide and soil amendment agent to turf rather than two applications; and

lower clean-up costs in manufacture.

[0071] The invention will now be described with reference to the following examples. It is to be understood that the examples are provided by way of illustration of the invention and that they are in no way limiting to the scope of the invention.

Examples

[0072] Example 1 (Composition of the invention)

[0073] Examples of some of the components useful in the invention are listed in Table 2.

[0074] Table 2

Component CAS. No Chemical name Concentration Function (g/kg)

5-dipropylamino-alpha, Imidacloprid 29091-21-2 alpha, alpha-trifluoro-4,6- 10.26 Active (technical) dinitro-o-toluidine (fine- ingredient powder form)

Polyisobutene

Polybutene Kinematic viscosity 40 degC 9003-27-4 equals 22,000 cSt, 5.0 Sticker PB1300 Kinematic viscosity 100 deg C equals 645 cSt

Calcium carbonate Calgrit prills 471-34-1 984.74 Solid carrier Predominantly 1.5-2.5 mm

1000

[0075] Example 2 (Process of the Invention)

[0076] Compositions of the invention were prepare using the following method:

[0077] -The Calgrit prills were placed in a stainless-steel vessel which is placed under a planetary mixer set to a slow mixing speed. An alternative mixing apparatus is a Nauta conical screw mixer.

[0078] -The fine-powder imidacloprid technical material is slowly added to the Calgrit prills while these prills are under agitation. The mixing is continued until the fine-powder imidacloprid has coated the prills and it was observed that the coated-prill contents of the mixing vessel were homogeneous and there was no observable region in the mixer with a high concentration of fine-powder imidacloprid.

[0079] -The polybutene PB 1300 was heated to 700C and the resultant warm liquid was slowly poured onto the fine powder-coated Calgrit prills with continuation of the gentle agitation provided in previous steps. The gentle mixing was continued until the coated granules appeared homogeneous and evenly-coated. Clusters of granules were broken apart and returned to the mixing vessel.

[0080] The granules were free of dust, and though they were slightly tacky, they were free-flowing. The walls of the vessel were substantially free from sticker and from adhered imidacloprid powder.

[0081] The granules may be applied to turf using a granule spreader or hand shaker at an effective rate.

[0082] Examples 3 - 5

[0083] The composition of Example may be prepared using the process of Example 2 and replacing the active imidacloprod with the following actives in the concentration specified in Table 3:

[0084] Table 3

Example No Active Concentration

3 chlorantraniliprole 1Og/kg

4 prodiamine 1Og/kg

hexazinone 1Og/kg

[0085] Example 6

[0086] Examples of some of the components useful in the invention are listed in Table 4.

[0087] Table 4

Component CAS. No Chemical name Concentration Function (g/kg)

5-dipropylamino-alpha, Prodiamine 29091-21-2 alpha, alpha-trifluoro-4,6- 10.26 Active (97.5%) dinitro-o-toluidine (fine- ingredient powder form)

Polyisobutene

Polybutene Kinematic viscosity 40 deg C 9003-27-4 equals 22,000 cSt, 5.0 Sticker PB1300 Kinematic viscosity 100 deg C equals 645 cSt

Calcium carbonate Calgrit prills 471-34-1 984.74 Solid carrier Predominantly 1.5-2.5 mm 1000

[0088] Example 7

[0089] Compositions of the invention of Example 6 were prepared using the following method:

[0090] -The Calgrit prills were placed in a stainless-steel vessel which is placed under a planetary mixer set to a slow mixing speed. An alternative mixing apparatus is a Nauta conical screw mixer.

[0091] -The fine-powder prodiamine technical material is slowly added to the Calgrit prills while these prills are under agitation. The mixing is continued until the fine-powder prodiamine has coated the prills and it was observed that the coated-prill contents of the mixing vessel were homogeneous and there was no observable region in the mixer with a high concentration of fine-powder prodiamine.

[0092] -The polybutene PB 1300 was heated to 700C and the resultant warm liquid was slowly poured onto the fine powder-coated Calgrit prills with continuation of the gentle agitation provided in previous steps. The gentle mixing was continued until the coated granules appeared homogeneous and evenly-coated. Clusters of granules were broken apart and returned to the mixing vessel.

[0093] The granules were free of dust, and though they were slightly tacky, they were free-flowing. The walls of the vessel were substantially free from sticker and from adhered prodiamine powder.

[0094] Example 8: Bioefficacy Example

[0095] Lawn comprising Common Couch (Cynodon dactylon) was divided into test squares 2mX1m in size.

[0096] - Squares (replicates of 4) were sprayed with Barricade EC (480 g/L prodiamine) at a rate equivalent to 960g/ha prodiamine.

[0097] - Other squares (replicates of 4) were sprayed with Barricade EC (480 g/L prodiamine) at a rate equivalent to 1680g/ha.

[0098] - Other squares (replicates of 4) were treated with granules of the invention as per example 1 (applied with a hand shaker) at a rate equivalent to 960g/ha (ie at a rate equivalent to 96 kg/ha of 1% prodiamine granules).

[0099] - Other squares (replicates of 4) were treated with granules of the invention as per example 1 (applied with a hand shaker) at a rate equivalent to 1680g/ha (ie at a rate equivalent to 168 kg/ha of 1% prodiamine granules).

[0100] - Other squares were taken as untreated controls.

[0101] 24 weeks after treatment the mean number of Crowsfoot weeds (Eleusine indica) per square were as shown in Table 5:

[0102] Table 5

treatment T=O weeks after treatment T=24 weeks after treatment untreated 0 6.60b Barricade 960g/ha 0 1.75a prodiamine Barricade 1680g/ha 1.25a prodiamine

Granules of example 6 0 2.00a (960g/ha prodiamine) Granules of example 6 0 1.75a (1680 g/ha prodiamine)

[0103] Note that treatments with different letter designations indicate a difference in efficacy.

[0104] 24 weeks after treatment the mean number of Paspalum weeds (Paspalum oleracea) per square were as shown in Table 4:

[0105] Table 4

treatment T=0 weeks after treatment T=24 weeks after treatment untreated 0 5.25c Barricade 960g/ha 0 2.5b prodiamine Barricade 1680g/ha 0.5a prodiamine

Granules of example 6 0 2.Oab (960g/ha prodiamine) Granules of example 6 0 0.5a (1680 g/ha prodiamine)

[0106] Note that treatments with different letter designations indicate a difference in efficacy.

[0107] For both weed types in the above tables, application of prodiamine was effective in terms of weed reduction (relative to control), and in both cases there was no significant difference between efficacy (per unit weight of applied prodiamine) between spray-applied prodiamine and granule-applied prodiamine.

[0108] Neither spray-applied prodiamine or granule-applied prodiamine was phytotoxic to the lawn (even at higher rates of application).

[0109] Example 9a (bioefficacy example kikuyu turf)

[0110] A trial was carried out on kikuyu turf (Pennisetum clandestinum) with the following parameters

" pH 6.2 * Organic matter (Walkley Black Method) 3.6% • Fertility - good • Drainage - moderate • Moisture - good * Plot dimensions 2m x 2m * Buffer length - 0.5m * Replication - 4 • Block design - randomised complete block • Target weed - Crowsfoot (Eleusine indica).

[0111] The trial involved a comparison of Barricade herbicide (480 g/L suspension concentrate of prodiamine) with Farmalinx granular herbicide (granules of example 1, comprising 1% = 1og/kg prodiamine).

[0112] The suspension concentrate (liquid) was applied using

• A handheld pressurised boom spray • Nozzle size - XR11004 • Nozzle spacing - 50cm " Droplet size - medium * Swath - 1m • Pressure - 200kpa • Speed - 1m/sec (= 3.6km/hr) • Water volume - 430 L/ha • Boom height - 50 cm above ground level at a spray angle of 110 deg.

[0113] The prodiamine granules were applied using a handheld granule applicator (Ronstar Shaker), and the granules were applied 1m above the plant canopy.

[0114] The application conditions were

* Time - 8.40 am • Air temperature - 16.2 deg C • Soil temperature - 16.8 deg c • Relative humidity - 98% * Cloud cover - 80% • Wind speed - 15 km/hr • Rainfall - 4mm (night).

[0115] The treatments were:

T1- untreated control T2 - 1 L/ha suspension concentrate (480 g/L prodiamine) T3 - 50 kg/ha prodiamine granules (1Og/kg prodiamine).

[0116] The assessment techniques were

• Phytotoxicity - every 7 days for the first 4 weeks, visual rating scale of 1-10 with 10 being best quality and 1 being dead turf. • Efficacy - monthly up to 6 months after treatment, weed preence in plot via quadrant assessments.

[0117] The results trial carried out on kikuyu turf are shown in Table 6

[0118] Table 6 - Table of Means, Crowsfoot (Eleusine indica) presence

treatment 4 Oct 4 Nov 2 Dec 3 Jan 3 Feb 2 March 1 April untreated 0.00 1.00 d 2.25 c 4.00 c 5.25 b 6.75 b 7.00 b Barricade 0.00 0.75 cd 1.75 bc 3.25 bc 4.75 b 5.50 b 5.50 b SC 1L/ha, formulation comprises prodiamine 480 g/L Coated 0.00 0.50 bc 1.25abc 1.50 ab 1.75 a 1.75 a 1.75 a granules 50 kg/ha, formulation comprises prodiamine 1Og/kg

[0119] Letters indicate level of significance. Treatments with differing letter designations indicate a difference in efficacy on the parameter in question.

[0120] Significantly decreased presence of Crowsfoot was found at 4,5,and 6 months after treatment (3 Feb, 2 March and 1 April) with the prodiamine granule (compared with the corresponding prodiamine suspension concentrate)No phytotoxicity was observed.

[0121] Example 9b (bioefficacy example - further target weeds)

[0122] A trial with the same parameters as Example 3a was carried out with changed target weeds and herbicide treatments as follows:

• Catsear (Hypochaerisradicata) • Nutgrass (Cyperus rotndus) • Pigweed (Portulaca oleracea) • Willowherb (Epilobium spp) • Wintergrass (Poa annua) • Wireweed (Polygonum aviculare)

[0123] Prodiamine suspension concentrate (Barricade 480 g/L prodiamine) treatments were applied at 1,2,3,4 and 8 L/ha.

[0124] Corresponding coated prodiamine granule treatments (10g/kg prodiamine granules, see example 1) were applied at 50, 100, 150, 200 and 400 kg/ha.

[0125] No significant efficacy difference was found between corresponding Barricade and prodiamine granule treatments, and no phytotoxicity was observed.

[0126] Example 10 - Liquid active

[0127] 30g metolachlor was sorbed into 30g porous silica powder (mesoporous silica gel) to provide a flowable powder comprising s-metolachlor. This loaded powder may be used at 20 g/kg in the formulation of Example 1 (replacing 1Og/L of imidacloprid).

Claims (44)

The claims defining the invention are as follows:

1. A broadcast granule composition comprising a granule core and coatings about the core the coatings comprising (i) a coating layer of powder comprising pesticide about the core; and (ii) a coating of sticker about the powder coating layer.

2. The broadcast granule composition of claim 1, wherein the pesticide comprises at least one selected from the group consisting of:

A) turf herbicides selected from the group consisting of terpene alcohols and saponified fatty acids, bromoxynil, MCPA, dicamba, prosulfuron, iodosulfuron, rimsulfuron, diclofop-methyl, dithiopyr, MCPA dimethylamine salt, Dicamba dimethylamine salt, quinclorac, DSMA, oryzalin, MCPA potassium salt, clopyralid potassium, diflufenican, metolachlor, metribuzin, MSMA, trifloxisulfuron sodium, bispyribac-sodium, pine oil, pendimethalin, propyzamide, florasulam, fluoroxpyr, halosulfuron-methyl. Carfentrazone, MCPA-sodium, carfentrazone-ethyl, diflufenican, clopyralid olamine, MCPA acid, indaziflam, foramsulfuron, dicamba acid, MCPA isooctyl ester, bromoxynil octanoate, prodiamine, s-metolachlor, siduron, isoxaben, florasulan and amicarbazone;

B) turf insecticides selected from the group consisting of chlorantraniliprole, abamectin, clofentezine, exotazole, diafenthiuron, fluopram, imidacloprid, fipronil, diazinon, indoxacarb, bifenthrin, cyantraniliprole, chlorpyrifos and beta-cyfluthrin;

C) forestry herbicides selected from the group consisting of Forestry herbicides may be selected from the group consisting of: imazopyr, metsulfuron methyl, sulfometuron, sulfometuron-methyl, triclopyr, aminopyralid, dicamba, fosamine, hexazinone, picloran and 2,4D; and

D) forestry insecticides may be selected from the group consisting of: azodiractin, acelepryn, abamectin, acetamiprid, acephile, bifenthrin, borate, carbaryl, chlorfenapyr, cyantraniliprole, cyfluthrin, deltamethrin, dimethoate, dinotefuran, amamectin benzoate, fenoxycarb, fipronil, floxicamid, fluvalinate, imidacloprid, lambda cyhalothrin, malathion, neem oils, inceticidal oils, pyrethroid, pymetrazine, pyrethrin, pyridalyl, Spinosad, spinetoram, spiromesifen, tolfenpyrad and trichlorfor.

3. The broadcast granule composition of claim 1 wherein the sticker has a ratio of kinematic viscosity at 40 0C to the kinematic viscosity 100°C of at least 8.

4. The broadcast granule composition of any one of the previous claims, wherein the sticker has a ratio of kinematic viscosity at 400 C to the kinematic viscosity 100°C of at least 11, preferably at least 14, more preferably at least 14 such as at least 17, at least20, at least23, at least26, at least28, or atleast30.

5. The broadcast granule composition of any one of the previous claims, wherein the sticking agent has a ratio of kinematic viscosity at 400 C to the kinematic viscosity 100°C is no more than 50 such as no more than 40 or no more than 35.

6. The broadcast granule composition of any one of the previous claims, wherein the kinematic viscosity of the sticker at 40 0 C is more than 150 centistokes.

7. The broadcast granule composition of any one of the previous claims, wherein the kinematic viscosity of the sticker at 100°C is more than 8 centistokes.

8. The broadcast granule composition of any one of the previous claims, wherein

(i) the kinematic viscosity at 40 0C of no more than 50,000 centistokes, and

(ii) a kinematic viscosity at 100 0C of no more than 2,000 centistokes.

9. The broadcast granule composition of any one of the previous claims, wherein, the sticking agent has a kinematic viscosity at 400 C of more than 1500 centistokes, preferably more than 5,000, 10,000, 15,000, 20,000 centistokes.

10. The broadcast granule composition of any one of the previous claims, wherein the kinematic viscosity at 100 0C of more than 50 centistokes, preferably more than 100, such as more than150, more than 200, more than 300, more than 400, or more than 500 centistokes.

11. The broadcast granule composition of any one of the previous claims, wherein the kinematic viscosity at 40 0C of no more than 40,000, preferably no more than ,000, such as no more than 20,000 centistokes.

12. The broadcast granule composition of any one of the previous claims, wherein the kinematic viscosity at 100 0C of no more than 1500, preferably no more than 1200, such as no more than 1000, no more than 900, no more than 800, no more than 700, no more than 600, or no more than 500 centistokes.

13. The broadcast granule composition of any one of the previous claims, wherein the concentration of pesticide in the granular composition is at least 0.05%, preferably at least 0.1%, preferably at least 0.3%, more preferably at least 0.5 % on a weight/weight basis.

14. The broadcast granule composition of any one of the previous claims, wherein the concentration of pesticide in the granular composition is no more than 10%, preferably no more than 5%, such as no more than 3%, no more than 2 %, on a weight/weight basis.

15. The broadcast granule composition of any one of the previous claims, wherein the concentration of sticker in the granule composition is at least 0.1%, preferably at least 0.2%, such as at least 0.3%, at least 0.4%, on a weight/weight basis.

16. The broadcast granule composition of any one of the previous claims, wherein the sticker is present in an amount of up to 4%, preferably up to 3% such as up to 2% or up to 1% on a weight/weight basis of the granular composition.

17. The broadcast granule composition of any one of the previous claims, wherein the granule core comprises one or more plant nutrients preferably selected from the group consisting of carbon, nitrogen, phosphorous, potassium, potassium, sulfur, calcium, magnesium, boron, chlorine, copper, iron, manganese, molybdenum, nickel and zinc.

18. The broadcast granule composition of any one of the previous claims, wherein the granule core comprises one or more materials selected from the group consisting of clay or mineral materials, calcium carbonate, ammonium nitrate, ammonium sulfate, ammoniated superphosphate, ammonium chloride, monoammonium phosphate, diammonium phosphate, calcium cyanamide, calcium nitrate, urea guanidine, guanidine nitrate, nitro guanidine, superphosphate, triple superphosphate, potassium nitrate, potash, potassium chloride, potassium sulfate, potassium metaphosphate, urea, urea phosphate, silicon dioxide, gums, insoluble metal oxides, minerals, bentonite, perlite, talc, kaolin, aluminum silicate, diatomaceous earth, attapulgite, barium sulfate, mica, calcium carbonate, precipitated silicates, aluminum silicate, zeolites and mixtures or combinations thereof.

19. The broadcast granule composition of any one of the previous claims, wherein the granule core comprises one or more chelates that bind plant nutrients, for example EDTA, amine-polycarboxylates, glucuronates and the like.

20. The broadcast granule composition of any one of the previous claims, wherein the granule core is a prilled or granulated composition.

21. The broadcast granule composition of any one of the previous claims, wherein the granule core comprises calcium carbonate, preferably in an amount of at least 30% w/w, more preferably at least 50% w/w, such as at least 70% w/w, or at least 80% w/w of the granule core composition.

22. The broadcast granule composition of any one of the previous claims, wherein the coating of sticker comprises at least one sticker selected from the group consisting of stearamide; polyolefins such as polyethylene, oxidized polyethylene, polypropylene, polyisobutylene, styrene-based polymer; polyolefin (block) copolymers; polyesters; polyesters (block) copolymers; polyethers, such as polyethylene oxide, polypropylene oxide; polyether (block) copolymer; vinyl resin such as polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyvinyl pyrrolidone, polyvinyl acetal, polyvinyl methyl acetamide; acrylic polymers; cellulose derivatives such as cellulose acetate; polyamides; polyamines; polyimides; polycarbonates; polysulfones; polysulfides; polysaccharides and blends of two or more thereof.

23. The broadcast granule composition of any one of the previous claims, wherein the coating of sticker comprises at least one sticking agent selected from the group consisting of polyolefins, such as polyethylene, polypropylene, polybutene and the like, polystyrene, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, polyacrylate, polymethyl (meth)acrylate, polyacrylonitrile, a polyvinyl ether, a polyvinyl ketone, a diene polymer, a copolymer of selected monomers, or a mixture of these polymers.

24. The broadcast granule composition of any one of the previous claims, wherein the coating of sticker comprises polybutene having a Kinematic viscosity of at least 200 centistokes (cSt) at 40°C.

25. The broadcast granule composition of any one of the previous claims, wherein the coating of sticking agent comprises polybutene having and a Kinematic viscosity of at least 300, centistokes (cSt) at 400 C

26. The broadcast granule composition of any one of the previous claims, wherein the coating of sticking agent comprises polybutene having and Kinematic viscosity of 400 cSt to 10,000 cSt at 100°C.

27. The broadcast granule composition of any one of the previous claims, wherein the coating of sticking agent comprises polybutene having no more than 10,000 cSt at 100°C preferably no more than 5,000 cSt at 100°C

28. The broadcast granule composition of any one of the previous claims, wherein the coating of sticker comprises polybutene of molecular weight (Mn) from 400 to 3000.

29. The broadcast granule composition of any one of the previous claims, wherein the pesticide powder is applied with a carrier powder and the ratio of pesticide powder to carrier powder is at least 1:30 such as at least 1:10 or at least 1:5.

30. The broadcast granule composition of any one of the previous claims, wherein the coating of pesticide powder further comprises a carrier powder selected from the group consisting of silicon dioxide, gums, insoluble metal oxides, minerals, bentonite, perlite, talc, kaolin, aluminum silicate, diatomaceous earth, attapulgite, barium sulfate, mica, calcium carbonate, precipitated silicates, aluminum silicate and zeolites.

31. The broadcast granule composition of any one of the previous claims, wherein the granule core diameter is no more than 5mm, preferably no more than 4mm such as no more than 3mm.

32. The broadcast granule composition of any one of the previous claims, wherein the granule core diameter is at least 0.5mm, preferably at least 1mm, such as at least 2mm.

33. The broadcast granule composition of any one of the previous claims, wherein powder comprising pesticide is of particle size no more than 150 microns, preferably no more than 100 microns, such as no more than 50 microns or no more than 20 microns.

34. The broadcast granule composition of any one of the previous claims, wherein

the granule core has an average diameter 1mm to 5mm; and

the powder comprising pesticide has an average diameter of no more than 100 microns.

35. The broadcast granule composition of any one of the previous claims, wherein

the amount of volatile material in the formulation is no more than 4% w/w of the granule composition; and

the amount of sticking agent in the formulation is about 1 g/kg to about 10 g/kg of the granule composition.

36. A method of preparing the broadcast granules, comprising:

(i) contacting a granule core with a powder comprising pesticide with agitation to deposit a coating of the powder about the granule core;

(ii) contacting the powder coated granule core with a heated sticker with agitation to overcoat the powder coated core with the heated sticker.

37. The method of claim 36 wherein agitating the core in the presence of the powder comprising pesticide is conducted in a rotating mixing vessel selected from a drum or pan or a mixing vessel with an agitator such as a rotating screw.

38. The method of any one of claims 34 to 36, wherein agitation of the granule core is provided by in a rotating drum such as a cement mixer.

39. The method of claim 38, wherein the rotation speed of the drum is no more than 1 revolution per 2 seconds, more preferably no more than 1 revolution per 5 seconds.

40. The method of claim 36 or claim 38 wherein the pesticide powder is added to the agitated granule core at a rate slow enough of agitation to adhere a substantially uniform coating of at least 80% of the pesticide is to the surface of the granule core, more preferably at least 90%, such as at least 95%, at least 96%, at least 97%, at least 98%, or at least 99% by weight.

41. The method of any one of claims 34 to 38, wherein the powder comprising pesticide is added to the agitated core over a time period of at least 5 minutes, preferably at least 10 minutes such as at least 15, at least 20 or at least 25 minutes.

42. The method of claim 36, wherein the agitation is provided in a vessel with a rotating screw impeller.

43. The method of claim 42, wherein the rotation speed of the screw impeller is no more than one rotation per 2 seconds, preferably no more than 1 rotation per 5 seconds.

44. The method of any one of claims 36 to 43 wherein the sticking agent is heated to a temperature of from 400 C to 1300 C (preferably 500 C to 800 C) prior to contact with the granule core.