NZ754997A - Granule composition and process for preparation thereof - Google Patents

Abstract

A granule composition comprising the pesticide clothianidin and fertiliser, the granules comprising a core of granular fertiliser having a coating of particulate clothianidin and a layer of sticking agent adhered to the particulate coated fertiliser granule, wherein the concentration of clothianidin is preferably at least 10g/Kg. is preferably at least 10g/Kg.

Description

GRANULE COMPOSITION AND PROCESS FOR PREPARATION THEREOF Field This invention relates to granules that contain both fertiliser materials and the insecticide clothianidin. The invention also and relates to a process for preparation of the granules and a method for their use in forestry management.

Background Clothianidin (1-(2-Chloro-1,3-thiazolylmethyl)methylnitroguanidine) is a neonicotinoid-type insecticide. It acts on the central nervous system of insects as an agonist of acetylcholine. Clothianidin has been used in forestry management applications as a 200g/L suspension concentrate formulation, and is used on eucalypt seedlings (from planting to 1 year old) to control of leaf feeding beetles and weevils including Paroptisterna Agricola and other Paroptisterna species, Cadmus australis, Liparetus jenkinski, Heteronx dimidiate and other Heteronx species, Gonipterus scutellatus and control of Psyllids including Creiis lituratus. The suspension concentrate is applied with an injection spear about 2cm below and to the side of the seedling root ball at or soon after planting. In order to benefit from the treatment, seedlings need to be actively growing. In general about 1.25 ml per seedling is sufficient. The suspension concentrate can be added to water or gel if these are added to the planting hole. On established eucalypt trees 1-5 years old in the size range 0.5 – 8 metres 2.5 – 10 ml per tree mixed with water for a total volume of at least 40 ml per tree based on tree height. Clothianidin suspension concentrate is applied to these more mature trees when monitoring of insect eggs, larvae or nymphs indicate that an economically damaging population of insects is expected. Application is by subsoil injection 10-15cm deep and in a continuous line 20-40cm from the tree trunks parallel to the row.

Clothianidin has also been prepared in granule form with a suitable carrier.

Clothianidin has a low water solubility making the preparation of granules problematic and often requiring the use of specific carriers and solvent. While granules may be prepared by addition of clothianidin dissolved in a solvent to a solid carrier this generally requires removal of the solvent from the resulting granules with the associated problems such as flammability, odour, additional energy requirements and further process steps and equipment requirements.

There is a need for granules containing clothianidin for use in the forestry and other agricultural industries which address the problems of the prior art.

Summary In one aspect there is provided a granular composition containing the pesticide clothianidin, the granules comprising a core of granular fertiliser a coating of particulate clothianidin about the core granule and a layer of sticking agent adhered to the fertiliser granule. The concentration of clothianidin in the granular composition is preferably at least 10 g/Kg of the coated granules.

The present inventors have experimented with different processes for preparing a fertiliser granule coated with a particulate clothianidin pesticide. The addition of the sticking agent after particulate clothianidin was found to very significantly improve the efficiency of the preparation of coated fertiliser granules. If the sticking agent is added to the fertiliser granules with mixing prior to particulate clothianidin it was found that the resultant coated granule was dusty unless higher levels of sticking agent were used. The use of higher levels of sticking agent resulted in the walls of the mixing vessel becoming coated with a layer of sticky matrix that entrained particulate clothianidin pesticide which were lost to the final product.

Cleaning of the walls of the mixing vessel was found to be time-consuming and to require significant labour input and clumps of product granules tended to form adding to the problems.

There is further provided a process for the preparation of granules containing clothianidin pesticide and fertiliser, the process comprising: contacting fertiliser granules with clothianidin in particulate form and agitating the mixture to coat the fertiliser granules with the particulate clothianidin; blending the particulate clothianidin coated granules with a sticking agent to form an adhered coating of sticking agent on the particulate clothianidin coated granules.

The process allows a higher loading of clothianidin coating of the fertiliser to be achieved than can readily be achieved by other coating processes. Accordingly in one embodiment the invention provides a granule composition containing clothianidin wherein the granule composition comprise a core fertiliser granule; and a coating about the core fertiliser granule comprising clothianidin and a sticking agent adhering the clothianidin to the core fertiliser granule wherein clothianidin is present an amount of at least 15 g/Kg of the clothianidin coated granule composition.

In a further aspect there is provided a method of controlling insects, (particularly leaf feeding beetles and weevils such as Paroptisterna Agricola and other Paroptisterna species, Cadmus australis, Liparetus jenkinski, Heteronx dimidiate and other Heteronx species, Gonipterus scutellatus and control of Psyllids including Creiis lituratus) in growing trees, particularly Eucalypt trees, the method comprising applying the granules herein described to the ground such as to the ground surface or subsurface for absorption of the released clothianidin by the tree roots.

Surprisingly we have found the granule composition of the invention to be useful in inhibiting bark beetle in pine trees. Bark beetles (Coleoptera:Scolytidae) are serious pests of pine forests throughout the world. This finding was surprising as control of the bark beetles is often ineffective using conventional control strategies, including use of insecticides.

Detailed Description The flash points reported herein are Cleveland open cup flash points referred to in ASTM D 92.

The term "(meth)acrylate" refers to acrylate and/or methacrylate.

As used herein the term “tree” refers to woody perennial plants including bushes, shrubs, and large trees. The term encompasses both deciduous and coniferous trees. The term includes trees throughout their lifetime from seedlings to saplings and full grown trees.

For the purposes of the disclosure contained herein, the term seedling is intended to mean any small tree developed from propagation such as from seeds, cuttings and other plant parts prior to transplanting in the ultimate location wherein it is to mature. The term “seedling” typically comprises the period of development from propagation such as post-germination to about 16 weeks post-propagation.

The term "growth medium" comprises in the simplest case the soil, in which the trees are grown, but is not limited to this and extends to other media in which plants may be grown.

The term "root zone" as used herein in relation to a tree, refers to that portion of the growth medium, such as soil, in which the tree is planted which is penetrated by plant roots of the tree.

The term bark beetle refers to insects Coleoptera:Scolytinae found in pine trees and specifically includes Hylastes ater, Hylurgus ligniperda, and Ips grandicollis, particularly in commercial plantations of Pinus spp such as Pinus radiata.

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.

The granules for the release of fertiliser and clothianidin pesticide are prepared by a process comprising: contacting fertiliser granules with clothianidin in particulate form and agitating the mixture to coat the fertiliser granules with the particulate clothianidin; blending the particulate clothianidin coated granules with a sticking agent the form an adhered coating about the particulate coated granules.

The granules comprise a core of fertiliser material and a surrounding layer of particulate clothianidin particles around the core. The method may be conducted in a vessel such as a drum, pan or mixing vessel, and include an initial step of adding the fertiliser cores to the mixing vessel and slowly adding particulate clothianidin particles to the cores under agitation to form a primary blend, and a subsequent step of slowly adding the sticker to the primary blend under agitation.

Sticking agent has been previously reported for use in retaining an active on a carrier but the use typically involves first adding sticker to the cores and then adding finely divided particles 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 fertiliser granule core and the surface of the finely divided clothianidin particles leading to the formation of a substantially uniform layer of finely divided clothianidin particles around the core.

The electrostatically enabled substantially uniform layer of clothianidin particles is then locked in place by the sticking agent.

The fertilizer may be a single nutrient or a composite of various nutrients.

Nutrients that may be used in the invention include, but not limited to ammonium nitrate, ammonium sulfate, ammoniated superphosphate, ammonium chloride, mono- ammonium phosphate, diammonium phosphate, calcium cyanamide, calcium nitrate, urea guanidine, guanidine nitrate and nitro guanidine, superphosphate and triple super-phosphate, potassium nitrate, potash, potassium chloride, potassium sulfate, potassium metaphosphate, urea, urea phosphate and mixtures or combinations thereof. Those of skill in the art will appreciate that other fertilizers may be used in the methods and systems described herein.

In another particular aspect, the fertilizer comprises at least one of nitrogen (“N”), phosphorus (“P”), potassium (“K”), NPK, NP, NK, and PK. These elements may be combined in different ratios. For example, in one aspect, the NPK ratios may be 1313, 270, 120, 050, 2114, 1515, or 1018. Other ratios of NPK will be evident to those of skill in the art. The fertiliser preferably comprises a low phosphorus fertiliser.

Suitable fertilizer granules for use as core granule herein include NPK type fertilizers which may include methylene urea nitrogen sources, phosphorus sources, single superphosphates, triple superphosphates, calcium phosphates, nitro phosphates, potassium phosphates, ammonium phosphates, ammoniated superphosphates and the like and mixtures thereof. Further fertilizer granules suitable for use in the methods of this invention include potassium sources such as muriate of potash, potassium sulfates, potassium phosphates, potassium hydroxides, potassium nitrates, potassium carbonates and bicarbonates, potassium magnesium sulfates and the like and mixtures thereof.

In another particular aspect, the fertilizer granule may contain secondary nutrients such as sulfur, magnesium, and calcium and/or micronutrients such as iron, manganese, zinc, copper, molybdenum, boron, and cobalt.

Additional fertilizer granules suitable for use in the granules of the invention include secondary nutrient sources such as elemental sulfur, calcium and magnesium salts including phosphates, oxides, sulfates, carbonates, chlorides, nitrates and the like and mixtures thereof . Still further fertilizer granules suitable for use in the methods of this invention include micronutrient sources such as iron, manganese, copper, boron, zinc and molybdenum salts such as phosphates, oxides, sulfates, carbonates, chlorides, nitrates, borates, molybdates and the like and mixtures thereof as well as chelates of micro nutrients such as EDTA chelates and the like.

Representative materials that may be used as dry micronutrient substrates in the methods of the present invention specifically include calcium nitrate, magnesium sulfate, magnesium nitrate, ferrous sulfate, ferrous nitrate, manganese sulfate, manganese nitrate, copper sulfate, copper nitrate, boric acid, sodium borate, zinc sulfate, zinc nitrate, sodium molybdate, ammonium molybdate and the like.

The core may if desired contain further active pesticide such as selected from the group consisting of fungicides, insecticides and herbicides. In one embodiment the fertiliser granule does not contain pesticide. It may for example be a commercially available fertiliser granule comprising a NPK (nitrogen, phosphorus and potassium containing) fertiliser.

The fertiliser granule may be coated or uncoated. The uncoated fertiliser may be coated in accordance with the invention to provide at least some control, if desired or the fertiliser may be of a controlled release type known in the industry. In a further embodiment the fertiliser granules used in the composition and process of the invention comprise a mixture of coated and uncoated fertiliser granules.

The fertiliser granule which forms the core of the granule for controlled release of fertiliser will typically include a control release coating about the fertiliser.

The fertilised granule may have at least a partial coating but it is preferred that the fertiliser have a complete coating providing controlled release. The coating may contain a mixture of impervious and porous materials. The coating may be a suitable controlled release coating material such as a sulfur coating, polymer coating such as a thermosetting or thermoplastic polymer or other suitable coating for providing controlled release of the fertiliser.

In one embodiment the fertiliser core granule is a controlled release fertiliser comprising a nutrient, such as described above, coated with a polymer layer, sulfur layer and polymer layer in that order. The fertilizers have good impact and abrasion resistance, undergo controlled release and are manufactured at low cost. In one embodiment the fertiliser granules have a controlled release coating of a polymer having polyurethane and urea polymer such as described in US 2003/0040435. The polyurea-polyurethane polymer coating may be biodegradable.

The core fertiliser granule is typically of size from 1 mm to 10 mm such as 1 mm to 5 mm and may be generally rounded or elongate. The specific dimensions of the granule are not narrowly critical and may depend on the method by which the fertiliser granules are formed such as by pan granulation, extrusion or a combination of extrusion and tumbling.

In the process of the invention fine particles such as powder of clothianidin are contacted with the fertiliser granules and the mixture is agitated, for example by tumbling in a rotating pan mixer or drum mixer or mixing in a mixing vessel such as with an impeller to coat the fertiliser granules with the clothianidin particles. The finely divided particles of clothianidin may have an average diameter of no more than 150 microns such as no more than 100 microns or from 1 to 100 microns.

The amount of clothianidin particles on a weight/weight basis in the formation may, in one embodiment, be between about 15g/kg and 80g/kg such as between 20g/kg and 60 g/kg of the final granule composition.

The particulate clothianidin coated fertiliser granules are blended with a sticking agent to form an adhered coating about the particulate-clothianidin coated fertiliser granules.

The sticking agent may be a range of materials. Preferred sticking agents are viscous materials and may be thermoplastic polymers which have the capacity to spread when coated on a clothianidin in the molten or semi-molten state. It is a particular advantage of the invention that the sticking agent can be used without the need for volatile solvents or aqueous carrier. .This significantly reduces the need to transport and remove hazardous volatile solvents and/or water and the energy required to deal with a remove these carriers. This also reduces the need for drying equipment and the cost associated therewith. The amount of volatile material in the formulation is typically less than 4 wt. % and preferably less than 2 wt. %.

Examples of suitable thermoplastic and high viscosity materials include 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.

Preferred are 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.

Representative examples of diene polymer include a butadiene polymer, an isoprene polymer, a chloroprene polymer, a butadiene-styrene copolymer, an ethylene-propylene-diene copolymer, styrene-isoprene copolymer and the like.

Representative examples of olefin copolymers include ethylene-propylene copolymer, butene-ethylene copolymer, butene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylate-copolymer include, ethylene-methacrylic acid copolymer, ethylene-meth acrylate copolymer, ethylene-vinyl acetate-carbon monoxide copolymer and the like.

The polymers may be plasticised with plasticiser having a high flash point such as having a flash point of at least 160°C.

Representative examples of copolymers of vinyl chlorides include vinyl chloride-vinyl acetate copolymer and vinylidene chloride-vinyl chloride copolymer.

In addition to the above-mentioned vinyl resins, one or more kinds of other coating materials can be including polyesters such as polycaprolactone, waxes, natural resins, fats and oils, and modified products of these. Representative examples of waxes include beeswax, Japan wax, paraffin and the like. Examples of natural resins include natural rubber, rosin and the like. Representative examples of fats and oils and modified products of these include hydrogenated oils, solid or semi-solid fatty acids, metal salts thereof, or the like.

The sticker will generally be mixed with the granules in the form of a liquid preferably at a temperature of no more than 130°C such as no more than 100°C or no more than 80°C.

In a preferred embodiment the sticking agent is a high viscosity material, preferably having a Kinematic viscosity of at least 1000 centistokes (cSt) at 40°C such as from 1000 cSt to 250,000 cSt. The highly viscous material will have a reduced viscosity at higher temperature such as a viscosity of no more than 10,000 cSt at 100°C preferably no more than 5,000 cSt at 100°C such as 10 cSt to 10,000 cSt or 10 to 5,000 cSt.

The amount of sticking agent present in the granule composition is typically 1 g/Kg to 50 g/Kg, preferably 4 g/Kg to 30 g/Kg such as 4 g/Kg to 20 g/Kg.

The more preferred sticking agent is polybutene and in particular polybutene of molecular weight (Mn) from 500 to 3000. Examples of specific grades of polybutene and their physical properties are provided in Table 1.

Table 1 Item Unit PB450 PB680 PB950 PB1300 PB1400 PB2400 Molecular weight Mn 450 680 950 1300 1400 2450 Kinematic Viscosity 40 ℃ cSt 190 1,700 7,200 22,000 27,000 206,000 100 ℃ cSt 14 80 230 645 810 4,700 Flash Point （COC ） ℃ 160 175 210 220 230 260 Pour Point ℃ -31 -14 0 3 5 17 Density @25 ℃ g/cm3 0.854 0.874 0.890 0.896 0.899 0.906 Color APHA 15 15 15 15 15 15 Density @25 ℃ 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 The most preferred sticking agent is polybutene of molecular weight (Mn) 950 to 1400, particularly polybutene of molecular weight (Mn) 1300.

The process of the invention typically involves contact of the sticking agent with the clothianidin coated core fertiliser granules optionally with heating of the thermoplastic polymer or viscous material sicker to reduce the viscosity. 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 particulate clothianidin coated fertiliser core granules. In one embodiment the sticking agent is heated to a temperature in the range of 40°C to 130°C such as 40°C to 80°C or 50°C to 80°C. 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.

The method of the invention may generally be conducted in a single reaction vessel such as a rotating drum or pan vessel despite the use of viscous or thermoplastic sticking agent. In single drum processing, there is a higher tendency for viscous material to generate clumps or balls of coated materials but the method significantly reduces the problems allowing the process to be conducted in a single vessel if desired. Single drum operation was previously regarded as unsuitable for highly viscous materials such as used in the preferred embodiment of the method of the invention. It is thus a particular advantage of the invention that it allows the use of viscous materials without volatile solvents. Volatile solvents often required in previous methods of coating granules are more hazardous to handle and transport and require additional infrastructure and expense to meet regulations for handling such materials.

The present inventors have found that the fertiliser granules can be coated with finely divided clothianidin and then highly viscous coating materials without the use of volatile solvents.

The viscous material and/or thermoplastic polymer may have a flash point of at least 160°C, preferably at least 200°C and no significant content of volatiles is required.

Those of skill in the art will appreciate that various fertilisers may be applied to the process and systems described herein. For example, the process and systems described herein can be used to prepare clothianidin granules with a range of core fertiliser granule types. Those of skill in the art, however, will appreciate that these methods and systems are applicable to a variety of fertiliser granule cores and various sticking agents. Variations in the combinations will be apparent to those of skill in the art and may be optimized to achieve the desired final product.

In a further aspect there is provided a composition of granules for release of fertiliser (optionally controlled release) and the pesticide clothianidin, the granules comprising a core of granular fertiliser having a coating of particulate clothianidin and a layer of sticking agent adhered to the particulate coated fertiliser granule.

The method allows the preparation of granules containing a higher loading of clothianidin than has generally been considered to be possible due to the problems associated with the use of high viscosity or thermoplastic sticking agents. It also avoids the requirement for carriers which need to be removed following coating of the granules.

The granules in accordance with the invention generally comprise at least 1.5% clothianidin by weight based on the total granule weight, more preferably at least 2 % w/w. Accordingly in one embodiment the invention provides a granule composition containing clothianidin wherein the granule composition comprise a core fertiliser granule; clothianidin in an amount of at least 15 g/Kg of the granule and a sticking agent adhering the clothianidin in the core fertiliser granule. For example, the granule composition may comprise clothianidin in an amount of 15 g/Kg to 80 g/Kg of the granules and even at least 20 g/Kg, such as 20 g/Kg to 80 g/Kg of the granule such as 20 g/Kg to 50 g/Kg.

As previously mentioned the process allows the use of volatile aqueous carriers such as latex or emulsion compositions to be avoided. Generally speaking the sticking agent will comprise no more than 5% w/w water such as no more than 3% w/w water. The sticking agent typically has a pour point of no more than 50 C, o o o preferably no more than 30 C such as -15 C to 30 C.

In one specific embodiment here is provided granules comprising a core of fertiliser material and surrounding layer of clothianidin particles around the core, and a sticking agent, and wherein: (i) The fertiliser cores have an average diameter between 1mm and 5mm, and (ii) The clothianidin particles have an average diameter <100 microns, and (iii) The amount of clothianidin particles on a weight/weight basis in the formation is between about 15 g/kg and 80 g/kg and preferably between g/kg and 60 g/kg, and (iv) The amount of volatile material in the formulation is less than 4% and preferably less than 2%, and wherein (v) The amount sticking agent in the formulation is between about 4 g/kg and about 30 g/kg.

The granules are prepared by a process in which the particulate clothianidin is contacted with the core fertiliser granules to coat the core fertiliser granules with the particulate clothianidin. The core fertiliser granules may be tumbled in a rotating vessel such as a drum or pan or mixed in a mixing vessel to provide intimate contact of the core fertiliser granules with the particulate clothianidin particles and take advantage of the generated electrostatic forces which are believed to be at least partly responsible for efficiency of this process. The particulate clothianidin is generally added to the fertiliser granules over a period of time to provide a build-up of the particles on the granules. For example the clothianidin particles may be added to the fertiliser granules over a period of from 5 minutes to two hours such as from 5 minutes to one hour, five minutes to 30 minutes or the like.

The sticking agent is optionally heated to reduce the viscosity of the sticking agent to a suitable temperature at which the viscosity is reduced to a Kinematic viscosity such as no more than 30,000 cSt, no than 10,000 cSt or from 1 cSt to 10,000 cSt such as 1 cSt to 5000 cSt or 1 cSt to 2000 cSt. The temperature may, for example be in the range of 20°C to 130°C such as 30°C to 80°C or 30°C to 50°C. The optionally heated sticking agent is added to the particulate clothianidin coated fertiliser over a period of time to build a coating about the clothianidin-coated fertiliser granules. For example the hot sticking agent may be added to the clothianidin-coated fertiliser granules over a period of from 5 minutes to two hours, such as from 5 minutes to one hour, five minutes to 30 minutes or the like.

The sticking agent (optionally with cooling) forms a more viscous semi- solid or solid coating on the granules which may flow in the mixing vessel. The process generally avoids the sticking agent transferring to the wall with the active clothianidin and thereby reduces build up and loss of the active when compared with corresponding processes in which the sticker is first added to granules followed by clothianidin particles.

Surprisingly we have found the granule composition of the invention to be useful in inhibiting bark beetle in pine trees. Bark beetles (Coleoptera:Scolytidae) are serious pests of pine forests throughout the world. Since most life processes such as feeding, mating, egg laying, and larval development occur safely beneath the bark of the host tree. The impact of the bark beetle on pine forestry has become severe. It is ubiquitous in pine plantings. As mature trees are continually harvested for wood, the many stumps left behind are infested by the beetle, which then spreads to the seedlings. The beetle has been known to cause high levels of mortality in crops of pine tree seedlings, such Pinus radiata seedlings, in Australia. It is also common in New Zealand and while it does not kill such a high proportion of trees in New Zealand it often causes a reduction in wood value by damaging the tree tissue and introducing fungi. While control of the bark beetles is often ineffective using conventional control strategies, including use of insecticides, we have found the granules of the invention to be effective particularly when used in treating pine trees at the time of planting seedlings or within six months of planting seedlings.

More detailed aspects of composition as follows:  Fertiliser core is preferably a sustained release fertiliser such as an encapsulated granule (more preferably a fully coated slow-release granule such as a granule with a release period of 3-18 months, preferably 6 – 12 months, more preferably about 9 months)  Fertiliser may have any ratio of NPK but in one embodiment the P/N ratio is less than 1/4, preferably less than 1/6.

 In another embodiment the NPK ratio is around 16,2,6 Basacote® starter 9M (NPK ratio of 165) granules may be used as core granules in the invention and are useful in forestry applications.

 Sticker chosen from the set low-volatile resins such as polymer resins, latex resins, wood rosin containing materials and polymer compositions with a glass point transition less than 0°C. , Low-volatile, viscous resins are preferred preferably polybutenes, preferably polybutenes such as polybutene PB1300 (<0.2% volatile). Other examples include Joncryl® 1124 (acrylic polymer), Rutocel® 60 RT6 (hydroxypropyl methylcellulose)  Preferably the sticker is warmed before addition to the mixing vessel, preferably in the temperature range 40 – 70 °C.

More detailed aspects of method of manufacture as follows: (Details based on 5kg batch size)  Time taken to form primary blend: minutes mixing to sufficiently coat granules. Care is taken to avoid loss of active as dust.

 Time taken to add sticker to primary blend: Sticker added very gradually over 15 minutes. Sticker is then blended for at least 30 minutes.

 Heating of sticker prior to addition of sticker to the primary blend Sticker is typically heated to about 60°C but this may not be necessary for small batch sizes.

There is provided a method of controlling leaf-eating insects in forests wherein a formulation of granules is located close to the roots of seedlings or young trees, and wherein the granules of the formulation comprise (i) a core of fertiliser material and (ii) a surrounding layer of clothianidin particles around the core and (iii) a substantially non-aqueous sticking agent. The distance at which the granules are deposited from the trunk of the trees will depend on their maturity. Generally the distance will be no more than 50 cm from the trunk such as no more than about 30 cm from the trunk.

For trees within one year of planting, deposition of the granules within 30 cm of the trunk is preferred such as about 20 cm from the trunk. The granules may be deposited on or in (i.e. beneath the surface of) the soil which may be undisturbed since planting or may be freshly tilled. The release of the fertiliser and clothianidin may be responsive to the present of moisture in the soil or application of water from rain or irrigation.

The composition may preferably be used on plants within six months of planting propagated seedlings. In a preferred embodiment the granules are placed in the ground at the time of planting. For example the granules may be placed in the holes created for planting of seed or seedlings. In the case of trees such as pine trees or eucalypts the granules may be placed in the holes in the ground for planting and the seedlings placed over the granules optionally with a coverage of growth medium such as soil or other material between the granules and the root zone of the seedling.

The clothianidin containing granules are useful in controlling leaf-eating insects. Specifically the granules may be applied to the soil near the roots of the plants to control beetles and weevils including Paroptisterna Agricola and other Paroptisterna species, Cadmus australis, Liparetus jenkinski, Heteronx dimidiate and other Heteronx species, Gonipterus scutellatus and control of Psyllids including Creiis lituratus.

The granules and method of the invention may be used to control insects in a range of forest trees such as pine, eucalypt and the like.

The granules in accordance with the invention provide significant advantages including:  The granules made using a first step of making a primary blend and a second step of adding substantially non-aqueous sticker to the primary blend.

 Capacity to make the product in a single mixing vessel using sequential addition of components and without a drying or solvent-removal step.

 Development of a final product with a low concentration of volatile components.

 Minimisation of vessel coating and associated clothianidin loss.

 Minimisation of labour requirements.

 The relatively high loading of clothianidin on fertiliser such as at least 15 g/Kg preferably at least 20g/Kg.

 The fertilising and insect control aspects provided in a single granule formulation.

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 Example 1 Table 1. Clothianidin 25g/kg coated fertiliser granule formulation Component CAS number Chemical name g/kg Function Basacote® Solid carrier / Starter 9M - - 967 fertiliser fertilizer granule Clothianidin (E)(2-Chloro Active technical 2108805 thiazolylmethyl) 25.2 ingredient (99.3%) methylnitroguanidine Polybutene Binding 90036 Polybutene 7.8 PB1300 agent/sticker 1000 Example 2 Table 2. Clothianidin 50g/kg coated fertiliser granule formulation Component CAS number Chemical name g/kg Function Basacote® Solid carrier / Starter 9M - - 935.8 fertiliser fertilizer granule Clothianidin (E)(2-Chloro technical 2108805 thiazolylmethyl) 50.4 Active ingredient (99.3%) methylnitroguanidine Polybutene Binding 90036 Polybutene 13.8 PB1300 agent/sticker 1000 Example 3 Formulation process Step 1. The required Basacote® Starter 9M fertilizer granules are placed in a stainless steel vessel which is placed under a planetary mixer set to a slow mixing speed. A Nauta® conical screw mixer could also be used.

Step 2. Gradually all the required clothianidin technical is added to the granules while it is mixing. The granules are left to mix until the active material has completely coated all the granules.

Step 3. Very gradually the required amount of Polybutene PB1300 is poured on to the granules while still mixing. The granules are mixed until it appears all the granules have been evenly coated with the polybutene. Clusters of granules that may be stuck together are broken apart and remixed in to the granules.

The granules may appear as a white and green granule, free of dust. It may be slightly tacky but mostly free flowing.

Example 4 Table 3. Clothianidin 25g/kg coated granule made using technical material This was a low-polybutene formulation.

Component g/kg Function Basacote® Starter 9M 967 Solid carrier / fertiliser fertilizer granule Clothianidin technical .2 Active ingredient (99.3%) Polybutene PB1300 2.6 Binding agent/sticker 1000 Example 5 Table 4. Clothianidin 50g/kg coated granule made using technical material.

This was a low-polybutene formulation.

Component g/kg Function Basacote® Starter 9M 967 Solid carrier / fertiliser fertilizer granule Clothianidin technical 50.4 Active ingredient (99.3%) Polybutene PB1300 2.6 Binding agent/sticker 1000 In Examples 4 and 5 some granule dustiness was observed.

Example 6 The granules of are used in control of beetles such as bark beetle in pine tree and beetles in eucalypt forestry by placing the granules in holes in the ground for receiving the seedlings and placing the seedling root zone over the granules, optionally with a coverage of growth medium between the granules and root zone.

The granules inhibit beetle infestation in the seedlings and during tree growth.

Claims (25)

Claims 1.

1. A granule composition comprising the pesticide clothianidin and fertiliser, the granules comprising a core of granular fertiliser having a coating of particulate clothianidin and a layer of sticking agent adhered to the particulate clothianidin coated fertiliser granule,

2. The granule composition of claim 1, wherein the concentration of clothianidin is preferably at least 10g/Kg.

3. The granule composition of claim 1 or claim 2, wherein the granule composition comprise a core fertiliser granule; and a coating about the core fertiliser granule comprising particulate clothianidin and a sticking agent adhering the particulate clothianidin to the core fertiliser granule wherein clothianidin is present an amount of at least 15 g/Kg of the clothianidin coated granule composition.

4. The granule composition of any one of claims 1 to 3, wherein the clothianidin is present in an amount of at least 20 g/Kg (such as from 15 g/Kg to 80 g/Kg or 20g/Kg to 60 g/Kg) of the clothianidin coated granule composition.

5. The granule composition of any one of the previous claims, wherein the sticking agent forms a layer about the coating of particulate clothianidin on the fertiliser granules.

6. The granule composition of any one of the previous claims, wherein the sticking agent is selected from the group consisting of viscous materials.

7. The granule composition of any one of the previous claims, wherein the sticking agent has a Kinematic viscosity of at least 1000 cSt at 40°C.

8. The granule composition of any one of the previous claims, wherein the sticking agent has a Kinematic viscosity in the range of from 1000 cSt to 250,000 cSt at 40°C.

9. The granule composition of any one of the previous claims, wherein the sticking agent has a Kinematic viscosity of no more than 10,000 cSt at 100°C.

10. The granule composition of any one of the previous claims, wherein the sticking agent has a Kinematic viscosity of no more than 5,000 cSt at 100°C, such as 10 cSt to 10,000 cSt or 10 cSt to 5,000 cSt.

11. The granule composition of any one of the previous claims, wherein the sticking agent is polybutene of molecular weight (Mn) in the range of from 500 to 3,000.

12. The granule composition of any one of the previous claims, wherein the sticking agent is present in an amount of 1g/Kg to 50 g/Kg.

13. The granule composition of any one of the previous claims, wherein the sticking agent is present in an amount of 4 g/Kg to 30 g/Kg.

14. The granule composition of any one of the previous claims, wherein the fertiliser core granules have a diameter in the range of from 1 mm to 5 mm.

15. The granule composition of any one of the previous claims wherein the core of granular fertiliser comprises an NPK fertiliser.

16. The granule composition of any one of the previous claims, wherein the core of granular fertiliser is a slow release granular fertiliser comprising a control release coating preferably selected from sulfur coating, polymer coating such as a thermosetting or thermoplastic polymer coating for providing controlled release of the fertiliser.

17. The granule composition of any one of the previous claims, wherein the sticking agent comprises no more than 10% w/w water and has a pour point of no more than 50°C.

18. A process for the preparation of a granule composition according to any one of the previous claims containing clothianidin pesticide and fertiliser, the process comprising: contacting fertiliser granules with clothianidin in particulate form and agitating the mixture to coat the fertiliser granules with the particulate clothianidin; blending the particulate clothianidin-coated granules with a sticking agent to form an adhered coating about the particulate coated granules.

19. The process of claim 18 wherein the sticking agent is heated to a temperature in the range of from 40°C to 130°C to reduce the viscosity prior to contact with the core fertiliser.

20. The process of claim 19 wherein the sticking agent is heated to a temperature in the range 40 C to 80 C.

21. The process of claim 18 or claim 19, wherein the heating of the sticking agent reduces to a Kinematic viscosity, such as, no more than 30,000 cSt.

22. The process of claim 18 or claim 19, wherein the heating of the sticking agent reduces the Kinematic viscosity to no more than 10,000 cSt.

23. The process of claim 18 or claim 19, wherein the heating reduces the Kinematic viscosity to within the range 1 cSt to 5000.

24. A method of controlling insects, (particularly leaf feeding beetles and weevils such as Paroptisterna Agricola and other Paroptisterna species, Cadmus australis, Liparetus jenkinski, Heteronx dimidiate and other Heteronx species, Gonipterus scutellatus and control of Psyllids including Creiis lituratus) in growing trees, particularly Eucalypt trees and pine trees, the method comprising applying the granules herein described to the ground or in the ground for absorption of the released clothianidin by the tree roots.

25. The method of claim 24 wherein the granules are placed in the ground, optionally in the holes created for tree planting, before planting of tree seedlings over the granules.