Agrochemical composition in the form of water dispersible granules

Abstract

The invention relates to a composition in the form of one or more water dispersible granule(s), comprising: a) at least one copper salt and / or sulfur compound, b) at least one polysaccharide, c) at least one water-soluble solvent, d) at least one surfactant, e) at least one carrier.

Description

AGROCHEMICAL COMPOSITION IN THE FORM OF WATER DISPERSIBLE GRANULESTECHNICAL FIELD OF THE INVENTION

[0001] This invention relates to a composition in the form of one or more water dispersible granule(s), a process for the manufacture of such water dispersible granule(s), and the use of said composition to treat an agricultural target against fungi and / or bacteria.PRIOR ART

[0002] Copper salts have been employed in agriculture for a long time for controlling phytopathogenic fungi and bacteria on crop plants. To ensure the efficacy of the copper treatment of cultures over an extended period, inorganic copper salts which are sparingly soluble or insoluble in water, such as copper oxychloride, copper hydroxide, or tribasic copper sulfate (TBCS) for example, are used frequently. However the use of Copper based fungicides are limited due to phytotoxicity to plant, and toxicity to the user, at higher concentrations in copper. In addition copper tends to accumulate in the soil: high levels of copper in the soil may be toxic to plant, soil microorganisms, leading to lower biological activity and loss of soil fertility. Therefore, there is a need to improve fungicidal and / or bactericidal efficacy of copper or copper salts, or to bring about the same level of fungicidal and / or bactericidal activity with a reduced amount of copper or copper salts. The same applies to sulfur compounds.

[0003] Among the various forms of agrochemical compositions to treat crops, Water Dispersible Granules (WDG) formulations are very useful. A Water dispersible granules formulation is a solid formulation that generally incorporates the active ingredient into granules, which disperse or dissolve quickly when added to water in the spray tank to give a fine particles suspension. These formulations provide a system for delivering solid active ingredients to their target and allow for the production of highly concentrated formulations, which are wettable and readily disintegrate on contact with water.

[0004] Due to their solid granular form, WDG formulations offer significant advantages over other known formulations such as ease of handling, ease of use, reduced worker exposure, reduced toxicity, and therefore offer a convenient form for delivery of fungicides and bactericides.

[0005] In order to be effective, the granules are required to maintain their physical integrity until they are delivered to the carrier liquid (usually water), where they must disintegrate rapidly into fine particles that remain suspended in the liquid phase in a homogeneous way.

[0006] One of the major problems with pesticidal treatments, especially fungicidal and bactericidal treatments, is that pesticides are generally prone to leaching from treated agricultural targets (including plant parts and soil). When applied on plant parts, such as leaves, they may for instance suffer run-off or loss caused by rapid watering, rain or other water exposures. As another example, pre-emergent agents (i.e. those agents that are applied to the soil before the germination of plants or weeds) need to stay where they are applied for a period while the plants and / or weeds are germinating. Dissipation of a pre-emergent agent by run-off by water exposure and the like, is obviously undesirable during the germination period.

[0007] To solve this problem, it is known to use polysaccharides, in particular Galactomannan, such as guar gums or guar derivatives, which are polysaccharides and well-known binding and retention agents. Polysaccharides such as guar gums have been claimed to be efficient retention and rainfastness agents in presence of certain biofungicides such as microbial biopesticides, providing an enhancement ofbiological efficacy. One may refer to document WO 2022 / 033874 on that matter.

[0008] The Applicant has discovered that the use of guar gums in water dispersible granules (WDG) containing copper salt(s) and / or sulfur compound(s) is especially interesting in order to favor a good retention of the copper salt or the sulfur compound on the agricultural target such as foliar cuticles upon application, an adequate rainfastness benefit for an enhanced biological efficacy.

[0009] However, from a practical point of view, the preparation of WDG with guar gum is highly problematic. The hydration of guar in water results in a paste presenting a high viscosity, which renders the extrusion process very difficult and cumbersome.

[0010] In addition, granules containing guar above 2 wt% (weight percentage) are very slow to disintegrate when they are mixed into the water tank before spraying application, and a low suspensibility related to particles aggregation of guar with other ingredients is obtained. This results in several application issues, such as high quantity of wet sieves residues, nozzles clogging etc.

[0011] The Applicant therefore sought a solution to this problem of balancing good properties such as retention, especially rainfastness, and biological efficacy, with an adequate viscosity of the paste that makes it (easily) processable into WDG.SUMMARY OF THE INVENTION

[0012] The Applicant has discovered that a WDG composition according to the following solves the aforementioned drawbacks.

[0013] The invention thus provides a composition in the form of one or more water dispersible granule(s), comprising: a) at least one copper salt and / or sulfur compound, b) at least one polysaccharide, c) at least one water-soluble solvent, d) at least one surfactant, e) at least one carrier.

[0014] The composition of the invention presents excellent processability, in particular a lower viscosity making it suited for the manufacture of the granules, especially by extrusion, while having good properties of retention, especially rainfastness, and biological efficacy, when it is applied after dilution in water, at the intended use rate on agricultural target.

[0015] Moreover, the corresponding composition can be efficiently processed for example by extrusion, and said composition has particularly high suspension stability when diluted in water prior to application, good suspensibility, high bioavailability of the active ingredient, and only very small amounts of residues form in the dilution water.

[0016] In the present text, the composition of the invention is also referred to as “WDG composition”, WDG being the acronym of Water Dispersible Granule(s) or Water Dispersible Granular formulation.

[0017] The composition of the invention is advantageously a fungicidal and / or bactericidal agrochemical composition, in that it is advantageously used to treat an agricultural target against phytopathogenic fungi and / or bacteria, the copper salt(s) and / or sulfur compound(s) having a fungicidal and / or a bactericidal effect on said agricultural target upon application.

[0018] Without being bound to any theory, the Applicant believes that this balance of advantages is achieved thanks to the addition of one or more water-soluble solvent(s).

[0019] The Applicant has discovered that the addition of such water-soluble solvent(s) c) as a specific solvent or solvent mixture, in combination with the ingredients a), b), d) and e) described above, lowers the viscosity of the paste obtained after the mixing of the ingredients and allows easy process of the paste, especially by extrusion, for forming the granules, while providing granules having better and faster disintegration in water before use, better particles suspensibility after disintegration, increased retention properties, rainfastness, and advantageously improved biological efficacy on final agricultural target.

[0020] In the composition of the invention, the copper salt and / or sulfur compound is the active ingredient or part of the active ingredient, that may be referred to as “active”, and which imparts fungicidal activity and / or bactericidal activity to the granule(s), thereby preventing and / orcontrolling and / or reducing the phytopathogenic fungal and / or bacterial infection on agricultural target such as crop plants or soil.

[0021] The polysaccharide plays the role of an efficient retention and rainfastness agent, which favors a good retention of copper salt or sulfur compound on the agricultural target upon application, by forming a layer around said agricultural target, which retains the copper salt and / or sulfur compound near the agricultural target and / or enhance biological efficacy.

[0022] The surfactant d), the carrier e), and the specific water-soluble solvent c) allow, in combination with the copper salt and / or sulfur compound and the polysaccharide, to form stable and processable granules while maintaining the good properties imparted by said copper salt and / or sulfur compound and polysaccharide.

[0023] As used herein, the term “sulfur compound” relates to any chemical compound containing sulfur. This includes the element sulfur itself (alone), typically in the form of a yellow powder. In other terms, the composition of the invention may comprise sulfur. The term "elemental sulfur" includes allotropes of elemental sulfur such as plastic (amorphous) sulfur, monoclinic sulfur, rhombic sulfur composed of S8 molecules, and other ring molecules such as S7 and S12.

[0024] As used herein, the term “fungicide(s)” is intended to refer to any agent or combination of agents capable of killing fungi and / or preventing and / or inhibiting fungal growth.

[0025] As used herein, the term “bactericide(s)” is intended to refer to any agent or combination of agents capable of killing bacteria and / or inhibiting bacterial growth.

[0026] The term “agricultural target” is intended to cover plant parts and soil. In one exemplary embodiment, the agricultural target is a plant part.

[0027] As used herein, the term “plant part” is to be understood as meaning all parts and organs of plants above and below the ground, such as shoot, leaf, flower and root, examples which may be mentioned being leaves, needles, stalks, stems, flowers, fruit bodies, fruits, seeds, roots, tubers and rhizomes. The plant parts also include harvested material and vegetative and generative propagation material (e.g., cuttings, tubers, rhizomes, off-shoots and seeds, etc.).

[0028] In one particular embodiment, the agricultural target is plant seed.

[0029] In another particular embodiment, the agricultural target is plant foliage or a foliar cuticle. As used herein, the term “foliage” is intended to mean all parts and organs of plants above the ground. Non-limiting examples include leaves, needles, stalks, stems, flowers, fruit bodies, fruits, etc.

[0030] In another exemplary embodiment, the agricultural target is soil.

[0031] According to the present invention, the term “rainfastness” (or “waterfastness”) refers to the ability of a substance to withstand being washed off by precipitation, condensation, guttation or irrigation.

[0032] According to the invention, the term “precipitation” refers to rainfall, and includes especially moderate rain (20 mm) as well as heavier rain (40 mm). In one embodiment, heavy morning dew may also be considered as falling under the term “precipitation”.

[0033] As used herein, the term “increased rainfastness”, “enhanced rainfastness” or “improved rainfastness” are equivalent and all refer to an increase in rainfastness.

[0034] Any standard methods known in the art, including but not limited to those disclosed in the Examples at the end of the present text, can be used to measure rainfastness.

[0035] The polysaccharide of the composition of the invention, preferably the galactomannan, and more preferably the guar gum, is used as a rainfastness agent for an active, i.e. copper salt and / or sulfur compound (fungicidal and / or bactericidal active), that is to say an ingredient which is capable to enhance the rainfastness of said active, when applied together within the granules.

[0036] Rainfastness may be assessed by several techniques.

[0037] For example, rainfastness may be assessed by comparing the biological efficacy of an active after exposure to water (for instance simulated rainfall) vs biological efficacy of said active without exposure to water (for instance simulated rainfall) (control) for a defined treatment with a given active.

[0038] According to another example, rainfastness may be assessed by comparing visually the deposit of a droplet of a dilution of the WDG containing or not any polysaccharide, in particular guar gum, after a simulated rain, or by dosage of copper or sulfur left onto the leaf or in the water collected after the washes. Inductively Coupled Plasma (ICP) method can be used to dose the copper or the sulfur. Comparing the transmittance (for example with a spectrophotometer at 600 nm) of the water collected after each wash step can also be used.

[0039] The composition of the invention may also comprise one or combinations of the following features: the ingredient a) of the composition according to the invention is preferably at least one copper salt, e.g. a copper salt; the at least one copper salt comprises copper oxychloride and / or copper hydroxide and / or tribasic copper sulfate; the at least one copper salt and / or sulfur compound is present in an amount of 5% to 90%, more preferentially 10% to 85% by weight, preferably of 20% to 80% by weight, morepreferably of 35% to 80% by weight, more preferably of 45% to 80% by weight, relative to the total weight of the composition; the at least one polysaccharide comprises a galactomannan; the at least one polysaccharide is present in an amount of 0.5% to 10% by weight, preferably 1% to 10% by weight, preferably 1% to 8% by weight, preferably 1% to 4% by weight, relative to the total weight of the composition. More preferably, the amount is of 1.5% to 7% by weight, and more preferably of 2% to 4% by weight, relative to the total weight of the composition; the at least one water-soluble solvent is selected in the group consisting of: N-alkyl pyrrolidones, dimethyl sulfoxide, dihydric alcohols, triethylene glycol, alkyl lactate, polyethylene glycols, polypropylene glycols, esteramides, and dioxolane derivatives; the at least one water-soluble solvent comprises at least one dihydric alcohol and / or at least an esteramide. Dihydric alcohol and esteramide solvents enable to lower the viscosity of the paste obtained after the mixing of the ingredients and processability of the paste, and in terms of retention properties, rainfastness, disintegration, suspensibility after disintegration, and biological efficacy; the at least one water-soluble solvent comprises a dihydric alcohol being a propylene glycol and / or an esteramide being methyl-5-(dimethylamino)-2-methyl-5-oxopentanoate; the at least one surfactant comprises at least one wetting agent and / or at least one dispersing agent. Advantageously, the surfactant is a surfactant mixture comprising at least one wetting agent and at least one dispersing agent; the at least one surfactant is present in an amount of 2% to 25% by weight, preferably of 3% to 20% by weight, even more preferably of 10% to 20% by weight, relative to the total weight of the composition; the at least one wetting agent comprises a mixture of:- at least one sulfosuccinate surfactant,- at least one C16-C22 alkyl sulfate and / or an alkyl ether sulfate containing C16-C22 alkyl; The Applicant has discovered that this specific mixture of wetting agent (surfactants) further improves the disintegration properties of the formulation, while maintaining the good properties of processability, retention, especially rainfastness, and biological efficacy. In other terms, this specific mixture of wetting agent decreases the disintegration time of the WDG in water before it is applied upon the agricultural target, and improves the suspensibility in solution of the particles resulting from the disintegration of the WDG. Rapid disintegration is important for the efficient dispersion of WDG formulations in water and is also an importantindex for evaluating the performance of WDG formulations. It also makes the use of the WDG easier and more convenient; the at least one sulfosuccinate surfactant is present in an amount of 1% to 50% by weight, relative to the total weight of the wetting agent; the at least one C16-C22 alkyl sulfate and / or alkyl ether sulfate containing C16-C22 alkyl is present in an amount of 1% to 90% by weight, relative to the total weight of the wetting agent; the at least one wetting agent is a sodium salt of alkyl or dialkyl naphthalene sulfonate; the at least one wetting agent is present in an amount of 2% to 10% by weight, preferably of 3% to 9% by weight, relative to the total weight of the composition; the at least one dispersing agent comprises at least one sodium salt of naphthalene sulfonate-formaldehyde condensate, optionally alkyl -substituted, and / or a salt of alkylbenzene sulfonate. This specific dispersing agent improves suspensibility of the granules once dispersed in water (or aqueous solvent when use), thereby improving the disintegration properties of the formulation, while maintaining the good properties of processability, retention, especially rainfastness, and / or biological efficacy; the at least one dispersing agent comprises a sodium polycarboxylate dispersing agent; the at least one dispersing agent thereof is present in an amount of 5% to 15% by weight, preferably of 7% to 14% by weight, even more preferably of 8% to 13% by weight, relative to the total weight of the composition; the at least one carrier is chosen from the ground natural minerals, preferably kaolins, clays, talc, or chalk, or from the ground synthetic materials, preferably highly-dispersed silica and silicates; the composition may contain one or more other active(s), in particular other fungicides and / or bactericides. According to an embodiment, the composition further comprises at least one multi-site contact fungicide. As used herein, the term “multi-site contact fungicide(s)” refers to contact fungicides that inhibit fungal growth through multiple sites of action and have contact and preventive activity. The term “contact fungicide” as used herein means a fungicide that remains at the site where it is applied but does not travel within the plant.

[0040] As used herein, the term “alkyl” or “alkyl group” means a saturated hydrocarbon radical, which may be straight, branched or cyclic, such as, for example, methyl, ethyl, n- propyl, iso-propyl, n-butyl, sec-butyl, t-butyl, pentyl, n-hexyl, cyclohexyl.

[0041] The present invention also relates to a process for the manufacture of a composition in the form of one or more water dispersible granule(s) as described above.

[0042] Said process comprises the following steps:- mixing a) at least one copper salt and / or sulfur compound, b) at least one polysaccharide, d) at least one surfactant, e) at least one carrier, to obtain a mixture,- grinding the mixture to obtain a powder,- adding water and c) at least one water-soluble solvent to the powder to obtain a wet dough,- granulating the wet dough to obtain one or more granule(s),- drying the granules, wherein the a) at least one copper salt and / or sulfur compound, b) at least one polysaccharide, c) at least one water-soluble solvent, d) at least one surfactant, and e) at least one carrier are as defined previously.

[0043] Preferably, the granulating step is carried out by extrusion.

[0044] Other ingredient(s) / adjuvant(s) may be provided and added to the composition in the mixing step, such as, but not limited to, a disintegrant, a sticker, a dispersant, an antifoam, a thickener, a carrier, an antifreeze agent, and / or a bactericide.

[0045] Another object of the invention is the use of a composition as disclosed above to treat an agricultural target, notably parts of a plant and / or soil, preferably against phytopathogenic fungi and / or bacteria.

[0046] The invention is further related to a process for the treatment of an agricultural target, preferably against fungi and / or bacteria, wherein the composition according to the invention is put, preferably sprayed, on such agricultural target.

[0047] According to the process, the composition according to the invention is advantageously diluted to a targeted use rate, preferentially in water, before being applied, preferably sprayed, on the agricultural target.

[0048] The agricultural target may be for example a plant or a plant part or a soil.BRIEF DESCRIPTION OF THE DRAWINGS

[0049] FIG. 1 shows photographs of leaves of magnolia covered with a copper salt with or without guar gum, in a rainfastness assessment test.DETAILED DESCRIPTION OF THE INVENTION

[0050] The composition of the invention

[0051] The invention relates to a composition, advantageously to a fungicidal and / or bactericidal agrochemical composition, in the form of one or more water dispersible granule(s) (generally in the form of water dispersible granules), comprising:a) at least one copper salt and / or sulfur compound, b) at least one polysaccharide, c) at least one water-soluble solvent, d) at least one surfactant, e) at least one carrier.

[0052] The Applicant has surprisingly discovered that such a WDG composition solves the processability issues usually encountered when humidifying guar, thereby obtaining a composition with a low viscosity perfectly suited for the preparation of granules, especially by extrusion, while showing excellent retention properties, in particular rainfastness, and / or biological efficacy.

[0053] Copper salt(s) and / or sulfur compound(s) (a)

[0054] Copper salts and sulfur compounds a) are the active ingredient, or part of the active ingredient, and may be referred to as the “active”. The active imparts fungicidal and / or bactericidal activity to the granule(s), and allows for preventing, controlling and / or reducing the phytopathogenic fungal and bacterial infection on crop plants.

[0055] The composition of the invention may contain only copper salt(s), or sulfur compound(s), or a combination of both copper salt(s) and sulfur compound(s).

[0056] The copper salt includes mono- or, preferably, divalent copper salts of inorganic and organic acids, for example copper oxychloride, copper octanoate, copper ammonium carbonate, copper arsenate, copper oxysulfate, copper formate, copper proprionate, copper oxyacetate, copper citrate, copper chloride, copper diammonium chloride, copper nitrate, copper carbonate, basic copper carbonate, copper pyrophosphate, copper phosphate, disodium copper EDTate, diammonium copper EDTate, copper oxalate, copper tartrate, copper gluconate, copper glycinate, copper glutamate, copper aspartate, copper glutonate, copper adipate, copper palmitate, copper stearate, copper caprylate, copper decanoate, copper undecylenate, copper neodecanoate, copper linoleate, copper oleate, copper borate, copper methanesulfonate, copper sulfamate, copper acetate, copper hydroxide, copper oxide, copper oxychloride sulfate, copper sulfate, basic copper sulfate, tribasic copper sulfate (TBCS), oxinecopper, copper bis(3-phenylsalicylate), copper dihydrazinium disulfate, dicopper chloride trihydroxide, tri copper dichloride dimethyldithiocarbamate.

[0057] Other copper compounds which are suitable are mixed salts with ammonium, alkali metals and alkaline earth metals. Examples are ammonium copper(II) sulfate, copper(II) magnesium sulfate, copper naphthenate, copper 8-quinolate and copper(II) potassium sulfate.Preferably copper oxychloride, copper octanoate, copper ammonium carbonate, copper arsenate, copper(II) acetate arsenite, copper oxysulfate, copper formate, copper propionate, copper oxyacetate, copper citrate, copper carbonate, copper chloride, copper diammonium chloride, copper nitrate, copper carbonate, basic copper carbonate, copper pyrophosphate, copper phosphate, disodium copper EDTate, diammonium copper EDTate and copper acetate, copper hydroxide, copper oxide, copper oxychloride sulfate, copper sulfate, basic copper sulfate, oxine-copper, copper bis(3-phenylsalicylate), copper dihydrazinium disulfate, dicopper chloride trihydroxide, copper naphthenate, copper 8-quinolate and tricopper dichloride dimethyl-dithiocarbamate are used, especially preferably copper acetate, copper carbonate, copper oxychloride, copper hydroxide, copper oxide, copper oxychloride sulfate, copper sulfate, basic copper sulfate, oxine-copper, copper bis(3-(phenylsalicylate ), copper dihydrazinium disulfate, dicopper chloride trihydroxide, copper octanoate, copper ammonium carbonate, copper arsenate, copper oxysulfate, copper naphthenate, copper 8-quinolate and tricopper dichloride dimethyidithiocarbamate.

[0058] According to an embodiment, the copper-based fungicide is selected from the group consisting of: cupric acetate, cupric chloride, cupric chlorate, cupric formate, cupric hexafluorosilicate, cupric nitrate, cupric chromate, copper sulfate pentahydrate, bordeaux mixture, copper hydroxide, cuprous oxide, copper oxychloride, copper oxychloride sulfate (COCS), tribasic copper sulfate such as cupric sulfate, tricupric hydroxide, hemihydrate, and any combination thereof.

[0059] Copper salts which are preferably used are copper salts which are largely insoluble in water, such as copper oxychloride, copper hydroxide, or tribasic copper sulfate.

[0060] Sulfur compounds include in particular the sulfur element itself, i.e. elemental sulfur, which is typically in the form of a powder.

[0061] Preferably, the at least one copper salt and / or sulfur compound is present in an amount of 5% to 90% by weight, more preferably 10% to 85% by weight, preferably of 20% to 80% by weight, more preferably of 35% to 80% by weight, more preferably of 45% to 80% by weight, relative to the total weight of the composition.

[0062] In one embodiment, the at least one copper salt and / or sulfur compound is present in an amount of 15% to 45% relative to the total weight of the composition.

[0063] The rate at which the composition according to the invention is applied will depend upon the particular type of fungus and / or bacteria to be controlled, the degree of control required and the timing and method of treatment. In general the composition of the presentinvention can be applied at an application rate lying in the range of from about 25 grams of per ha (g / ha) to about 5000 g / ha of total active ingredients.

[0064] In one embodiment, the composition of the invention is preferably applied at a rate of 100 - 2000 g / ha of metallic copper, more preferentially at a rate of 250 - 1500 g / ha of metallic copper, even more preferentially at a rate of 500 - 1000 g / ha of metallic copper. In some embodiments, the composition of the invention is preferably applied at a rate of 250 to 750 g / ha or metallic copper.

[0065] Prior to use, the composition according to the invention is preferably diluted 2-5000 times with an aqueous solvent, preferably water, to contain between 0.0001 and 10 % (w / v) of the copper salt, prior to contacting a plant, plant part or soil with the composition.

[0066] The composition of the invention may further include other biological active ingredients, such as pesticides, growth regulators, repellents, safeners, biostimulants, micro or macronutrients, and / or fertilizers. Nutrients refer to chemical elements and compounds which are desired or necessary to promote or improve plant growth. The term “biostimulant” is preferably intended to mean a compound which may enhance metabolic or physiological processes such as respiration, photosynthesis, nucleic acid uptake, ion uptake, nutrient delivery, or a combination thereof.

[0067] For example, these biological active ingredients may be chosen from fungicides, insecticides, acaricides, algicides, molluscicides, miticides, nematicides, bactericides, biocides, herbicides and rodenticides.

[0068] In a specific embodiment, these biological actives ingredients may be chosen from fungicides, especially among strobilurin fungicides, succinate dehydrogenase inhibitor (SDHI) fungicides, triazole fungicides, dicarboxamide fungicides, phenylpyrrole (PP) fungicides, phenyl acetamide fungicides, benzophenone fungicides, pyrimidines fungicides, picolinamide fungicides.

[0069] In a specific embodiment, these actives may be chosen from multi-site contact fungicides.

[0070] Preferably, these actives may be chosen from multi-site contact fungicides selected from dithiocarbamate fungicides, phthalimide fungicides, chloronitrile fungicides, sulfamide fungicides, guanidine fungicides, triazine fungicides, and quinone fungicides.

[0071] Multi-site contact fungicides inhibit fungal growth through multiple sites of action and have contact and preventive activity. The term “contact fungicide” as used herein refers to a fungicide that remains at the site where it is applied but does not travel within the plant. Suchcontact fungicides are convenient since they provide better retention of the fungicides on the agricultural target and satisfying biological efficacy.

[0072] Even more preferably, the additional biological active ingredients may be chosen from fluazinam, folpet, captan or dithianon, those being multi-site contact fungicides.

[0073] When other biological active ingredients are present in the composition, they may be included at a dose between 0.5% to 60% by weight, preferably between 1 to 40% by weight, based on the total weight of the actives.

[0074] Polysaccharide (b)

[0075] The polysaccharide preferably comprises a galactomannan.

[0076] Galactomannans are polysaccharides consisting of a mannose backbone with galactose side groups, more specifically, a (l-4)-linked beta-D-mannopyranose backbone with branch points from their 6-positions linked to alpha-D-galactose.

[0077] Naturally occurring galactomannans are available from numerous sources, including guar gum, guar splits, locust bean gum, cassia gum, fenugreek gum, and tara gum. Additionally, galactomannans may also be obtained by classical synthetic routes or may be obtained by chemical modification of naturally occurring galactomannans.

[0078] Preferably, the at least one polysaccharide is present in an amount of 0.5% to 10% by weight, preferably 1% to 10% by weight, preferably of 1.5% to 8% by weight, and more preferably of 2% to 4% by weight, relative to the total weight of the composition.

[0079] Preferably, the galactomannan comprises at least one guar gum.

[0080] When the galactomannan comprises at least one guar gum, the at least one guar gum is preferably present in an amount of 0.5% to 10% by weight, preferably 1% to 10% by weight, preferably of 1.5% to 8% by weight, and more preferably of 2% to 4% by weight, relative to the total weight of the composition.

[0081] The guar gum may be a guar gum derivative, which may be a derivatized or non- derivatized guar gum derivative.

[0082] In the present application, “guar” designates the plant Cyanopsis tetragonoloba. Cyamopsis tetragonoloba (guar) gums as defined below.

[0083] In the present application, “guar seeds” designates seeds derived from guar. Guar seeds comprise the hull, which is more or less fibrous, the germ, and two “guar splits” or “endosperm halves”, which constitute the endosperm of guar. The splits (or endosperm) is / are rich in galactomannans. The guar seeds generally consist of 35% to 40% by weight of endosperm, 42% to 47% by weight of germ, and 14% to 17% by weight of hull.

[0084] In the present application, “guar flour” or “guar powder” designates a powder derived from the guar endosperm.

[0085] In the present application, “native guar” designates macromolecular chains of the galactomannan type, derived from guar endosperm, not having been subjected to chemical modification by the grafting of chemical groups. Native guar comprises macromolecules containing a principal chain of Dmannopyranose units linked in the beta (1-4) position substituted by Dgalactopyranose units in the beta (1-6) position. Native guar has a mannose / galactose ratio of about 2.

[0086] In the present application, “Cyamopsis tetragonoloba (guar) gum guar” (also referred to as “guar gum”) designates a product substantially consisting of native guar, in the form of guar splits, or of guar flour or powder. In more details, “guar gum” refers to the mucilage found in the seed of the leguminous plant Cyamopsis tetragonolobus. The water soluble fraction (85%) is called “guaran,” which consists of linear chains of (l,4)-.p-D mannopyranosyl units- with -D-galactopyranosyl units attached by (1,6) linkages. The ratio of D-galactose to D- mannose in guaran is about 1 :2. Guar gum typically has a weight average molecular weight of between 2,000,000 and 5,000,000 g / mol. Guars having a reduced molecular weight, such as for example, from about 50,000 to about 2,000,000 g / mol are also known.

[0087] In one embodiment, native (i.e. not derivatized) polysaccharide gums, such as for instance native guar gum, cassia gum or tamarind seed gum, are suitable guars according to the present invention.

[0088] As used herein, the “average molecular weight” of the guar gum means the weight average molecular weight of said guar gum.

[0089] According to any of the invention embodiments, the guar gum may have an average molecular weight (Mw) of between 2,000 Daltons and 5,000,000 Daltons. In one embodiment, the guar gum of the invention may have an average molecular weight (Mw) of between 100,000 Daltons and 4,500,000 Daltons, for instance between 500,000 Daltons and 4,000,000 Daltons, for instance between 1,000,000 Daltons and 3,500,000 Daltons, for instance between 2,000,000 and 3,500,000 Daltons.

[0090] In another embodiment, the guar gum may have an average molecular weight (Mw) of between about 100,000 Daltons and 2,000,000 Daltons, for instance between about 300,000 Daltons and 1,800,000 Daltons, for instance between about 350,000 Daltons and 1,700,000 Daltons, for instance between about 400,000 Daltons and 1,500,000 Daltons.

[0091] The average molecular weight of the guar gum may be measured by GPC (Gel Permeation Chromatography). Measurements may be carried out for instance using Shodex OH Pak columns and Agilent Refractive Index Detector.

[0092] The guar gum may be crosslinked or not.

[0093] According to any of the invention embodiments, the guar gum is not crosslinked.

[0094] According to any of the invention embodiments, the guar gum may be crosslinked. It may be for instance treated with a crosslinking agent. Borax (sodium tetraborate) for instance is commonly used as a processing aid in the reaction step of the water-guar splits process to partially crosslink the surface of the guar splits and thereby reduces the amount of water absorbed by the guar splits during processing. Other crosslinkers, such as, for example, glyoxal or metals like titanium, zirconium or aluminium, are also widely used.

[0095] Processes for making derivatives of guar gum splits are generally known. Typically, guar splits are reacted with one or more derivatizing agents under appropriate reaction conditions to produce a guar polysaccharide having the desired substituent groups.

[0096] Other galactomannans of interest are the modified galactomannans, including derivatized guar polymers, such as carboxymethyl guar, carboxymethylhydroxypropyl guar, cationic hydroxypropyl guar, hydroxyalkyl guar, including hydroxyethyl guar, hydroxypropyl guar, hydroxybutyl guar and higher hydroxylalkyl guars, carboxylalkyl guars, including carboxymethyl guar, carboxylpropyl guar, carboxybutyl guar, and higher carboxyalkyl guars, the hydroxyethylated, hydroxypropylated and carboxymethylated derivative of guaran, the hydroxethylated and carboxymethylated derivatives of carubin, and the hydroxypropylated and carboxymethylated derivatives of cassia-gum.

[0097] In one embodiment, the polysaccharide content, in particular guar, is between 0.01% and 0.16 % by weight in the final dilution, preferably between 0.03% and 0.08% by weight, even more preferably between 0.04% and 0.07% by weight in the final dilution to be applied on the agricultural target.

[0098] Water-soluble solvent(s) (c)

[0099] The composition of the invention comprises at least one water-soluble solvent.

[0100] The addition of one or more water-soluble solvent(s) lowers the viscosity of the paste obtained after the mixing of the ingredients and allows easy process of the paste, especially extrusion, for forming the granules, while providing granules, in combination with the other ingredients, with good disintegration in water or aqueous solution before use, goodparticle suspensibility after disintegration, and achieving good biological efficacy and good retention and rainfastness properties.

[0101] Hence, the addition of one or more water-soluble solvent(s) solves the problems of processability while maintaining and even improving efficacy and convenience of the granules.

[0102] According to the present invention, a “water soluble solvent” is a solvent having a water solubility, at 25°C and at atmospheric pressure (i.e. 1.013xl0A5 Pa), advantageously equal or greater than 300g / L (gram of solvent per liter of water), more preferentially greater than 600g / L, even more preferentially that mixes fully in water in all proportions forming a homogeneous clear solution.

[0103] The water-soluble solvent is preferably selected from the group consisting of: N-alkyl pyrrolidones (for example N-butyl pyrrolidone), dimethyl sulfoxide, dihydric alcohols (for example propylene glycol), triethylene glycol, glycerol, alkyl lactate (for example ethyl lactate), tetrahydrofurfuryl alcohol, gamma-butyrolactone, alkyl carbonates, alkylene carbonates, polyethylene glycols, ethylene glycol alkyl ethers (for example ethylene glycol monopropyl ether or ethylene glycol n-butyl ether), alkyl carbonates, alkylene carbonates, polyethylene glycol alkyl ethers (for example polyethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol n-butyl ether), polypropylene glycols (for example dipropylene glycol) and polypropylene glycol alkyl ethers (for example dipropylene glycol dimethyl ether), esteramide such as Methyl-5-(dimethylamino)-2-methyl-5-oxopentanoate, dioxolane derivatives such as 2, 2-dimethyl-4-hydroxymethyl- 1,3 -di oxolane, N,N-dimethyl lactamide.

[0104] More preferably, the water-soluble solvent is selected from the group consisting of: N-alkyl pyrrolidones (for example N-butyl pyrrolidones), dimethyl sulfoxide, dihydric alcohols (for example propylene glycol), triethylene glycol, alkyl lactate (for example ethyl lactate), polyethylene glycols, polypropylene glycols (for example dipropylene glycol), esteramide such as Methyl-5-(dimethylamino)-2-methyl-5-oxopentanoate, dioxolane derivatives such as 2, 2-dimethyl-4-hydroxymethyl- 1,3 -di oxolane, N,N-dimethyl lactamide.

[0105] Even more preferably, the water-soluble solvent is selected from the group consisting of: dimethyl sulfoxide, propylene glycol, N-butyl pyrrolidone, Ethyl lactate, Polyethylene glycol 400 or 600, Methyl-5-(dimethylamino)-2-methyl-5-oxopentanoate.

[0106] Even more preferably, the water-soluble solvent is preferably selected from propylene glycol, and Methyl-5-(dimethylamino)-2-methyl-5-oxopentanoate.

[0107] Preferably, the water-soluble solvent comprises at least one dihydric alcohol and / or at least one esteramide.

[0108] Dihydric alcohol and esteramide solvents are specific water-soluble solvent(s) which lead to very good and unexpected results and properties, especially with respect to the processability of the paste and retention and rainfastness properties.

[0109] The esteramide may be chosen in the group containing: Methyl-5- (dimethylamino)-2-methyl-5-oxopentanoate, which is commercialized by the company Solvay under the name of Rhodiasolv® PolarClean).

[0110] Preferably the solvent added to solve processability issues is present in an amount of 3% to 15% by weight, preferably of 4% to 10% by weight, relative to the total weight of the composition.

[0111] Surfactant (d)

[0112] The composition of the invention further comprises d) at least one surfactant. This means that the at least one surfactant may be, for example, a mixture of surfactants.

[0113] The at least one surfactant comprises at least one wetting agent and / or at least one dispersing agent.

[0114] Preferentially the composition comprises at least one wetting agent and one dispersing agent.

[0115] Suitable surfactants may be chosen in the following group: alkyl ether carboxylates; sodium salts of fatty acids; acyl glutamates; sarcosinates; alkyl sulfosuccinates, such as dioctyl sulfosuccinate, taurates such as methyl oleyl taurate; alkyl phosphate esters, e.g., monophosphoric acid alkyl esters and hypophosphoric acid alkyl esters, alkoxylated phosphate esters; alkyl sulfates, alkyl ether sulfates; alkylbenzenesulfonic acids, such as, for example, phenolsulfonic acids, naphthalene-and dibutylnaphthalenesulfonic acids, or dodecylbenzenesulfonates, alkyl naphthalene sulfonates, alkyl methyl ester sulfonates, or mono- or dialkylsuccinic acid ester sulfonates, lignosulfonates, sodium salt of naphtalene sulfonate-formaldehyde condensate that may optionally be alkyl substituted: Geropon® L Wet Max (wetting agent - manufactured by Solvay), Supragil® WP (wetting agent - manufactured by Solvay), Supragil® MNS 90, Supragil MNS 88-E (dispersant surfactant - manufactured by Solvay); sugar surfactants, in particular, sorbitol esters, such as, for example, sorbitan fatty acid esters (sorbitan monooleate, sorbitan tristearate) and esters of mono- or polyhydric alcohols, such as, for example, alkyl(poly)glycosides and N-alkylgluconamides.

[0116] Other suitable surfactants include sulfosuccinates (for example dioctyl sulfosuccinate), polyoxyethylene / propylene oxides, alkoxylated tri styrylphenols for example ethoxylated tri styrylphenols or ethoxylated propoxylated trystyrylphenols, alkoxylated tri styrylphenol sulfate for example ethoxylated tri styrylphenol sulfate, alkoxylated tri styrylphenol phosphate for example ethoxylated tri styrylphenol phosphate, alkoxylated alcohols for example ethoxylated alcohols or ethoxylated propoxylated alcohols, alkyl- and alkylarylsulfonates, alkylbenzenesulfonic acids, such as, for example, phenolsulfonic acids, naphthalene-and dibutylnaphthalenesulfonic acids, or dodecylbenzenesulfonates, alkylnaphthalenesulfonates, alkyl methyl ester sulfonates, or mono- or dialkylsuccinic acid ester sulfonates.

[0117] Suitable surfactants also include the polycarboxylate type, for example those such as hydrophobically modified comb-like polymers, for example polyacrylic acid, polymethacrylic acid, polymaleic acid, polymaleic anhydride, a copolymer of maleic acid or maleic anhydride with an olefin (such as isobutylene or diisobutylene), a copolymer of acrylic acid and itaconic acid, a copolymer of methacrylic acid and itaconic acid, a copolymer of maleic acid or maleic anhydride and styrene, a copolymer of acrylic acid and methacrylic acid, a copolymer of acrylic acid and methacrylate, a copolymer of acrylic acid and vinyl acetate, a copolymer of styrene and methacrylic acid, modified copolymers of styrene and methacrylic acid, a copolymer of maleic acid or maleic anhydride and acrylic acid, polymethyl methacrylate-polyethylene glycol graft copolymer, an N-methyl fatty acid (e.g. Cs-Cis)- sarcosinate, a carboxylic acid such as a resin acid or a fatty acid ( e.g. Cs-Cis) or a salt of such a carboxylic acid. The abovementioned copolymers may also be in the form of their salts, e.g. alkali metal salts (preferably Li, Na, K), alkaline earth metal salts (preferably Ca, Mg), ammonium or various amines.

[0118] Preferably the at least one wetting agent is present in an amount of 2% to 10% by weight, preferably of 3% to 9% by weight, relative to the total weight of the composition.

[0119] Preferably said wetting agent comprises a mixture of:- at least one sulfosuccinate surfactant,- at least one C16-C22 alkyl sulfate and / or an alkyl ether sulfate containing C16-C22 alkyl.

[0120] The sulfosuccinate surfactant, also referred to as sulfosuccinate-based surfactant, is an agriculturally acceptable salt of mono-ester of sulfosuccinic acid, an agriculturally acceptable salt of di-ester of sulfosuccinic acid, each of which is optionally alkoxylated, or a mixture thereof.

[0121] For example, the sulfosuccinate surfactant may be a sodium salt of alkyl ester of sulfosuccinic acid.

[0122] Preferably, the sulfosuccinate surfactant is according to the general formula (I):

[0123] (Formula (I))wherein Ri and R2, same or different, is:wherein R3 is H, C1-C4, alkyl, alkenyl, hydroxyalkyl or hydroxy alkenyl;R4 is C1-C22 alkyl, alkenyl, hydroxyalkyl or hydroxy alkenyl; n is 0 or an integer of 1 to 100;X+is H or a cation.

[0124] Preferably, in the general formula (I), Ri and R2, same or different, is:R4 is C1-C22 alkyl, alkenyl, hydroxyalkyl or hydroxy alkenyl;X+is H or a cation.

[0125] Preferably, the C 16-C22 alkyl sulfate is according to the general formula (II):R.5OSO3-M+(Formula (II)) wherein R5 is a C16-C22 alkyl or hydroxyalkyl group, either linear or branched;M+is a cation.

[0126] Preferably, the alkyl ether sulfate containing C16-C22 alkyl is represented by the general formula (III):R6(AO)HOS( M* (FORMULA(IN)) wherein Re is a C16-C22 alkyl or hydroxyalkyl group, either linear or branched;AO is ethylene oxide (EP), propylene oxide (PO) or mixture thereof; n represents degree of alkoxylation and is an integer of 1 to 100;M+is a cation.

[0127] According to an embodiment, the composition of the invention further comprises a C1-C14 alkyl sulfate or an alkyl ether sulfate containing C1-C14 alkyl. Preferably, according to this embodiment, the at least one C16-C22 alkyl sulfate and / or alkyl ether sulfate containing C16-C22 alkyl is at least 5 wt% of the total weight of the latter and the C1-C14 alkyl sulfate or alkyl ether sulfate containing C1-C14 alkyl.

[0128] Preferably, the sulfosuccinate surfactant is present in an amount of 1% to 50% by weight, based on total weight of the wetting agent d).

[0129] Preferably, the C 16-C22 alkyl sulfate and / or alkyl ether sulfate containing Ci6- C22 alkyl is present in an amount of 1% to 90% by weight, relative to the total weight of the wetting agent.

[0130] The term C 16-C22 corresponds to a hydrocarbon chain having between 16 and 22 carbon atoms, the lower and upper limit 16 and 22 being included in this range.

[0131] In one embodiment the wetting surfactant in a salt of alkyl or dialkyl naphthalene sulfonate, such as sodium salt of diisopropyl naphthalene sulfonate.

[0132] The dispersing agent, also called “dispersant”, is preferably present in an amount of 5% to 15% by weight, preferably of 7% to 14% by weight, more preferably of 8% to 13% by weight, relative to the total weight of the composition.

[0133] When the surfactant comprises a sulfonate, the sulfonate is preferably an alkaryl sulfonate salt or an alkaryl sulfonate ester or an alkaryl sulfonate formaldehyde condensate thereof, more preferably an alkylbenzene sulfonate salt / ester, an alkylnaphthalene sulfonate salt / ester, an alkylbenzene sulfonate salt / ester condensed with formaldehyde or an alkylnaphthalene sulfonate salt / ester condensed with formaldehyde, more preferably an alkylbenzene sulfonate salt / ester condensed with formaldehyde or an alkylnaphthalene sulfonate salt / ester condensed with formaldehyde. The surfactant may comprise Supragil® MNS 90 (dispersant surfactant - manufactured by Solvay) or Supragil® MNS 88-E.

[0134] An “alkaryl” is an alkyl -substituted aryl radical.

[0135] The composition may include other dispersing agents (dispersants).

[0136] Suitable dispersants are in particular dispersants of the polycarboxylate type, for example those such as hydrophobically modified comb-like polymers, for example polyacrylic acid, polymethacrylic acid, polymaleic acid, polymaleic anhydride, a copolymer of maleic acid or maleic anhydride with an olefin (such as isobutylene or diisobutylene), a copolymer of acrylic acid and itaconic acid, a copolymer of methacrylic acid and itaconic acid, a copolymer of maleic acid or maleic anhydride and styrene, a copolymer of acrylic acid and methacrylic acid, a copolymer of acrylic acid and methacrylate, a copolymer of acrylic acidand vinyl acetate, a copolymer of styrene and methacrylic acid, modified copolymers of styrene and methacrylic acid, a copolymer of maleic acid or maleic anhydride and acrylic acid, polymethyl methacrylate-polyethylene glycol graft copolymer, anN-methyl fatty acid (e.g. Cs- Ci8)-sarcosinate, a carboxylic acid such as a resin acid or a fatty acid ( e.g. Cs-Cis) or a salt of such a carboxylic acid. The abovementioned copolymers may also be in the form of their salts, e.g. alkali metal salts (preferably Li, Na, K), alkaline earth metal salts (preferably Ca, Mg), ammonium or various amines.

[0137] Further preferred are dispersants from the group comprising sodium or potassium salts of the copolymers of maleic acid and olefins (e.g. Geropon® T / 36 from Solvay; Duramax® D-305 from Dow); and sodium salts of copolymers of methacrylic acid and styrene (Tersperse® 2700 from Huntsman; Atlox Metasperse® 500S or Metasperse® 550S from Croda).

[0138] Carrier (e)

[0139] The composition of the invention further comprises at least one carrier.

[0140] Preferably, the carrier is present in an amount of 1% to 20% by weight relative to the total weight of the composition.

[0141] The composition may include various mineral and water-soluble powders, which may act as carriers. Examples of mineral powders that may be used in the present invention include diatomaceous earth, talc, clay, bentonite, and calcium carbonate. Examples of water-soluble powders that may be used in the present invention include saccharides, urea and various types of salts. Saccharides include lactose, fructose, and glucose. Salts include alkali metal salts and sodium salts of sulfuric acid, phosphoric acid, hydrochloric acid, nitric acid or carbonic acid. These powders may be used singularly or in combination in the granule formulation.

[0142] Other examples of carriers or fillers are ground natural minerals, such as kaolins, clays, talc, chalk, and ground synthetic materials, such as highly-dispersed silica, silicates.

[0143] Preferably, the composition comprises at least kaolin as a carrier.

[0144] Other ingredients

[0145] The composition according to the invention may optionally also comprise further ingredients (adjuvants) which are suitable for the formulation. These are understood as meaning the following classes of substances, without limitation.

[0146] Stickers, dispersants, disintegrants, uptake adjuvants, antifoams, thickeners, carriers, buffers, drift retardants, pigments, neutralizers, antifreeze agents, pH modifiers, stabilizers, anti-caking agents, colorants, UV filters, preservatives, formulation aids, antioxidants and bactericides.

[0147] Typically, 0.1% to 99% by weight, preferably 0.1% to 40% by weight, of carriers are present in the composition in the form of granules. Typically, 0.1% to 20% by weight of other adjuvants are present.

[0148] The importance and the corresponding use of the above mentioned substances depends on the intended type of formulation and on the nature of the active ingredient.

[0149] Examples of disintegrant the disintegrant are ammonium sulfate, lactose, maltose, sodium sulfate, ammonium bicarbonate, ammonium phosphate, sodium bicarbonate, magnesium sulfate, hydrogen carbonate, sodium chloride, sodium citrate, kaolin, 10 gypsum, calcium carbonate, sodium dihydrogen carbonate, sodium dihydrogen phosphate, ammonium citrate, sodium acetate bentonite, aluminium chloride, citric acid, succinic acid, or a combination thereof. The granule may optionally include various mineral and water-soluble powders, which may act as fillers.

[0150] Examples of mineral powders that may be used in the present invention include diatomaceous earth, talc, clay, bentonite, and calcium carbonate.

[0151] Examples of water-soluble powders that may be used in the present invention include saccharides, urea and various types of salts. Saccharides include lactose, fructose, and glucose. Salts include alkali metal salts and sodium salts of sulfuric acid, phosphoric acid, hydrochloric acid, nitric acid or carbonic acid. These powders may be used singularly or in combination in the granule formulation.

[0152] Examples of antifoams are silicone emulsions (such as, for example, Silikon® SRE, Wacker or Rhodorsil® from Solvay), long-chain alcohols, fatty acids, organofluorine compounds and their mixtures.

[0153] Bactericides may be added to stabilize the formulation. Examples of suitable bactericides are Proxel® from ICI or Acticide® RS from Thor Chemie and Kathon® MK from Lanxess.

[0154] Process for manufacturing the WPG

[0155] The invention also provides a method of producing one or more water dispersible granule(s).

[0156] The method involves the following ingredients previously described: a) the active component including the copper salt and / or sulfur compound, b) the polysaccharide, c) the water-soluble solvent, d) the surfactant, and e) the carrier, and optionally other ingredient(s) / adjuvant(s), such as a disintegrant, a sticker, a dispersant, an antifoam, a thickener, a carrier, an antifreeze agent and a bactericide.

[0157] The method also includes a step of mixing a) the copper salt and / or sulfur compound, b) the polysaccharide, d) the surfactant, and e) the carrier, to obtain a mixture (mixing step). These ingredients are advantageously mixed together first since they are in the form of powders and thus can be readily and conveniently mixed together.

[0158] The mixture is then preferably grinded to obtain a powder.

[0159] A step of forming the mixture obtained previously into water dispersible granules (WDG) is then carried out (formation of the granules / granulation step).

[0160] During the step of mixing, the ingredients may be combined with an appropriate amount of water and the water-soluble solvent as determined by one having ordinary skill in the art. It is contemplated that the above components may be added in any order. In addition, any of the above components may be pre-dissolved in water with the water-soluble solvent to aid in the mixing step, provided that the ultimate solubility in water is not significantly affected. Optional ingredients may also be added at various points throughout the method of producing a granule.

[0161] In one embodiment, the mixing step may be carried out with a wet milling machine, such as a ball mill. Alternatively, the mixing step may be carried out with a masticating extruder, such as a kneader. Alternatively still, it is also contemplated that the mixing of the above components may be carried out with other mixer types, such as various blending mixers, as will be appreciated by one of ordinary skill in the art. Depending on the mixing step used, a dough or slurry is formed. The dough or slurry can be formed into the granules through additional steps described below.

[0162] The step of forming the mixture into granules may be further defined as including the steps of granulating the mixture into wet granules and drying the wet granules (drying step) to form the water dispersible granules. Alternatively, the step of forming the mixture into granules may comprise utilizing a spray dryer or fluidized bed to form the granules that are dried through the granulating process.

[0163] Furthermore, the step of granulating the mixture into wet granules described above may comprise radially extruding the mixture into wet granules. Alternatively, the step of granulating the mixture may comprise pan-granulating the mixture into wet granules.

[0164] The step of drying of the wet granules may be performed with one or more ovens, air-dry systems, or alternative drying systems, as will be appreciated by one of ordinary skill in the art.

[0165] If a spray dryer is used to perform the step of drying the wet granules, the hotair inlet temperature of the spray dryer is typically set to a temperature lower than, or equal to, the melting point of the active component used in the granule.

[0166] Alternatively, the hot-air inlet temperature of the spray dryer may be set to a temperature which is 20 °C less than the melting point of the active component.

[0167] The granules may be sieved in order to yield granules of relatively uniform size. In this context, the granules have a particle size ranging from 5 to 100 mesh, or from 10 to 40 mesh.

[0168] According to a preferred embodiment, the method is performed according to the following.

[0169] The copper salt or sulfur compound is micronized / grinded through a suitable micronizer (micronizing step). This micronized material is then post-mixed to have homogenous powder. In some cases, the copper salt or sulfur compound is micronized in presence of the at least surfactant and / or carrier.

[0170] The micronized particles distribution (d90) is preferably below 25 microns, more preferably below 20 microns, even preferably below 15 microns, even more preferably below 12 microns.

[0171] The micronized copper salt or sulfur compound, a disintegrant, a wetting agent, a dispersant, at least one polysaccharide (preferably a guar derivative gum), and a carrier are mixed in required quantity in a blender to have pre-blended mixture in the form of homogenous powder (mixing step).

[0172] Water or water-soluble solvent(s) or water-soluble aprotic solvent(s) or a blend of water and said solvent(s) is admixed with the post-mixed mixture obtained previously to obtain a homogenous wet dough (dough preparation step).

[0173] The dough obtained previously is granulated to obtain the granules - WDG, preferably by extrusion (granulation step).

[0174] The granules are then dried (drying step). Preferably, the drying is carried out at 45°C during 24h.EXAMPLES

[0175] Comparative Example 1 - Preparation of WPG with water (no other solvent)

[0176] Water dispersible granules are prepared using water, no other solvent being added.

[0177] The WDGs are prepared according to the protocol below.

[0178] Copper oxychloride (57%) is micronized / grinded through a suitable micronizer, and post-mixed to obtain a homogenous powder.

[0179] The micronized copper oxychloride, Supragil® MNS / 90 (an alkyl naphthalene sulfonate dispersant - commercialized by Solvay), sodium dodecylbenzene sulfonate (anionic surfactant), kaolin Argirec™ B24 (carrier / disintegrant - commercialized by Imerys), AgRHEA™ SticGuard (guar gum derivative commercialized by Solvay), a blended surfactant (wetting agent) composed of a sulfosuccinate surfactant and a C16-C22 alkyl sulfate, are mixed in a blender to have pre-blended mixture in the form of homogenous powder.

[0180] Water is admixed with the post-mixed mixture obtained previously to obtain an homogenous wet dough, the latter being then extruded to obtain the WDG.

[0181] The granules are then dried at 45°C during 24h.

[0182] The ingredients of the granular composition and their relative quantities in said composition are summarized in Table 1 below.

[0183] Tests of suspensibility and disintegration are then carried out. The results obtained are also summarized in Table 1 below.

[0184] The protocol implemented to evaluate disintegration of the WDG is the following. 2.5g of a WDG sample are weighted to make up a 250 ml dilution in water in a 250 ml measuring cylinder. The stoppered cylinder is inverted at 180° (turned by hand through 180 degrees, which represents a half inversion) and brought back to its initial position, the whole operation being completed in approximately 2 seconds. The number of inversions required for complete dispersion of the sample is recorded.

[0185] According to method CIPAC MT 184 (Collaborative International Pesticides Analytical Council), the stability of the suspension that forms upon dispersion of the water dispersible granules described herein in water can be determined by measuring how much of the sample remains suspended after a period of time (i.e., the total suspensibility). The total suspensibility of a sample can be determined using said CIPAC Method 184.

[0186] This method is intended to determine the suspensibility, which is defined as the percentage of one or more active ingredient(s) remaining in suspension after a given time. Themethod is applicable to formulations forming suspensions on dilution with water at sample concentration between 0.1 % and 10 %. The cylinders containing the suspension are placed in a bath water at 30°C. In the examples, the WDG sample concentration is fixed at 1% and the measurement is done after 30 minutes at 30°C.

[0187] Table 1

[0188] Disintegration performance is considered optimized when inferior to 30 inversions.

[0189] Suspensibility is considered optimized when superior to 70%.

[0190] Therefore, based on the results, the disintegration of composition 1 is optimized whereas its suspensibility is not.

[0191] Moreover, the granules composition 1 are sticky and difficult to extrude since the paste presents a high viscosity.

[0192] Example 1 - Preparation of WPG with a water-soluble solvent

[0193] Water dispersible granules are prepared using the same protocol as comparative example 1, except that a water-soluble solvent, namely propylene glycol, is used as a solvent in addition to water.

[0194] The ingredients and results are summarized in Table 2 below, wherein the composition of comparative example 1 is shown on the left column for convenience.

[0195] Table 2

[0196] In composition 2, the ratio water / Propylene glycol is 50 / 50 by weight.

[0197] The disintegration value between 9 and 12 of composition 2 is below 30 and its suspensibility value 83.1 is above 70.

[0198] The addition of propylene glycol to water strongly increases the suspensibility, while just slightly decreasing the ease of disintegration, still far below 30 inversions, thereby making the composition more convenient because more readily usable by the end user.

[0199] Therefore, the use of propylene glycol with water allows for achieving great properties of both disintegration and suspensibility, while taking advantage of the convenience of the granular form of the composition. Moreover, these granules are easy to extrude thanks to the relatively low viscosity of the paste / slurry, not sticky, and display high attrition resistance making them resistant to abrasion and less prone to dusting when handled and shipped.

[0200] Example 2 - Preparation of WPG with a water-soluble aprotic solvent

[0201] Water dispersible granules are prepared using the same protocol as comparative example 1, except that a water-soluble aprotic solvent, namely methyl-5-(dimethylamino)-2- methyl-5-oxopentanoate (Rhodiasolv® Polarclean - commercialized by Solvay), is used as a solvent in addition to water.

[0202] The ingredients and results are summarized in Table 3 below, wherein the composition of comparative example 1 is shown on the left column for convenience.

[0203] Table 3

[0204] In composition 3, the ratio water / Rhodiasolv® Polarclean is 80 / 20 by weight.

[0205] The disintegration value 7 of composition 3 is well below 30 and its suspensibility value is far above 70.

[0206] The addition of Rhodiasolv® Polarclean to water strongly increases the suspensibility, and does not impact negatively the ease of disintegration, thereby making the composition more convenient because more readily usable by the end user.

[0207] Therefore, the use of Rhodiasolv® Polarclean with water allows to achieve great properties of both disintegration (rapid disintegration) and suspensibility, while taking advantage of the convenience of the granular form of the composition. Moreover, these granules are easy to extrude thanks to the relatively low viscosity of the paste / slurry, not sticky, and present high attrition resistance making them resistant to abrasion and less prone to dusting when being handled and shipped.

[0208] Example 3 - Influence of the dispersing agent

[0209] Two other compositions are prepared using the same protocol as example 1, except that the concentration of the dispersing agent Supragil® MNS / 90 is increased.

[0210] The ingredients and results are summarized in Table 4 below.

[0211] Table 4

[0212] The suppression of Sodium Dodecyl benzene sulfonate and optimization of the concentration of Supragil® MNS / 90 from 8 to 12 increases the suspensibility to above 80,||with a satisfying disintegration performance below 30 inversions.

[0213] Both compositions 4 and 5 are easy to extrude thanks to the relatively low viscosity of the paste / slurry, and the granules are not sticky and present high attrition resistance making them resistant to abrasion and less prone to dusting when being handled and shipped.

[0214] The disintegration and suspensibility values of the granules of compositions 4 and 5 make them excellent fungicidal and / or bactericidal agrochemical composition, with high convenience and good bioavailability of the copper salt particles, related to the homogeneous suspension obtained after dilution in water.

[0215] Example 4 - Tribasic Copper Sulfate WPG

[0216] Water dispersible granules are prepared using the same protocol as example 1, except that the copper salt, Copper oxychloride, is replaced with Tribasic Copper Sulfate, the dispersing agent is Geropon® T36, which is a sodium polycarboxylate dispersing agent commercialized by Solvay, and the wetting agent is Supragil® WP which is a diisopropyl naphthalene sulfonate wetting agent commercialized by Solvay.

[0217] The ingredients and results are summarized in Table 5 below.

[0218] Table 5

[0219] The disintegration performance of composition 6 is 15 and its suspensibility is 79, far above 70.

[0220] Moreover, composition 6 is easy to extrude thanks to the relatively low viscosity of the paste / slurry, and the granules are not sticky and present high attrition resistance making them resistant to abrasion and less prone to dusting when being handled and shipped.

[0221] Hence, Supragil® WP (an alkyl naphthalene sulfonate surfactant - commercialized by Solvay) is a suitable wetting agent in the fungicidal and / or bactericidal agrochemical composition of the invention.

[0222] Example 5 - Rainfastness performance

[0223] Tests to evaluate rainfastness performance are carried out on magnolia leaves. The protocol is detailed below.

[0224] According to the present invention, the term “rainfastness” (or “waterfastness”) refers to the ability of a substance to withstand being washed off by precipitation, condensation, guttation or irrigation As used herein, the term “increased rainfastness”, “enhanced rainfastness” or “improved rainfastness” are equivalent and all refer to an increase in rainfastness. Any standard methods known in the art, including but not limited to those disclosed in the Examples, can be used to measure rainfastness. The guar gum of the invention may be used as a rainfastness agent for a beneficial active, that is to say an ingredient which is capable of enhancing the rainfastness of said active, preferably when applied together with said beneficial active.

[0225] Assessing rainfastness inherently requires that the formulation being examined is in the form of a dry deposit on a surface. Magnolia plants were used as the surface.

[0226] Rainfastness Lab-scale method: The WDG are diluted at 4% (by weight) in water. Droplets of this solution (0.2 mL of) of a treatment were placed onto a leaf and allowed to dry. The dried spray solution was clearly visible for the naked eye due to the content of copper in the spray solution (blue spot). Then leaves were washed using a burette with 4 mL of deionized water in 9 seconds. The resulting eluent was collected into a bottle below the device. 3 washes were done. Rainfastness may be assessed by visually comparing the deposit of a droplet of the diluted WDG containing or not any polysaccharide after a simulated rain. Rainfastness may also be assessed by comparing the transmittance (with a spectrophotometer at 600 nm) of the water collected after each wash step.

[0227] The results of rainfastness may be assessed visually based on Figure 1.

[0228] On this Figure, the left column I represents leaves of magnolia initially treated(A) with a composition comprising a copper salt with no guar. The right column II representsleaves of magnolia initially treated (A) with a composition comprising a copper salt and a guar gum, and refers to the composition 2 of the invention.

[0229] After a first washing, we can see that the composition of column I without guar gum is completely washed away (I - B), whereas the composition of column II with guar gum seems untouched (II - B).

[0230] A second and a third washing were performed, but do not seem to remove the composition of column II (II - C and D).

[0231] Therefore, the guar gum imparts a high rainfastness to the copper salt, the latter being thus able to withstand being washed off by precipitation, condensation, guttation or irrigation.

[0232] Transmittance tests are then carried out on the samples after the first, the second, and the third washing steps.

[0233] The results are summarized in Table 6, which corresponds to the left column I of Figure 1, and Table 7, which corresponds to the right column II of Figure 1.

[0234] Table 6Table 7

[0235] According to Table 6, transmittance values could be recorded only after the first washing, where only a small fraction of the diluted composition remained on the leaves.

[0236] On the contrary, according to Table 7, transmittance values could be recorded after all of the three washing steps, with a mean value of nearly 100%, thereby showing that all the copper from the applied diluted composition remained on the leaves.

[0237] The strong rainfastness properties imparted to the copper salt by the guar gum (polysaccharide) is the reason why the latter is part of the fungicidal and / or bactericidal agrochemical composition of the invention.

Claims

CLAIMS1. Composition in the form of one or more water dispersible granule(s), comprising: a) at least one copper salt and / or sulfur compound, b) at least one polysaccharide, c) at least one water-soluble solvent, d) at least one surfactant, e) at least one carrier.

2. Composition according to claim 1, wherein the at least one copper salt comprises copper oxychloride and / or copper hydroxide and / or tribasic copper sulfate.

3. Composition according to claim 1 or claim 2, wherein the at least one copper salt and / or sulfur compound is present in an amount of 5% to 90% by weight, preferentially of 10% to 85% by weight, preferably of 20% to 80% by weight, preferably of 35% to 80% by weight, more preferably of 45% to 80% by weight, relative to the total weight of the composition.

4. Composition according to any of the preceding claims, wherein the at least one polysaccharide comprises a galactomannan.

5. Composition according to any of the preceding claims, wherein the at least one polysaccharide is present in an amount of 0.5% to 10% by weight, preferably 1% to 10% by weight, preferably of 1% to 8% by weight, and more preferably of 1% to 4% by weight, relative to the total weight of the composition.

6. Composition according to any of the preceding claims, wherein the at least one water-soluble solvent is selected in the group consisting of: N-alkyl pyrrolidones, dimethyl sulfoxide, dihydric alcohols, triethylene glycol, alkyl lactate, polyethylene glycols, polypropylene glycols, esteramides, and dioxolane derivatives.

7. Composition according to claim 6, wherein the at least one water-soluble solvent comprises a dihydric alcohol being a propylene glycol and / or an esteramide being methyl-5- (dimethylamino)-2-methyl-5-oxopentanoate.

8. Composition according to any of the preceding claims, wherein the at least one surfactant comprises at least one wetting agent and / or at least one dispersing agent.

9. Composition according to any of the preceding claims, wherein the at least one surfactant is present in an amount of 2% to 25% by weight, preferably of 3% to 20% by weight, even more preferably of 10% to 20% by weight, relative to the total weight of the composition.

10. Composition according to claim 8, wherein the at least one wetting agent comprises a mixture of:- at least one sulfosuccinate surfactant,- at least one C16-C22 alkyl sulfate and / or an alkyl ether sulfate containing C16-C22 alkyl.

11. Composition according to claim 10, wherein the at least one sulfosuccinate surfactant is present in an amount of 1% to 50% by weight, relative to the total weight of the wetting agent.

12. Composition according to claim 10, wherein the at least one C16-C22 alkyl sulfate and / or alkyl ether sulfate containing C16-C22 alkyl is present in an amount of 1% to 90% by weight, relative to the total weight of the wetting agent.

13. Composition according to claim 8, wherein the at least one wetting agent is a sodium salt of alkyl or dialkyl naphthalene sulfonate.

14. Composition according to claim 8, wherein the at least one dispersing agent comprises at least one sodium salt of naphthalene sulfonate-formaldehyde condensate, optionally alkylsubstituted, and / or a salt of alkylbenzene sulfonate.

15. Composition according to claim 8, wherein the at least one dispersing agent comprises a sodium polycarboxylate dispersing agent.

16. Composition according to any of the preceding claims, wherein the at least one carrier is chosen from the ground natural minerals, preferably kaolins, clays, talc, or chalk, or from the ground synthetic materials, preferably highly-dispersed silica and silicates.

17. Process for the manufacture of a composition in the form of one or more water dispersible granule(s) according to any of claims 1 to 16, said process comprising the following steps:- mixing a) at least one copper salt and / or sulfur compound, b) at least one polysaccharide, d) at least one surfactant, e) at least one carrier, to obtain a mixture,- grinding the mixture to obtain a powder,- adding water and c) at least one water-soluble solvent to the powder to obtain a wet dough,- granulating the wet dough to obtain one or more granule(s),- drying the granules, wherein the a) at least one copper salt and / or sulfur compound, b) at least one polysaccharide, c) at least one water-soluble solvent, d) at least one surfactant, and e) at least one carrier are as defined in any of claims 1 to 16.

18. Process according to claim 17, wherein the granulating step is carried out by extrusion.

19. Use of a composition according to any of claims 1 to 16 to treat an agricultural target, notably parts of a plant and / or soil, against phytopathogenic fungi and / or bacteria.

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