Agrochemical compositions in the form of water-dispersible granules

Abstract

The present invention relates to a composition in the form of one or more 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.

Description

Technical Field

[0001] The present invention relates to compositions in the form of one or more water-dispersible granules, methods for manufacturing such water-dispersible granules, and the use of said compositions for treating agricultural targets to resist fungi and / or bacteria. Background Technology

[0002] Copper salts have long been used in agriculture to control plant pathogenic fungi and bacteria on crops. To ensure the efficacy of copper treatments on cultures over extended periods, inorganic copper salts that are slightly soluble or insoluble in water, such as copper oxychloride, copper hydroxide, or tribasic copper sulfate (TBCS), are often used. However, the use of copper-based fungicides is limited due to their phytotoxicity to plants and to users at higher concentrations. Furthermore, copper tends to accumulate in soil: high levels of copper in the soil can be toxic to plants and soil microorganisms, leading to reduced biological activity and loss of soil fertility. Therefore, there is a need to improve the fungicidal and / or bactericidal efficacy of copper or copper salts, or to achieve the same level of fungicidal and / or bactericidal activity with reduced amounts of copper or copper salts. The same applies to sulfur compounds.

[0003] Among the various forms of agrochemical compositions used to treat crops, water-dispersible granule (WDG) formulations are highly useful. WDG formulations are solid formulations that typically incorporate the active ingredient into granules. When the granules are added to water in a spray can, they rapidly disperse or dissolve to obtain a fine-particle suspension. These formulations provide systems for delivering solid active ingredients to their targets and allow for the production of highly concentrated formulations that are wettable and readily disintegrate upon contact with water.

[0004] Due to its solid particulate form, WDG formulations offer significant advantages over other known formulations, such as ease of handling, ease of use, reduced worker exposure, reduced toxicity, and thus provide a convenient form for delivering fungicides and bactericides.

[0005] For it to be effective, the granules need to maintain their physical integrity until they are delivered to a carrier liquid (usually water), in which they must rapidly disintegrate into fine particles that remain suspended in the liquid phase in a uniform manner.

[0006] One of the main problems with pest control treatments, especially fungicides and bactericides, is that pest control agents are often easily leached from the treated agricultural targets (including plant parts and soil). When applied to plant parts (such as leaves), they can suffer runoff or loss, for example, due to rapid watering, rain, or other water exposure. As another example, pre-emergence agents (i.e., those applied to the soil before the plants or weeds germinate) need to remain in the application site for a period of time. Runoff of pre-emergence agents during the germination period, triggered by water exposure, is clearly undesirable.

[0007] To address this issue, it is known to use polysaccharides, particularly galactomannans such as guar gum or guar derivatives, which are well-known binders and retainers. Polysaccharides like guar gum have been claimed to be highly effective retainers and rain repellents in the presence of certain biofungicides (such as microbial biocide pests), thus providing enhanced bioavailability. For further information, see document WO 2022 / 033874.

[0008] The applicant has found that the use of guar gum in water-dispersible granules (WDG) containing copper salts and / or sulfur compounds to facilitate the good retention of copper salts or sulfur compounds on agricultural targets (such as leaf cuticles) upon application is of particular interest for sufficient rain resistance benefits to enhance biological efficacy.

[0009] However, from a practical standpoint, preparing WDG using guar gum is highly problematic. The hydration of guar gum in water produces a highly viscous paste, which makes the extrusion process extremely difficult and cumbersome.

[0010] Furthermore, when granules containing more than 2 wt% (weight percentage) of guar beans are mixed into the water tank before spray application, their disintegration is very slow, resulting in low suspension rates associated with particle aggregation of guar beans and other ingredients. This leads to several application problems, such as large amounts of wet screen residue and nozzle clogging.

[0011] Therefore, the applicant sought a solution to the problem of balancing good properties (such as retention, especially rain resistance) and bioefficacy with sufficient viscosity of the paste to make it (easily) processable into WDG. Summary of the Invention

[0012] The applicant has discovered that the above-mentioned disadvantages are resolved by the following WDG composition.

[0013] Therefore, the present invention provides a composition in the form of one or more water-dispersible granules, the composition comprising:

[0014] a) At least one copper salt and / or sulfur compound,

[0015] b) At least one polysaccharide,

[0016] c) At least one water-soluble solvent,

[0017] d) At least one surfactant,

[0018] e) At least one carrier.

[0019] The compositions of the present invention exhibit excellent processability, particularly low viscosity, making them suitable for manufacturing granules (especially by extrusion), while having good retention properties (especially rain resistance) and bioavailability when diluted in water and applied to agricultural targets at the intended use rate.

[0020] Furthermore, the corresponding compositions can be efficiently processed, for example, by extrusion, and the compositions exhibit particularly high suspension stability, good suspension rate, high bioavailability of active ingredients, and form only a very small amount of residue in the diluted water when diluted before application.

[0021] In this document, the compositions of the present invention are also referred to as “WDG compositions”, where WDG is an abbreviation for water-dispersible granules or water-dispersible granule formulations.

[0022] The compositions of the present invention are advantageously fungicidal and / or bactericidal agricultural chemical compositions because they are advantageously used to treat agricultural targets to resist plant pathogenic fungi and / or bacteria, and the copper salts and / or sulfur compounds have fungicidal and / or bactericidal effects on said agricultural targets when applied.

[0023] Unbound by any theory, the applicant believes that this advantageous balance was achieved by adding one or more water-soluble solvents.

[0024] The applicant has discovered that adding such a water-soluble solvent c) as a specific solvent or solvent mixture in combination with the above-mentioned components a), b), d) and e) reduces the viscosity of the paste obtained after mixing the components and allows for easy processing of the paste (especially by extrusion) to form granules, while the provided granules have better and faster disintegration in water before use, better particle suspension after disintegration, improved retention properties, rain resistance, and beneficially improved bioefficacy on the final agricultural target.

[0025] In the compositions of the present invention, copper salts and / or sulfur compounds are active ingredients or part of active ingredients, which may be referred to as "active substances," and they impart fungicidal and / or bactericidal activity to the granules, thereby preventing and / or controlling and / or reducing plant pathogenic fungal and / or bacterial infections on agricultural targets such as crop plants or soil.

[0026] Polysaccharides act as efficient retention and rain-resistant agents. By forming a layer around the agricultural target, they facilitate the good retention of copper salts or sulfur compounds on the agricultural target upon application. This layer retains the copper salts and / or sulfur compounds near the agricultural target and / or enhances biological efficacy.

[0027] The combination of surfactants (d), carriers (e), and specific water-soluble solvents (c) with copper salts and / or sulfur compounds and polysaccharides allows for the formation of stable and processable granules while retaining the desirable properties imparted by the copper salts and / or sulfur compounds and polysaccharides.

[0028] As used herein, the term "sulfur compound" refers to any compound containing sulfur. This includes elemental sulfur itself (alone), typically in the form of a yellow powder. In other words, the compositions of the present invention may contain sulfur. The term "elemental sulfur" includes allotropes of elemental sulfur, such as plastic (amorphous) sulfur, monoclinic sulfur, orthorhombic sulfur composed of S8 molecules, and other cyclic molecules such as S7 and S12.

[0029] As used herein, the term "fungicide" is intended to refer to any agent or combination of agents capable of killing fungi and / or preventing and / or inhibiting fungal growth.

[0030] As used herein, the term "bactericide" is intended to refer to any agent or combination of agents capable of killing bacteria and / or inhibiting bacterial growth.

[0031] The term "agricultural target" is intended to cover both plant parts and soil. In one exemplary embodiment, the agricultural target is a plant part.

[0032] As used herein, the term "plant part" should be understood to mean all parts and organs of a plant, both above and below ground, such as stems, leaves, flowers, and roots. Examples that may be mentioned include leaves, needles, culms, stems, flowers, fruit bodies, fruits, seeds, roots, tubers, and rhizomes. Plant parts also include harvested material as well as material for vegetative and reproductive propagation (e.g., cuttings, tubers, rhizomes, offshoots, and seeds).

[0033] In one particular embodiment, the agricultural target is plant seeds.

[0034] In another specific embodiment, the agricultural target is the plant's branches and leaves or leaf cuticle. As used herein, the term "branches and leaves" is intended to mean all parts and organs of a plant above ground. Non-limiting examples include leaves, needles, culms, stems, flowers, fruits, etc.

[0035] In another exemplary embodiment, the agricultural target is soil.

[0036] According to the present invention, the term "rain resistance" (or "water resistance") refers to the ability of a material to withstand being washed away by precipitation, condensate, runoff, or irrigation.

[0037] According to the present invention, the term "precipitation" refers to rainfall, and particularly includes moderate rain (20 mm) and heavier rain (40 mm). In one embodiment, heavy morning dew may also be considered as falling under the term "precipitation".

[0038] As used in this article, the terms “increased rain resistance,” “enhanced rain resistance,” or “improved rain resistance” are equivalent and all refer to an increase in rain resistance.

[0039] Any standard methods known in the art, including but not limited to those disclosed in the examples at the end of this document, can be used to measure rain resistance.

[0040] The polysaccharides, preferably galactomannans, and more preferably guar gum, of the compositions of the present invention are used as rain-resistant agents for active substances, namely copper salts and / or sulfur compounds (fungicides and / or bactericides), i.e., components that enhance the rain resistance of said active substances when applied together in granules.

[0041] Rain resistance can be assessed using several techniques.

[0042] For example, rain resistance can be assessed by comparing the bioefficacy of a given active substance after exposure to water (e.g., simulated rainfall) with the bioefficacy of the active substance without exposure to water (e.g., simulated rainfall) (control) under a limited treatment with the active substance.

[0043] According to another example, rain tolerance can be assessed by visually comparing droplet deposits of WDG dilutions containing or without any polysaccharides (especially guar gum) after simulated rain, or by measuring the dosage of copper or sulfur in the water remaining on the leaves or collected after washing. Inductively coupled plasma (ICP) methods can be used for copper or sulfur dosage determination. Comparisons can also be made using the transmittance of the water collected after each washing step (e.g., at 600 nm using a spectrophotometer).

[0044] The compositions of the present invention may also contain one or a combination of the following features:

[0045] - Component a) of the composition according to the invention is preferably at least one copper salt, for example, a copper salt;

[0046] - At least one copper salt includes copper oxychloride and / or copper hydroxide and / or ternary copper sulfate;

[0047] - At least one copper salt and / or sulfur compound are present in an amount of 5% to 90% by weight, more preferably 10% to 85% by weight, more preferably 20% to 80% by weight, more preferably 35% to 80% by weight, and more preferably 45% to 80% by weight relative to the total weight of the composition;

[0048] - At least one polysaccharide includes galactomannan;

[0049] - 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, and preferably 1% to 4% by weight, relative to the total weight of the composition. More preferably, this amount is 1.5% to 7% by weight, and more preferably 2% to 4% by weight, relative to the total weight of the composition.

[0050] - The at least one water-soluble solvent is selected from the group consisting of: N-alkylpyrrolidone, dimethyl sulfoxide, diol, triethylene glycol, alkyl lactate, polyethylene glycol, polypropylene glycol, ester amide, and dioxolane derivatives.

[0051] - At least one water-soluble solvent comprises at least one diol and / or at least one ester amide. The diol and ester amide solvents can reduce the viscosity of the paste obtained after mixing the components, as well as improve the processability of the paste, and achieve the retention properties, rain resistance, disintegration, post-disintegration suspension rate and bioavailability;

[0052] - At least one water-soluble solvent contains propylene glycol as a diol and / or methyl-5-(dimethylamino)-2-methyl-5-oxovalerate as an ester amide;

[0053] - The at least one surfactant comprises at least one wetting agent and / or at least one dispersant. Advantageously, the surfactant is a mixture of surfactants comprising at least one wetting agent and at least one dispersant;

[0054] - At least one surfactant is present in an amount of 2% to 25% by weight, preferably 3% to 20% by weight, or even more preferably 10% to 20% by weight, relative to the total weight of the composition;

[0055] -The at least one wetting agent comprises a mixture of the following:

[0056] - At least one sulfosuccinate surfactant,

[0057] - At least one C 16 -C 22 Alkyl sulfates and / or containing C 16 -C 22Alkyl alkyl ether sulfates; the applicant has discovered that this specific wetting agent (surfactant) mixture further improves the disintegration properties of formulations while maintaining good processability, retention (especially rain resistance), and bioavailability. In other words, this specific wetting agent mixture reduces the disintegration time of WDG in water before application to agricultural targets and improves the suspension rate of particles generated by WDG disintegration in solution. Rapid disintegration is important for the efficient dispersion of WDG formulations in water and is also an important indicator for evaluating the performance of WDG formulations. It also makes the use of WDG easier and more convenient;

[0058] - 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;

[0059] - at least one C 16 -C 22 Alkyl sulfates and / or containing C 16 -C 22 The alkyl alkyl ether sulfate is present in an amount of 1% to 90% by weight relative to the total weight of the wetting agent;

[0060] - At least one wetting agent is a sodium salt of an alkyl or dialkyl naphthalene sulfonate;

[0061] - At least one wetting agent is present in an amount of 2% to 10% by weight, preferably 3% to 9% by weight, relative to the total weight of the composition;

[0062] - The at least one dispersant comprises a sodium salt of at least one naphthalene sulfonate-formaldehyde condensate—optionally alkyl-substituted—and / or a salt of an alkylbenzene sulfonate. This particular dispersant improves the suspension rate of the granules after dispersion in water (or an aqueous solvent at the time of use), thereby improving the disintegration characteristics of the formulation while maintaining good processability, retention (especially rain resistance), and / or bioefficacy.

[0063] - At least one dispersant comprises sodium polycarboxylate dispersant;

[0064] - At least one of its dispersants is present in an amount of 5% to 15% by weight, preferably 7% to 14% by weight, or even more preferably 8% to 13% by weight, relative to the total weight of the composition;

[0065] - At least one carrier is selected from ground natural minerals, preferably kaolin, clay, talc or chalk; or from ground synthetic materials, preferably highly dispersed silica and silicates;

[0066] The composition may contain one or more other active substances, particularly other fungicides and / or bactericides. According to embodiments, the composition further comprises at least one multi-site contact fungicide. As used herein, the term "multi-site contact fungicide" refers to a contact fungicide that inhibits fungal growth through multiple sites of action and has contact and preventative activity. As used herein, the term "contact fungicide" means a fungicide that remains at the site of application and does not migrate within the plant.

[0067] As used herein, the term "alkyl" or "alkyl group" means a saturated hydrocarbon group that can be straight-chain, branched, or cyclic, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, n-hexyl, and cyclohexyl.

[0068] The present invention also relates to a method for manufacturing compositions as described above in the form of one or more water-dispersible granules.

[0069] The method includes the following steps:

[0070] - Mix a) at least one copper salt and / or sulfur compound, b) at least one polysaccharide, d) at least one surfactant, and e) at least one carrier to obtain a mixture.

[0071] - Grind the mixture to obtain a powder.

[0072] - Add water and c) at least one water-soluble solvent to the powder to obtain a wet mass.

[0073] - Granulate the wet material to obtain one or more granules.

[0074] - Dry the granules.

[0075] Wherein 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 previously defined.

[0076] Preferably, the granulation step is performed by extrusion.

[0077] Other ingredients / auxiliaries may be provided during the mixing step and added to the composition, such as, but not limited to, disintegrants, binders, dispersants, defoamers, thickeners, carriers, antifreeze agents and / or bactericides.

[0078] Another object of the present invention is the use of the compositions disclosed above for treating agricultural targets, particularly plant parts and / or soil, to preferably resist plant pathogenic fungi and / or bacteria.

[0079] The present invention further relates to a method for treating agricultural targets, preferably resistant to fungi and / or bacteria, wherein the composition according to the invention is placed, preferably sprayed, onto such agricultural targets.

[0080] According to this method, the composition according to the invention is advantageously diluted in water to the target utilization rate before application, preferably spraying, onto an agricultural target.

[0081] Agricultural targets can be, for example, plants or plant parts or soil. Attached Figure Description

[0082] Figure 1 Photographs show magnolia leaves covered with copper salts containing or without guar gum during rain resistance assessment tests. Detailed Implementation

[0083] The composition of the present invention

[0084] This invention relates to a composition, advantageously to a fungicidal and / or bactericidal agricultural chemical composition, in the form of one or more water-dispersible granules (typically in the form of water-dispersible granules), the composition comprising:

[0085] a) At least one copper salt and / or sulfur compound,

[0086] b) At least one polysaccharide,

[0087] c) At least one water-soluble solvent,

[0088] d) At least one surfactant,

[0089] e) At least one carrier.

[0090] The applicant has unexpectedly discovered that this WDG composition solves the processability problems typically encountered when wetting guar beans, resulting in a composition with low viscosity that is perfectly suited for the preparation of granules (especially by extrusion), while exhibiting excellent retention properties (particularly rain resistance) and / or bioefficacy.

[0091] Copper salts and / or sulfur compounds (a)

[0092] Copper salts and sulfur compounds a) are active ingredients or part of active ingredients and may be referred to as “active substances”. Active substances impart fungicidal and / or bactericidal activity to granules and allow for the prevention, control, and / or reduction of plant pathogenic fungal and bacterial infections on crop plants.

[0093] The compositions of the present invention may contain only copper salts, or sulfur compounds, or a combination of both copper salts and sulfur compounds.

[0094] Copper salts include monovalent or preferably divalent copper salts of inorganic and organic acids, such as copper oxychloride, copper octanoate, ammonium copper carbonate, copper arsenate, copper oxysulfate, copper formate, copper propionate, copper oxyacetate, copper citrate, copper chloride, diammonium chloride, copper nitrate, copper carbonate, basic copper carbonate, copper pyrophosphate, copper phosphate, disodium copper ethylenediaminetetraacetate, diammonium ethylenediaminetetraacetate, copper oxalate, copper tartrate, copper gluconate, copper glycine, copper glutamate, copper aspartate, etc. Copper gluconate, copper adipic acid, copper palmitate, copper stearate, copper octanoate, copper decanoate, copper undecanoate, copper neodecanoate, copper linoleate, copper oleate, copper borate, copper methanesulfonate, copper aminosulfonate, copper acetate, copper hydroxide, copper oxide, copper oxychloride, copper sulfate, basic copper sulfate, ternary copper sulfate (TBCS), quinoline copper, bis(3-phenylsalicylic acid) copper, dihydrazine disulfate, basic copper chloride, dimethyl dithiocarbamate, copper trichloride.

[0095] Other suitable copper compounds are mixed salts with ammonium, alkali metals, and alkaline earth metals. Examples are copper(II)ammonium sulfate, copper(II)magnesium sulfate, copper naphthenate, 8-hydroxyquinoline copper, and copper(II)potassium sulfate. Preferred compounds include copper oxychloride, copper octoate, copper ammonium carbonate, copper arsenate, copper(II) arsenite acetate, copper oxysulfate, copper formate, copper propionate, copper oxyacetate, copper citrate, copper carbonate, copper chloride, diammonium chloride, copper nitrate, copper carbonate, basic copper carbonate, copper pyrophosphate, copper phosphate, disodium copper ethylenediaminetetraacetate, diammonium ethylenediaminetetraacetate and copper acetate, copper hydroxide, copper oxide, copper oxychloride, copper sulfate, basic copper sulfate, quinoline copper, and bis(3-phenylsalicylic acid)copper. The preferred materials include copper dihydrazine disulfate, basic copper chloride, copper naphthenate, 8-hydroxyquinoline copper, and copper trichloride dimethyl dithiocarbamate, particularly copper acetate, copper carbonate, copper oxychloride, copper hydroxide, copper oxychloride, copper sulfate, basic copper sulfate, quinoline copper, bis(3-phenylsalicylic acid) copper, copper dihydrazine disulfate, basic copper chloride, copper octoate, ammonium copper carbonate, copper arsenate, copper oxysulfate, copper naphthenate, 8-hydroxyquinoline copper, and copper trichloride dimethyl dithiocarbamate.

[0096] According to the embodiments, the copper-based fungicide is selected from the group consisting of: copper acetate, copper chloride, copper chlorate, copper formate, copper hexafluorosilicate, copper nitrate, copper chromate, copper sulfate pentahydrate, Bordeaux mixture, copper hydroxide, cuprous oxide, copper oxychloride, copper oxychloride (COCS), ternary copper sulfate (such as copper sulfate, copper trihydride, hemihydrate), and any combination thereof.

[0097] The preferred copper salts are those that are largely insoluble in water, such as copper oxychloride, copper hydroxide, or ternary copper sulfate.

[0098] Sulfur compounds specifically include the element sulfur itself, i.e., elemental sulfur, which is typically in powder form.

[0099] Preferably, 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, more preferably 20% to 80% by weight, more preferably 35% to 80% by weight, and even more preferably 45% to 80% by weight relative to the total weight of the composition.

[0100] In one embodiment, 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.

[0101] The application rate of the composition according to the invention will depend on the specific type of fungus and / or bacteria to be controlled, the required level of control, and the duration and method of treatment. Typically, the composition of the invention can be applied at a rate ranging from about 25 g / ha to about 5000 g / ha of total active ingredient.

[0102] In one embodiment, the composition of the present invention is preferably applied at a ratio of 100-2000 g / ha of metallic copper, more preferably at a ratio of 250-1500 g / ha of metallic copper, and even more preferably at a ratio of 500-1000 g / ha of metallic copper. In some embodiments, the composition of the present invention is preferably applied at a ratio of 250 to 750 g / ha of metallic copper.

[0103] Before use, before bringing the plant, plant parts or soil into contact with the composition according to the invention, the composition is preferably diluted 2-5000 times with an aqueous solvent (preferably water) to contain a copper salt between 0.0001% and 10% (w / v).

[0104] The compositions of the present invention may further comprise other bioactive ingredients, such as pesticides, growth regulators, repellents, safeners, biostimulants, micronutrients or macronutrients, and / or fertilizers. Nutrients refer to chemical elements and compounds desired or necessary for promoting or improving plant growth. The term "biostimulant" is preferably intended to mean compounds that can enhance metabolic or physiological processes such as respiration, photosynthesis, nucleic acid uptake, ion uptake, nutrient delivery, or combinations thereof.

[0105] For example, these bioactive ingredients can be selected as fungicides, insecticides, acaricides, algaecides, molluscicides, miticides, nematicides, bactericides, biocides, herbicides, and rodenticides.

[0106] In specific embodiments, these bioactive ingredients can be selected from fungicides, particularly fungicides selected from succinate dehydrogenase inhibitors (SDHI), triazole fungicides, dicarboxamide fungicides, phenylpyrrole (PP) fungicides, phenylacetamide fungicides, benzophenone fungicides, pyrimidine fungicides, and pyridinecarboxamide fungicides.

[0107] In specific embodiments, these active substances may be selected from multi-site contact fungicides.

[0108] Preferably, these active substances can be selected from multi-site contact fungicides, specifically dithiocarbamate fungicides, phthalimide fungicides, chlorinated nitrile fungicides, sulfonamide fungicides, guanidine fungicides, triazine fungicides, and quinone fungicides.

[0109] Multi-site contact fungicides inhibit fungal growth through multiple sites of action and possess both contact and preventative activity. As used herein, the term "contact fungicide" refers to a fungicide that remains at the site of application but does not migrate within the plant. Such contact fungicides are convenient because they offer better retention of the fungicide on the agricultural target and satisfactory bioefficacy.

[0110] Even more preferably, the additional bioactive ingredient may be selected from fluazinam, captan, thiophanate-methyl, or dithiazoline, which are multi-site contact fungicides.

[0111] When other bioactive ingredients are present in the composition, they may be included in a dose of 0.5% to 60% by weight, preferably 1% to 40% by weight, based on the total weight of the active substances.

[0112] Polysaccharide (b)

[0113] The polysaccharide preferably includes galactomannan.

[0114] Galactomannan is a polysaccharide composed of a mannose backbone and galactose side groups (more specifically, a β-D-pyranomannan backbone linked by (1-4) wherein α-D-galactose is linked from its 6-position branch point).

[0115] Naturally occurring galactomannans can be obtained from many sources, including guar gum, guar split, locust bean gum, cassia gum, fenugreek gum, and tara gum. In addition, galactomannans can also be obtained through classical synthetic routes or through chemical modification of naturally occurring galactomannans.

[0116] Preferably, at least one polysaccharide is present in an amount of 0.5% to 10% by weight, more preferably 1% to 10% by weight, more preferably 1.5% to 8% by weight, and more preferably 2% to 4% by weight relative to the total weight of the composition.

[0117] Preferably, the galactomannan contains at least one type of guar gum.

[0118] When the galactomannan contains at least one guar gum, the at least one guar gum is preferably present in an amount of 0.5% to 10% by weight, more preferably 1% to 10% by weight, more preferably 1.5% to 8% by weight, and more preferably 2% to 4% by weight relative to the total weight of the composition.

[0119] Guar gum can be a guar gum derivative, which can be either derivatized or non-derivatized.

[0120] In this application, "guar bean" refers to the plant guar bean (Cyanopsis tetragonoloba). Guar bean gum (Cyamopsis tetragonoloba) is defined as follows.

[0121] In this application, "guar bean seed" refers to the seed derived from the guar bean. A guar bean seed comprises a shell (which is more or less fibrous), a germ, and two "guar bean plates" or "endosperm halves" that constitute the guar bean's endosperm. The plates (or endosperm) are rich in galactomannan. A guar bean seed typically consists of 35% to 40% by weight endosperm, 42% to 47% by weight germ, and 14% to 17% by weight shell.

[0122] In this application, "guar bean powder" or "guar bean powder" refers to powder derived from guar bean endosperm.

[0123] In this application, "natural guar bean" refers to a macromolecular chain of galactomannan type derived from guar bean endosperm that has not been chemically modified by grafting chemical groups. Natural guar beans contain macromolecules with a backbone containing D-mannopyranose units linked at the β(1-4) positions, which are replaced by D-galactopyranose units at the β(1-6) positions. The mannose / galactose ratio of natural guar beans is approximately 2.

[0124] In this application, "guar gum" (also known as "guar bean gum") refers to a product consisting essentially of natural guar beans (in the form of guar bean flakes, or guar bean powder or powder). More specifically, "guar gum" refers to the mucilage found in the seeds of the guar bean, a legume. The water-soluble portion (85%) is referred to as "guar sugar," which consists of a straight chain of (1,4)-β-D-mannopyranosyl units and -D-galactopyranosyl units attached by (1,6) bonds. The ratio of D-galactose to D-mannose in the guar sugar is approximately 1:2. Guar gum typically has a weight-average molecular weight between 2,000,000 and 5,000,000 g / mol. Guar beans with reduced molecular weights, such as from about 50,000 to about 2,000,000 g / mol, are also known.

[0125] In one embodiment, a natural (i.e., non-derivative) polysaccharide gum, such as natural guar gum, cassia gum, or tamarind seed gum, is a suitable guar gum according to the invention.

[0126] As used herein, the “average molecular weight” of guar gum refers to the weight-average molecular weight of the guar gum.

[0127] According to any embodiment of the invention, guar gum may have an average molecular weight (Mw) 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) between 100,000 Daltons and 4,500,000 Daltons, for example between 500,000 Daltons and 4,000,000 Daltons, for example between 1,000,000 Daltons and 3,500,000 Daltons, for example between 2,000,000 and 3,500,000 Daltons.

[0128] In another embodiment, guar gum may have an average molecular weight (Mw) between about 100,000 Daltons and 2,000,000 Daltons, for example between about 300,000 Daltons and 1,800,000 Daltons, for example between about 350,000 Daltons and 1,700,000 Daltons, for example between about 400,000 and 1,500,000 Daltons.

[0129] The average molecular weight of guar gum can be measured using GPC (gel permeation chromatography). For example, it can be measured using a Shodex OH Pak column and an Agilent refractive index detector.

[0130] Guar gum can be cross-linked or non-cross-linked.

[0131] According to any of the embodiments of the present invention, guar gum is not cross-linked.

[0132] According to any of the embodiments of the invention, guar gum can be crosslinked. Guar gum can be treated, for example, with a crosslinking agent. Borax (sodium tetraborate) is commonly used as a processing aid in the reaction steps of the water-guar flake process to partially crosslink the surface of the guar flakes, and thereby reduce the amount of water absorbed by the guar flakes during processing. Other crosslinking agents, such as glyoxal, or metals such as titanium, zirconium, or aluminum, are also widely used.

[0133] Methods for manufacturing derivatives of guar gum are generally known. Typically, guar gum is reacted with one or more derivatizing agents under appropriate reaction conditions to produce guar gum polysaccharides with desired substituents.

[0134] Other galactomannans of interest are modified galactomannans, including derivatized guar polymers such as carboxymethyl guar, carboxymethyl hydroxypropyl guar, cationic hydroxypropyl guar, hydroxyalkyl guar including hydroxyethyl guar, hydroxypropyl guar, hydroxybutyl guar and higher hydroxyalkyl guar, carboxyl guar including carboxymethyl guar, carboxypropyl guar, carboxybutyl guar and higher carboxylalkyl guar, hydroxyethylated, hydroxypropylated and carboxymethylated derivatives of guar sugar, hydroxyethylated and carboxymethylated derivatives of carrubin, and hydroxypropylated and carboxymethylated derivatives of cassia gum.

[0135] In one embodiment, the polysaccharide content, particularly guar bean, is between 0.01% and 0.16% by weight in the final dilution, preferably between 0.03% and 0.08% by weight, and even more preferably between 0.04% and 0.07% by weight in the final dilution to be applied to the agricultural target.

[0136] Water-soluble solvents (c)

[0137] The compositions of the present invention contain at least one water-soluble solvent.

[0138] Adding one or more water-soluble solvents reduces the viscosity of the paste obtained after mixing the ingredients and allows for easy processing (especially extrusion) of the paste to form granules. At the same time, the granules provided in combination with other ingredients have good disintegration in water or aqueous solutions before use, good particle suspension after disintegration, and achieve good bioavailability as well as good retention and rain resistance.

[0139] Therefore, adding one or more water-soluble solvents solves the processability problem while maintaining and even improving the efficacy and convenience of granules.

[0140] According to the present invention, a "water-soluble solvent" is a solvent having a water solubility of advantageously equal to or greater than 300 g / L (grams of solvent per liter of water) at 25°C and atmospheric pressure (i.e., 1.013 x 10^5 Pa), more preferably greater than 600 g / L, and even more preferably a solvent that can be completely mixed in water in all proportions to form a homogeneous and transparent solution.

[0141] The water-soluble solvent is preferably selected from the group consisting of: N-alkylpyrrolidone (e.g., N-butylpyrrolidone), dimethyl sulfoxide, diol (e.g., propylene glycol), triethylene glycol, glycerol, alkyl lactate (e.g., ethyl lactate), tetrahydrofurfuryl alcohol, γ-butyrolactone, alkyl carbonate, alkylene carbonate, polyethylene glycol, alkyl glycol ethers (e.g., ethylene glycol monopropyl ether or ethylene glycol n-butyl ether), alkyl carbonate, alkylene carbonate, alkyl polyethylene glycol ethers (e.g., polyethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol n-butyl ether), polypropylene glycol (e.g., dipropylene glycol) and polypropylene glycol alkyl ethers (e.g., dipropylene glycol dimethyl ether), esteramides such as methyl-5-(dimethylamino)-2-methyl-5-oxopentanoate, dioxolane derivatives such as 2,2-dimethyl-4-hydroxymethyl-1,3-dioxolane, and N,N-dimethyllactic acid amide.

[0142] More preferably, the water-soluble solvent is selected from the group consisting of: N-alkylpyrrolidone (e.g., N-butylpyrrolidone), dimethyl sulfoxide, diol (e.g., propylene glycol), triethylene glycol, alkyl lactate (e.g., ethyl lactate), polyethylene glycol, polypropylene glycol (e.g., dipropylene glycol), ester amides such as methyl-5-(dimethylamino)-2-methyl-5-oxovalerate, dioxolane derivatives such as 2,2-dimethyl-4-hydroxymethyl-1,3-dioxolane, and N,N-dimethyllactic acid amide.

[0143] Even more preferably, the water-soluble solvent is selected from the group consisting of: dimethyl sulfoxide, propylene glycol, N-butylpyrrolidone, ethyl lactate, polyethylene glycol 400 or 600, and methyl-5-(dimethylamino)-2-methyl-5-oxovalerate.

[0144] Even more preferably, the water-soluble solvent is preferably selected from propylene glycol and methyl-5-(dimethylamino)-2-methyl-5-oxovalerate.

[0145] Preferably, the water-soluble solvent comprises at least one diol and / or at least one ester amide.

[0146] Diols and esteramide solvents are one or more specific water-soluble solvents that result in very good and unexpected results and properties, especially regarding the processability of pastes as well as retention and rain resistance.

[0147] Esteramides may be selected from the group including: methyl-5-(dimethylamino)-2-methyl-5-oxovalerate, which is commercialized by Solvay under the name Rhodiasolv® PolarClean.

[0148] Preferably, the solvent added to address the processability problem is present in an amount of 3% to 15% by weight, preferably 4% to 10% by weight, relative to the total weight of the composition.

[0149] Surfactant (d)

[0150] The compositions of the present invention further comprise d) at least one surfactant. This means that at least one surfactant may be, for example, a mixture of surfactants.

[0151] At least one surfactant comprises at least one wetting agent and / or at least one dispersant.

[0152] Preferably, the composition comprises at least one wetting agent and a dispersant.

[0153] Suitable surfactants can be selected from the following group: alkyl ether carboxylates; sodium salts of fatty acids; acyl glutamate salts; sarcosine salts; alkyl sulfosuccinates such as dioctyl sulfosuccinate, taurines such as methyl oleoyl taurine; alkyl phosphates, such as alkyl monophosphates and alkyl hypophosphite, alkoxylated phosphates; alkyl sulfates, alkyl ether sulfates; alkylbenzene sulfonic acids, such as phenol sulfonic acids, naphthalene sulfonic acids and dibutyl naphthalene sulfonic acids, or dodecylbenzene sulfonates, alkyl naphthalene sulfonates, alkyl methyl ester sulfonates, or mono- or dialkyl succinate sulfonates, lignin sulfonates, sodium salts of naphthalene sulfonates that may optionally be alkyl-substituted – formaldehyde condensates: Geropon® L Wet Max (wetting agent – ​​manufactured by Solvay), Supragil® WP (wetting agent – ​​manufactured by Solvay), Supragil® MNS 90, Supragil MNS88-E (dispersant surfactant – (Manufactured by Solvay); sugar surfactants, especially sorbitol esters, such as sorbitol fatty acid esters (sorbitol monooleate, sorbitol tristearate), and esters of monools or polyols, such as alkyl (poly)glycosides and N-alkyl glucosamides.

[0154] Other suitable surfactants include sulfosuccinates (e.g., dioctyl sulfosuccinate); polyoxyethylene / propylene oxide; alkoxylated tristyrene phenol, such as ethoxylated tristyrene phenol or ethoxylated propoxylated tristyrene phenol; alkoxylated tristyrene phenol sulfate, such as ethoxylated tristyrene phenol sulfate; alkoxylated tristyrene phenol phosphate, such as ethoxylated tristyrene phenol phosphate; alkoxylated alcohols, such as ethoxylated alcohols or ethoxylated propoxylated alcohols; alkyl sulfonates and alkyl aryl sulfonates; alkylbenzene sulfonic acids, such as phenol sulfonic acid, naphthalene sulfonic acid and dibutylnaphthalene sulfonic acid; or dodecylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl methyl ester sulfonates; or mono- or dialkyl succinate sulfonates.

[0155] Suitable surfactants also include polycarboxylates, such as those hydrophobically modified comb polymers, such as polyacrylic acid, polymethacrylic acid, polymaleic acid, polymaleic anhydride, copolymers of maleic acid or maleic anhydride with olefins (such as isobutylene or diisobutylene), copolymers of acrylic acid and itaconic acid, copolymers of methacrylic acid and itaconic acid, copolymers of maleic acid or maleic anhydride and styrene, copolymers of acrylic acid and methacrylic acid, copolymers of acrylic acid and methyl acrylate, copolymers of acrylic acid and vinyl acetate, copolymers of styrene and methacrylic acid, modified copolymers of styrene and methacrylic acid, copolymers of maleic acid or maleic anhydride and acrylic acid, polymethyl methacrylate-polyethylene glycol graft copolymers, and N-methyl fatty acids (e.g., C8-C4). 18 )-sarcosine salts, carboxylic acids such as resin acids or fatty acids (e.g., C8-C) 18 The copolymers described above may also be in the form of their salts, such as alkali metal salts (preferably Li, Na, K), alkaline earth metal salts (preferably Ca, Mg), ammonium, or various amines.

[0156] Preferably, at least one wetting agent is present in an amount of 2% to 10% by weight, preferably 3% to 9% by weight, relative to the total weight of the composition.

[0157] Preferably, the wetting agent comprises a mixture of the following:

[0158] - At least one sulfosuccinate surfactant,

[0159] - At least one C 16 -C 22 Alkyl sulfates and / or containing C 16 -C 22 Alkyl ether sulfates.

[0160] Sulfosuccinate surfactants (also known as sulfosuccinate-based surfactants) are agriculturally acceptable salts of sulfosuccinate monoesters, sulfosuccinate diesters, or mixtures thereof, each optionally alkoxylated.

[0161] For example, sulfosuccinate surfactants can be sodium salts of alkyl sulfosuccinates.

[0162] Preferably, the sulfosuccinate surfactant is prepared according to general formula (I):

[0163]

[0164] Where R1 and R2 are the same or different, are:

[0165]

[0166] Where R3 is H, C1-C4 alkyl, alkenyl, hydroxyalkyl, or hydroxyalkenyl;

[0167] R4 is C1-C 22 Alkyl, alkenyl, hydroxyalkyl, or hydroxyalkenyl;

[0168] n is 0 or an integer from 1 to 100;

[0169] X + It is H or a cation.

[0170] Preferably, in general formula (I), R1 and R2, whether the same or different, are:

[0171]

[0172] R4 is C1-C 22 Alkyl, alkenyl, hydroxyalkyl, or hydroxyalkenyl;

[0173] X + It is H or a cation.

[0174] Preferably, C 16 -C 22 Alkyl sulfates are defined according to general formula (II):

[0175] (Formula (II))

[0176] Where R5 is the C of a straight chain or a branched chain. 16 -C 22 Alkyl or hydroxyalkyl;

[0177] M + It is a cation.

[0178] Preferably, it contains C 16 -C22 Alkyl ether sulfates are represented by general formula (III):

[0179] (Formula (III))

[0180] Where R6 is the C of a straight chain or a branched chain. 16 -C 22 Alkyl or hydroxyalkyl;

[0181] AO is ethyleneoxy (EP), propyleneoxy (PO), or a mixture thereof;

[0182] n represents the degree of alkoxylation and is an integer from 1 to 100;

[0183] M + It is a cation.

[0184] According to embodiments, the compositions of the present invention further comprise C1-C 14 Alkyl sulfates or those containing C1-C 14 Alkyl alkyl ether sulfates. Preferably, according to this embodiment, at least one C 16 -C 22 Alkyl sulfates and / or containing C 16 -C 22 Alkyl alkyl ether sulfates are the latter and C1-C 14 Alkyl sulfates or those containing C1-C 14 At least 5 wt% of the total weight of alkyl ether sulfates.

[0185] Preferably, the sulfosuccinate surfactant is present in an amount of 1% to 50% by weight based on the total weight of the wetting agent (d).

[0186] Preferably, C 16 -C 22 Alkyl sulfates and / or containing C 16 -C 22 The alkyl ether sulfate is present in an amount of 1% to 90% by weight relative to the total weight of the wetting agent.

[0187] Term C 16 -C 22 For hydrocarbon chains having between 16 and 22 carbon atoms, the lower limit of 16 and the upper limit of 22 are included in this range.

[0188] In one embodiment, the wetting surfactant is a salt of alkyl or dialkyl naphthalene sulfonate, such as the sodium salt of diisopropyl naphthalene sulfonate.

[0189] The dispersing agent (also known as "dispersant") is preferably present in an amount of 5% to 15% by weight, more preferably 7% to 14% by weight, and more preferably 8% to 13% by weight relative to the total weight of the composition.

[0190] When the surfactant contains a sulfonate / ester, the sulfonate / ester is preferably an alkylaryl sulfonate or alkylaryl sulfonate, or an alkylaryl sulfonate / ester formaldehyde condensate thereof, more preferably an alkylbenzene sulfonate / ester, an alkylnaphthalene sulfonate / ester, an alkylbenzene sulfonate / ester condensed with formaldehyde, or an alkylnaphthalene sulfonate / ester condensed with formaldehyde, more preferably an alkylbenzene sulfonate / ester condensed with formaldehyde or an alkylnaphthalene sulfonate / ester condensed with formaldehyde. The surfactant may include Supragil® MNS 90 (dispersant surfactant - manufactured by Solvay) or Supragil® MNS 88-E.

[0191] "Alkaryl" is an aryl group that is alkyl-substituted.

[0192] The composition may contain other dispersing agents (dispersants).

[0193] Suitable dispersants, especially polycarboxylate-type dispersants, such as those hydrophobically modified comb polymers, such as polyacrylic acid, polymethacrylic acid, polymaleic acid, polymaleic anhydride, copolymers of maleic acid or maleic anhydride with olefins (such as isobutylene or diisobutylene), copolymers of acrylic acid and itaconic acid, copolymers of methacrylic acid and itaconic acid, copolymers of maleic acid or maleic anhydride with styrene, copolymers of acrylic acid and methacrylic acid, copolymers of acrylic acid and methyl acrylate, copolymers of acrylic acid and vinyl acetate, copolymers of styrene and methacrylic acid, modified copolymers of styrene and methacrylic acid, copolymers of maleic acid or maleic anhydride with acrylic acid, polymethyl methacrylate-polyethylene glycol graft copolymers, N-methyl fatty acids (e.g., C8-C4), etc. 18 )-sarcosine salts, carboxylic acids such as resin acids or fatty acids (e.g., C8-C) 18 The copolymers described above may also be in the form of their salts, such as alkali metal salts (preferably Li, Na, K), alkaline earth metal salts (preferably Ca, Mg), ammonium, or various amines.

[0194] Further preferred are dispersants from the group consisting of: sodium or potassium salts of 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).

[0195] Carrier (e)

[0196] The composition of the present invention further comprises at least one carrier.

[0197] Preferably, the carrier is present in an amount of 1% to 20% by weight relative to the total weight of the composition.

[0198] The composition may comprise various minerals and water-soluble powders that can act as carriers. Examples of mineral powders that can be used in this invention include diatomaceous earth, talc, clay, bentonite, and calcium carbonate. Examples of water-soluble powders that can be used in this invention include sugars, urea, and various types of salts. Sugars include lactose, fructose, and glucose. Salts include alkali metal salts and sodium salts of sulfuric acid, phosphoric acid, hydrochloric acid, nitric acid, or carbonate. These powders may be used alone or in combination in granule formulations.

[0199] Other examples of carriers or fillers are ground natural minerals such as kaolin, clay, talc, and chalk; and ground synthetic materials such as highly dispersed silica and silicates.

[0200] Preferably, the composition contains at least kaolin as a carrier.

[0201] Other ingredients

[0202] The compositions according to the invention may optionally contain additional ingredients (adjuvants) suitable for formulation. These should be understood to refer to, but are not limited to, substances of the following categories.

[0203] Adhesives, dispersants, disintegrants, absorption aids, defoamers, thickeners, carriers, buffers, drift inhibitors, pigments, neutralizers, antifreezes, pH adjusters, stabilizers, anti-caking agents, colorants, UV filters, preservatives, formulation additives, antioxidants, and bactericides.

[0204] Typically, 0.1% to 99% by weight, preferably 0.1% to 40% by weight, of the carrier are present in the composition in the form of granules. Typically, 0.1% to 20% by weight of other excipients are present.

[0205] The importance and corresponding uses of the substances mentioned above depend on the type of formulation intended and the nature of the active ingredient.

[0206] Examples of disintegrants include ammonium sulfate, lactose, maltose, sodium sulfate, ammonium bicarbonate, ammonium phosphate, sodium bicarbonate, magnesium sulfate, bicarbonate, sodium chloride, sodium citrate, kaolin, gypsum, calcium carbonate, sodium dihydrogen carbonate, sodium dihydrogen phosphate, ammonium citrate, sodium acetate bentonite, aluminum chloride, citric acid, succinic acid, or combinations thereof. Granules may optionally contain various minerals and water-soluble powders, which can act as fillers.

[0207] Examples of mineral powders that can be used in this invention include diatomaceous earth, talc, clay, bentonite, and calcium carbonate.

[0208] Examples of water-soluble powders that can be used in this invention include sugars, urea, and various types of salts. Sugars include lactose, fructose, and glucose. Salts include alkali metal salts and sodium salts of sulfuric acid, phosphoric acid, hydrochloric acid, nitric acid, or carbonate. These powders can be used alone or in combination in granule formulations.

[0209] Examples of defoamers include polysiloxane emulsions (such as Silikon® SRE, Wacker, or Rhodorsil® from Solvay), long-chain alcohols, fatty acids, organofluorine compounds, and mixtures thereof.

[0210] Bactericides can be added to stabilize the formulation. Examples of suitable bactericides are Proxel® from Imperial Chemical Industries (ICI), Acticide® RS from Thor Chemie, and Kathon® MK from Lanxess.

[0211] Methods for manufacturing WDG

[0212] The present invention also provides a method for producing one or more water-dispersible granules.

[0213] The method involves the following previously described components: a) an active component comprising copper salts and / or sulfur compounds, b) polysaccharides, c) a water-soluble solvent, d) a surfactant, and e) a carrier, and optionally other components / auxiliaries such as disintegrants, adhesives, dispersants, defoamers, thickeners, carriers, antifreeze agents, and bactericides.

[0214] The method further includes the step of mixing a) a copper salt and / or sulfur compound, b) polysaccharide, d) surfactant, and e) carrier to obtain a mixture (mixing step). These components are advantageously mixed together first because they are in powder form and therefore can be easily and conveniently mixed together.

[0215] The mixture is then preferably ground to obtain a powder.

[0216] Then proceed to the step of forming the previously obtained mixture into water-dispersible granules (WDG) (granule forming / granulation step).

[0217] During the mixing step, the components can be combined with appropriate amounts of water and water-soluble solvents, as determined by those skilled in the art. Consider that the above components can be added in any order. Furthermore, any of the above components can be pre-dissolved in water and water-soluble solvents to aid the mixing step, provided that the final solubility in water is not significantly affected. Optional components can also be added at different points throughout the process of producing the granules.

[0218] In one embodiment, the mixing step can be performed using a wet mill (such as a ball mill). Alternatively, the mixing step can be performed using a plasticizing extruder (such as a kneader). It is also considered that the mixing of the above components can be performed using other types of mixers (such as various blending mixers), as will be understood by those skilled in the art. Depending on the mixing step used, agglomerates or slurries are formed. Agglomerates or slurries can be formed into granules through additional steps described below.

[0219] The step of forming the mixture into granules can be further defined as including granulating the mixture into wet granules and drying the wet granules (drying step) to form water-dispersible granules. Alternatively, the step of forming the mixture into granules may include using a spray dryer or fluidized bed to form granules dried by the granulation process.

[0220] Furthermore, the above-described step of granulating the mixture into wet granules may include radially extruding the mixture into wet granules. Alternatively, the step of granulating the mixture may include disc granulating the mixture into wet granules.

[0221] The drying step of wet granules can be carried out using one or more ovens, air-drying systems, or alternative drying systems, as will be understood by those skilled in the art.

[0222] If a spray dryer is used for the drying step of wet granules, the hot air inlet temperature of the spray dryer is typically set to be below or equal to the melting point of the active ingredient used in the granules.

[0223] Alternatively, the hot air inlet temperature of the spray dryer can be set to a temperature 20°C lower than the melting point of the active component.

[0224] Granules can be sieved to produce granules with a relatively uniform size. In this context, the granules have a particle size ranging from 5 to 100 mesh, or from 10 to 40 mesh.

[0225] According to a preferred embodiment, the method is performed as follows.

[0226] The copper salt or sulfur compound is micronized / ground using a suitable micronizer (micronization step). The micronized material is then post-mixed to obtain a homogeneous powder. In some cases, the copper salt or sulfur compound is micronized in the presence of at least a surfactant and / or a carrier.

[0227] The particle size distribution (d90) of the micronized material is preferably less than 25 micrometers, more preferably less than 20 micrometers, even more preferably less than 15 micrometers, and even more preferably less than 12 micrometers.

[0228] The micronized copper salt or sulfur compound, disintegrant, wetting agent, dispersant, at least one polysaccharide (preferably a guar gum derivative) and carrier are mixed in a mixer in the desired amounts to obtain a pre-blended mixture in the form of a uniform powder (mixing step).

[0229] The water or water-soluble solvent or water-soluble aprotic solvent, or a blend of water and said solvent, is mixed with the previously obtained post-mixture to obtain a homogeneous wet agglomerate (agglomerate preparation step).

[0230] The previously obtained agglomerate is granulated to obtain granules – WDG, preferably by extrusion (granulation step).

[0231] The granules are then dried (drying step). Preferably, drying is carried out at 45°C for 24 hours. Example

[0232] Comparative Example 1 – Preparation of WDG with Water (No Other Solvents)

[0233] Water-dispersible granules are prepared using water, without the addition of other solvents.

[0234] WDG was prepared according to the following procedure.

[0235] Copper oxychloride (57%) was micronized / ground using a suitable micronizer and then mixed to obtain a uniform powder.

[0236] The mixture contains micronized copper oxychloride, Supragil® MNS / 90 (alkyl naphthalene sulfonate dispersant – commercially available from Solvay), sodium dodecylbenzene sulfonate (anionic surfactant), and Argirec kaolin. TM B24 (carrier / disintegrant – commercialized by Imerys), AgRHEA TM SticGuard (a guar gum derivative commercially available from Solvay), composed of sulfosuccinate surfactant and C 16 -C 22 Alkyl sulfate-based blending surfactants (wetting agents) are mixed in a mixer to obtain a pre-blended mixture in the form of a uniform powder.

[0237] Water is mixed with the previously obtained post-mixed mixture to obtain a uniform wet pellet, which is then extruded to obtain WDG.

[0238] The granules were then dried at 45°C for 24 hours.

[0239] The components of the particulate composition and their relative amounts in the composition are summarized in Table 1 below.

[0240] Then, suspension rate and disintegration tests were performed. The results are summarized in Table 1 below.

[0241] The following procedure was performed to evaluate the disintegration properties of WDG. 2.5 g of WDG sample was weighed to prepare a 250 ml dilution in water in a 250 ml graduated cylinder. The graduated cylinder, with the stopper closed, was inverted 180° (a 180° rotation by hand indicates a half-inversion) and returned to its initial position. The entire operation was completed within approximately 2 seconds. The number of inversions required for complete sample dispersion was recorded.

[0242] According to method CIPAC MT 184 (Collaborative International Pesticides Analytical Council), the stability of the suspension formed after the water-dispersible granules described herein are dispersed in water can be determined by measuring the amount of sample that remains suspended after a period of time (i.e., the total suspension). The total suspension of the sample can be determined using the aforementioned CIPAC method 184.

[0243] This method aims to determine the suspension percentage, defined as the percentage of one or more active ingredients that remain suspended after a given time. The method is applicable to formulations that form a suspension after dilution with water, with sample concentrations between 0.1% and 10%. A graduated cylinder containing the suspension is placed in a water bath at 30°C. In this example, the WDG sample concentration was fixed at 1%, and measurements were taken after 30 minutes at 30°C.

[0244]

[0245] Table 1

[0246] When there are fewer than 30 flips, the disintegration performance is considered optimized.

[0247] When the suspension rate is higher than 70%, the suspension rate is considered to be optimized.

[0248] Therefore, based on the results, the disintegration of composition 1 is optimized, while its suspension rate is not optimized.

[0249] In addition, granule composition 1 is sticky and difficult to extrude because the paste exhibits high viscosity.

[0250] Example 1 – Preparation of WDG with Water-Soluble Solvents

[0251] Water-dispersible granules were prepared using the same method as in Comparative Example 1, except that a water-soluble solvent, propylene glycol, was used in addition to water.

[0252] The composition and results are summarized in Table 2 below, in which, for convenience, the composition of Comparative Example 1 is shown in the left column.

[0253]

[0254] Table 2

[0255] In composition 2, the water / propylene glycol ratio is 50 / 50 by weight.

[0256] Composition 2 has a disintegration value between 9 and 12, which is below 30, and a suspension value of 83.1, which is above 70.

[0257] Adding propylene glycol to water significantly improves suspension while only slightly reducing the ease of disintegration (still well below 30 inversions), making the composition more convenient for end users to use.

[0258] Therefore, the use of propylene glycol and water allows for the simultaneous achievement of excellent disintegration and suspension properties, while taking advantage of the convenience of the composition's particulate form. Furthermore, due to the relatively low viscosity of the paste / slurry, these granules are easy to extrude, non-sticky, and exhibit high abrasion resistance, making them wear-resistant and dust-free during handling and transportation.

[0259] Example 2 – Preparation of WDG using water-soluble aprotic solvents

[0260] Water-dispersible granules were prepared using the same method as in Comparative Example 1, except that a water-soluble aprotic solvent, namely methyl-5-(dimethylamino)-2-methyl-5-oxovalerate (Rhodiasolv® Polarclean – commercially available from Solvay), was used as the solvent in addition to water.

[0261] The composition and results are summarized in Table 3 below, in which, for convenience, the composition of Comparative Example 1 is shown in the left column.

[0262]

[0263] Table 3

[0264] In composition 3, the ratio of water to Rhodiasolv® Polarclean is 80 / 20 by weight.

[0265] Composition 3 has a disintegration value of 7, which is much lower than 30, and a suspension value much higher than 70.

[0266] Adding Rhodiasolv® Polarclean to water significantly improves suspension without negatively affecting the ease of disintegration, making the composition more convenient and easier for the end user to use.

[0267] Therefore, the use of Rhodiasolv® Polarclean with water allows for the simultaneous achievement of excellent properties of disintegration (rapid disintegration) and suspension, while taking advantage of the convenience of the composition's particulate form. Furthermore, due to the relatively low viscosity of the paste / slurry, these granules are easy to extrude, non-sticky, and exhibit high abrasion resistance, making them wear-resistant and dust-free during handling and transportation.

[0268] Example 3 – The Effect of Dispersants

[0269] Two other compositions were prepared using the same method as in Example 1, except that the concentration of the dispersant Supragil® MNS / 90 was increased.

[0270] The components and results are summarized in Table 4 below.

[0271]

[0272] Table 4

[0273] The use of sodium dodecylbenzenesulfonate was eliminated, and the concentration of Supragil® MNS / 90 was optimized from 8 to 12, resulting in a suspension rate of over 80%, with satisfactory disintegration performance of less than 30 flips.

[0274] Because of the relatively low viscosity of the paste / slurry, both compositions 4 and 5 are easy to extrude, and the granules are not sticky and exhibit high abrasion resistance, making them wear-resistant and dust-free during handling and transportation.

[0275] The disintegration and suspension ratio values ​​of the granules of compositions 4 and 5 make them excellent fungicidal and / or bactericidal agrochemical compositions with high convenience and good bioavailability of copper salt granules associated with the homogeneous suspension obtained after dilution in water.

[0276] Example 4 – Ternary Copper Sulfate WDG

[0277] Water-dispersible granules were prepared using the same method as in Example 1, except that the copper salt (copper oxychloride) was replaced with ternary copper sulfate, the dispersant was Geropon® T36 (a sodium polycarboxylate dispersant commercially available from Solvay), and the wetting agent was Supragil® WP (a diisopropylnaphthalene sulfonate wetting agent commercially available from Solvay).

[0278] The components and results are summarized in Table 5 below.

[0279]

[0280] Table 5

[0281] Composition 6 has a disintegration performance of 15 and a suspension rate of 79%, which is much higher than 70.

[0282] In addition, due to the relatively low viscosity of the paste / slurry, combination 6 is easy to extrude, and the granules are non-sticky and exhibit high abrasion resistance, making them wear-resistant and dust-free during handling and transportation.

[0283] Therefore, Supragil® WP (alkyl naphthalene sulfonate surfactant – commercially available from Solvay) is a suitable wetting agent in the fungicidal and / or bactericidal agrochemical compositions of the present invention.

[0284] Example 5 – Rain Resistance

[0285] The rain resistance performance was evaluated using magnolia leaves. The procedure is detailed below.

[0286] According to the present invention, the term "rain resistance" (or "water resistance") refers to the ability of a substance to withstand being washed away by precipitation, condensate, runoff, or irrigation. As used herein, the terms "increased rain resistance," "enhanced rain resistance," or "improved rain resistance" are equivalent and all refer to an increase in rain resistance. Any standard methods known in the art (including, but not limited to, those disclosed in the examples) can be used to measure rain resistance. The guar gum of the present invention can be used as a rain-resistant agent for beneficial active substances, i.e., preferably a component that enhances the rain resistance of said active substance when applied together with said beneficial active substance.

[0287] Assessing rain resistance inherently requires the preparation being examined to be in the form of a dry deposit on a surface. Magnolia plants were used as the surface.

[0288] Laboratory-scale method for rain resistance: Dilute WDG in water at 4% (by weight). Place a droplet of this treated solution (0.2 mL) onto a leaf and allow it to dry. The dried spray solution is clearly visible to the naked eye due to the copper content (blue spots) in the spray solution. Then wash the leaf with 4 mL of deionized water over 9 seconds using a burette. Collect the resulting eluent in a bottle at the bottom of the apparatus. Perform 3 washes. Rain resistance can be assessed by visually comparing the deposits of diluted WDG droplets containing or without any polysaccharides after simulated rain. Rain resistance can also be assessed by comparing the transmittance of the water collected after each washing step (using a spectrophotometer at 600 nm).

[0289] Based on Figure 1 The results of the visual assessment of rain resistance.

[0290] In this figure, column I on the left represents magnolia leaves (A) initially treated with a copper salt-containing composition without guar gum. Column II on the right represents magnolia leaves (A) initially treated with a composition containing copper salt and guar gum, and refers to composition 2 of the present invention.

[0291] After the first wash, we can see that the composition in column I without guar gum was completely washed away (I-B), while the composition in column II with guar gum appears to be unaffected (II-B).

[0292] A second and third wash were performed, but neither appeared to remove the composition of column II (II – C and D).

[0293] Therefore, guar gum imparts high rain resistance to copper salts, allowing them to withstand being washed away by precipitation, condensation, effluent, or irrigation.

[0294] Then, after the first, second, and third washing steps, the transmittance of the sample was tested.

[0295] The results are summarized in Table 6 (corresponding to...). Figure 1 The left column I) and Table 7 (which corresponds to Figure 1 In the right column II).

[0296]

[0297] Table 6

[0298]

[0299] Table 7

[0300] According to Table 6, transmittance values ​​could only be recorded after the first wash, with only a small portion of the diluted composition remaining on the leaves.

[0301] Conversely, according to Table 7, transmittance values ​​could be recorded after all three washing steps, with an average of almost 100%, thus showing that all the copper from the applied diluted composition remained on the leaves.

[0302] The strong rain-resistant properties imparted to copper salts by guar gum (polysaccharide) are the reason why guar gum is part of the fungicidal and / or bactericidal agricultural chemical composition of the present invention.

Claims

1. A composition in the form of one or more water-dispersible granules, the composition 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. The composition according to claim 1, wherein, The at least one copper salt includes copper oxychloride and / or copper hydroxide and / or ternary copper sulfate.

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

4. The composition according to any one of the preceding claims, wherein, The at least one polysaccharide includes galactomannan.

5. The composition according to any one 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, more preferably 1% to 8% by weight, and more preferably 1% to 4% by weight relative to the total weight of the composition.

6. The composition according to any one of the preceding claims, wherein, The at least one water-soluble solvent is selected from the group consisting of: N-alkylpyrrolidone, dimethyl sulfoxide, diol, triethylene glycol, alkyl lactate, polyethylene glycol, polypropylene glycol, ester amide, and dioxolane derivatives.

7. The composition according to claim 6, wherein, The at least one water-soluble solvent contains propylene glycol as a diol and / or methyl-5-(dimethylamino)-2-methyl-5-oxovalerate as an ester amide.

8. The composition according to any one of the preceding claims, wherein, The at least one surfactant contains at least one wetting agent and / or at least one dispersant.

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

10. The composition according to claim 8, wherein, The at least one wetting agent comprises a mixture of the following: - At least one sulfosuccinate surfactant, - At least one C 16 -C 22 Alkyl sulfates and / or containing C 16 -C 22 Alkyl ether sulfates.

11. The 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. The composition according to claim 10, wherein, The at least one C 16 -C 22 Alkyl sulfates and / or containing C 16 -C 22 The alkyl ether sulfate is present in an amount of 1% to 90% by weight relative to the total weight of the wetting agent.

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

14. The composition according to claim 8, wherein, The at least one dispersant comprises a sodium salt of at least one naphthalene sulfonate-formaldehyde condensate—optionally alkyl-substituted—and / or a salt of an alkylbenzene sulfonate.

15. The composition according to claim 8, wherein, The at least one dispersant comprises sodium polycarboxylate dispersant.

16. The composition according to any one of the preceding claims, wherein, The at least one carrier is selected from ground natural minerals, preferably kaolin, clay, talc or chalk; or from ground synthetic materials, preferably highly dispersed silica and silicates.

17. A method for manufacturing a composition in the form of one or more water-dispersible granules according to any one of claims 1 to 16, the method comprising the steps of: - Mix a) at least one copper salt and / or sulfur compound, b) at least one polysaccharide, d) at least one surfactant, and e) at least one carrier to obtain a mixture. - Grind the mixture to obtain a powder. - Add water and c) at least one water-soluble solvent to the powder to obtain a wet mass. - Granulate the wet material to obtain one or more granules. - Dry the granules. Wherein 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 one of claims 1 to 16.

18. The method according to claim 17, wherein, The granulation step is performed by extrusion.

19. Use of the composition according to any one of claims 1 to 16 for treating agricultural targets, particularly plant parts and / or soil, to resist plant pathogenic fungi and / or bacteria.

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