Solid compositions as soluble precursors of environmentally friendly and effective metal-based biocides, their preparation and use - Patents.com

Abstract

The present invention relates to a solid composition comprising a homogeneous mixture of at least one inorganic metal source, the metal being copper(II) and / or zinc(II) and a carboxylic acid having at least two carboxyl groups, the molar ratio metal / acid being between 1 and 2. This composition is advantageous as a precursor for preparing a biocidal solution having high biocidal activity, being easy to apply, being low or non-(phyto)toxic and having very good persistence. It also relates to a process for preparing said precursor, a process for preparing a biocidal solution from said precursor, a plant protection method and the use as a biocide.

Description

[Technical field]

[0001] The present invention relates to solid compositions that are particularly suitable as precursors for the preparation of highly effective metal-based biocidal solutions. In particular, the present invention relates to metal-based solid compositions that are soluble (especially in water) and that can form insoluble or slightly soluble compounds once the solution is applied to plants, plant products, seeds, tubers and / or fruits, thereby providing significantly better biocidal activity over an extended period of time and reducing the risk of leaching in soil.

[0002] The present invention also relates to a process for preparing a biocidal solution from said solid composition and its subsequent application to plants, plant products, seeds, tubers and / or fruits.

[0003] The invention also relates to the use of said compositions as biocides, in particular fungicides and / or bactericides, for example in the agricultural, lawn and garden, forestry and general disinfection fields. [Background technology]

[0004] Biocides relate to a large family of chemicals that provide botanical, medical, veterinary, household and industrial antimicrobial agents and disinfectants of liquids and surfaces such as water, floors, pools and work surfaces.

[0005] In particular, agrochemicals / phytomedicinals such as fungicides and bactericides are important protective agents for agriculture. Indeed, agricultural crops are subject to many diseases, especially by certain infectious diseases belonging to the bacterial and fungal families. These are an ever-present threat for many crops, and the control of diseases is of great economic importance, since bacterial or fungal proliferation on plants inhibits the production of leaves, fruits or seeds, reducing the overall quality and / or yield of cultivated crops. Moreover, certain fungi produce mycotoxins in infected crops, thereby causing health problems for humans and animals.

[0006] Fungicides are known in the art as chemical or biological agents used to reduce, inhibit or destroy fungi. Bactericides are known in the art as chemical or biological agents used to reduce, inhibit or destroy bacteria.

[0007] The use of copper, particularly copper(II) ions, to protect and treat crops against certain phytopathogenic fungi and bacteria has long been known.

[0008] For example, copper sulfate is known to be a very good fungicide, but is highly phytotoxic, especially since it is acidic. When neutralized in combination with an alkaline agent such as calcium hydroxide or sodium hydroxide, its phytotoxicity decreases, but is still present. For example, one of the most ancient and still used neutralized forms is commonly known as "Bordeaux mixture", which is a suspension of copper sulfate and lime in ratios that change over time. For example, it was used as early as 1882 to control downy mildew on grapes.

[0009] Other copper(II)-based fungicides are known, including copper oxychloride, copper hydroxide, copper carbonate, and cuprous oxide. Unfortunately, like Bordeaux mixture, they are very poorly soluble in water at neutral pH. For example, copper hydroxide has a very low solubility in water (approximately 0.5 mg / L at 20 °C).

[0010] The biocidal activity of copper(II)-based fungicides is determined by the amount of free Cu available (bio) for consumption by fungi. 2+ ions, and free Cu 2+ The amount of released soluble aqueous copper ions is proportional to the amount of released ions. Therefore, insoluble conventional copper(II)-based fungicides are usually applied to plants in large quantities to effectively suppress the development of pathogenic fungi. 2+ The amount of Cu is on the order of a few ppm at pH 7 and even less at higher pH levels. 2+ The ions ensure sufficient antifungal activity.

[0011] However, despite their biocidal effects, conventional copper(II)-based fungicides have many drawbacks, as described below.

[0012] First, these copper(II)-based compounds are phytotoxic, causing, but not limited to, leaf necrosis and burns, especially when used in high doses and / or repeatedly and / or on vulnerable plants / cultivars.

[0013] Second, the available Cu 2+ The relatively large amounts of copper-based compounds required to achieve adequate levels of copper have a significant impact on cost-effectiveness and, above all, contribute to high soil residue contamination.

[0014] Third, Cu released from solid / insoluble compounds that are applied / deposited on plants, e.g., by spraying. 2+ The amount of ions is uncontrollable because it varies in an unpredictable manner as a function of local environmental conditions such as ambient humidity, dissolved carbon dioxide, and temperature. 2+ The amount of phytotoxicity may be altered, potentially resulting in an increased risk of phytotoxicity in, for example, more fragile varieties.

[0015] Secondly, many other drawbacks of conventional copper(II)-based fungicides result from their insolubility in water, which generally requires their use in the form of a suspension in water. This requirement for the use of a suspension leads, inter alia, to the following: clogging issues with applicators and spray systems commonly used in such applications; Problems of suspension instability due to settling of the solid composition (leading to the need for an appropriate remixing step and / or leading to an uncontrollable decrease in the solids / water ratio of said suspension); and Poor coverage / spread on plants and / or uneven coverage.

[0016] To reduce or avoid clogging and settling, agitation means integrated into the application system is sometimes used, but this leads to more complex and expensive systems, and agitation does not generally eliminate the problem entirely.

[0017] Finally, Cu 2+ The solid compound particles that constitute the ion reservoir are partially lost by leaching during rainfall, leading to a decrease or disappearance of their biocidal activity. For this reason, conventional copper(II)-based fungicides generally need to be applied repeatedly to the same crop (typically 6-10 times a year, but up to 20 times depending on the climate, crop characteristics and crop management), with negative impacts on cost-effectiveness and soil contamination due to leaching.

[0018] Also, known insoluble copper compounds such as copper hydroxide, copper carbonate, and cuprous oxide can be used in the presence of ligands / chelating agents to increase solubility and reduce the amount of Cu. 2+ It has also been disclosed that the bioavailability of

[0019] In particular, WO 91 / 13552 reports that a complex of copper(II) with four ammonia molecules results in the solubilization of copper and the availability of Cu. 2+ It is known that due to its high levels it is possible to increase the fungicidal activity. However, due to its high solubility, this "copper complex" is easily completely leached out and has a very low residue in plants. This requires shorter application intervals and more frequent applications, which in turn eliminates the positive effect of solubility on the overall biocidal effect (the amount of metal applied increases overall) and increases the environmental impact.

[0020] US Patent No. 6,562,757 discloses a plant protection composition comprising a copper source (e.g., copper(II) hydroxide) in the presence of a small amount of a chelating compound (e.g., calcium citrate or calcium malate, whose acids have been previously neutralized with calcium hydroxide). According to US Patent No. 6,562,757, this allows the insoluble copper source to be partially dissolved (potentially up to 43%), thereby allowing the gradual release of bioavailable Cu with controlled partial dissolution. 2+ However, the amount of bioavailable Cu ions can be increased. 2+ The problem of using the suspension for spraying is not solved, since the amount of ions is still very low and the precursor composition is still partially insoluble.

[0021] Also known is a commercial product for use as a fertilizer and for the protection of some plants, sold under the name Dentamet®. This product is sold as a solution of copper(II) sulfate and zinc(II) sulfate (2% and 4% in terms of metals, respectively) in the presence of citric acid, adjusted to a pH of 2.5. Unfortunately, due to the solubility of copper sulfate and zinc sulfate, this product is very leaching out and has a very low residual capacity in plants, the adverse effects of which have already been mentioned. It should be noted that when the Dentamet solution is evaporated, a mixture of the components of the solution, namely copper(II) sulfate, zinc(II) sulfate and citric acid, is obtained in solid form. Moreover, liquid fungicides / fertilizers are less popular with users, due to their shorter shelf life and the larger and heavier transport volumes (higher transport costs) compared to powder / solid products.

[0022] It should also be noted that most copper(II)-based fungicides commercially available for plant protection, including Dentamet products, are considered hazardous due to their phytotoxicity as well as their GHS classification of H400 or H410, i.e. highly toxic to aquatic organisms (with long-term effects).

[0023] However, health and environmental regulations worldwide are becoming increasingly stringent, for example requiring fewer chemical residues in crops and soils and the use of less toxic and more environmentally friendly biocides. In particular, the maximum approved application rate for copper (at least in Europe) is 28 kg / ha for 7 years, but in future this maximum application rate will be reduced as much as possible to minimize soil accumulation and exposure of non-target organisms to copper.

[0024] Thus, there remains a need for metal-based biocides (particularly bactericides and / or fungicides) that (i) have high biocidal activity while requiring lower amounts of metal per treated surface (e.g., crop surface) over time than conventional copper(II)-based fungicides, (ii) are easy to apply, avoiding, for example, clogging and settling problems, (iii) are low or non-(phyto)toxic, and (iii) exhibit a good balance between ease of leaching and persistence in plants. Summary of the Invention [Problem to be solved by the invention]

[0025] The present invention aims inter alia to overcome the above-mentioned drawbacks of the prior art.

[0026] More precisely, it is an object of the present invention to provide a solid composition which is particularly suitable as a precursor for preparing metal-based biocidal solutions.

[0027] In particular, it is an object of the present invention to provide a solid composition which is particularly suitable as a precursor for preparing metal-based biocide solutions exhibiting high biocidal activity, in particular requiring a lower amount of metal per treated surface than conventional copper(II)-based fungicides.

[0028] Another object of the present invention is to provide a solid composition that is particularly suitable as a precursor for the preparation of metal-based biocide solutions, with acceptable or no phytotoxicity.

[0029] It is yet another object of the present invention to provide a solid composition that is particularly suitable as a precursor for the preparation of metal-based biocidal solutions that exhibit low or no toxicity to fish, birds, mammals and bees.

[0030] It is yet another object of the present invention to provide a solid composition which is particularly suitable as a precursor for preparing metal-based biocide solutions and which can be easily applied, e.g. avoiding clogging and settling problems.

[0031] It is yet another object of the present invention to provide a metal-based solid composition that is particularly suitable as a precursor for the preparation of biocidal solutions and that exhibits a balance between the properties of high elution (high solubility) and high retention (low solubility) in plants.

[0032] It is yet another object of the present invention to provide a solid composition which is particularly suitable as a precursor for the preparation of metal-based biocide solutions, which is cost-effective, environmentally friendly and simplifies the process of its preparation and its application to plants, plant products, seeds, tubers and / or fruits.

[0033] Another object of the present invention is to provide a solution to the shortcomings of the prior art that is simple and inexpensive to manufacture and use. [Means for solving the problem]

[0034] The present invention relates to a solid composition comprising a homogeneous mixture of a solid compound (A) and a solid compound (B), Compound (A) is a source of at least one inorganic metal, the metal being copper(II) or zinc(II); Compound (B) is a carboxylic acid having at least two carboxyl groups, In a composition having a metal / acid molar ratio of 1 to 2, When the metal is copper(II), said at least one inorganic metal source is copper(II) hydroxide; When the metal is zinc(II), said at least one source of inorganic metal is zinc(II) oxide.

[0035] The present invention therefore consists in a new and progressive approach, since it is possible to find a solution to the shortcomings of the prior art. The inventors have indeed found that by homogeneously combining solid inorganic sources of copper(II) and / or zinc(II) with specific chelating molecules in a specific stoichiometry (metal / acid molar ratio), it is possible to arrive at solid compositions that are highly soluble in aqueous media and therefore suitable as precursors for preparing solutions to be applied to plants. Furthermore, it has been surprisingly found that from said solutions, irreversibly insoluble or slightly soluble compounds can be obtained (for example by evaporation of water) that show high biocidal activity and a good balance between dissolution and persistence, and that said compounds have no or very low phytotoxicity. Finally, it has also been found that the insoluble or slightly soluble compounds obtained have very low or no toxicity (to fish, birds, mammals, bees, etc.).

[0036] Thus, the present invention takes into account the state of the art in the area of ​​metal-based biocides and solves the problems posed and exposed above.

[0037] The present invention is a surprising and inventive invention, especially in the sense that it combines the advantages of solubility (before / during application to the plant) on the one hand and insolubility (after and once applied to the plant) on the other hand. Indeed, the present invention provides solid precursors that are soluble in water and can form advantageous clear solutions, but which irreversibly form advantageous insoluble or slightly soluble compounds (with no or low (phyto)toxicity) when, for example, said solutions are applied to plants and the water evaporates.

[0038] The present invention also relates to a process for the preparation of a solid composition according to the invention, comprising the step of mixing solid compound (A) with solid compound (B) by applying a mechanical action to obtain a homogeneous mixture.

[0039] The present invention also relates to a method of preparing a biocidal solution, the method comprising the step of combining a solid composition according to the present invention with a solvent, said solvent comprising water.

[0040] The present invention further relates to a method for preventing or inhibiting the growth of live pathogenic organisms on plants, plant products, seeds, tubers and / or fruits, the method comprising, in order, the steps of: a) preparing a biocidal solution according to the first method of the present invention; and b) applying said solution to plants, plant products, seeds, tubers and / or fruits.

[0041] Finally, the present invention also relates to the use of the solid composition according to the invention as a biocide in: i) In agriculture, including field crops, horticulture, arboriculture and viticulture, as pre- and / or post-harvest treatments; ii) lawns and gardens (including professional lawns); iii) Forestry; iv) Disinfection in general.

[0042] Other features and advantages of the invention will become more apparent from the following description of preferred embodiments.

[0043] When ranges are given herein, they include the endpoints unless expressly stated otherwise, and further, all integer values ​​and subdomain values ​​within a numerical range are expressly included as if expressly stated.

[0044] The composition according to the invention comprises a homogeneous mixture of a solid compound (A) and a solid compound (B).

[0045] By "intimate mixture" in the sense of the present invention is meant, as generally accepted in the chemical community, a mixture of at least two solid particles of different nature / composition, which is uniform and shows an intimate bonding or interlocking of said solid particles, e.g. an interaction between the particles of compounds (A) and (B) and / or a coating of the particles of compound (B) by the particles of compound (A).

[0046] The various devices or techniques that can be used to obtain a homogeneous mixture according to the invention are known in the art that allow mechanical action and include, for example, advantageously, mixing by ball milling and mixing by twin screw extrusion.

[0047] The compound (A) according to the invention is a source of at least one inorganic metal, the metal being copper(II) or zinc(II).

[0048] Copper(II) is advantageous because it has a long history of proven effectiveness against fungi and bacteria. Zinc(II) is an advantageous alternative to copper(II) because it is also known to have biocidal activity (albeit generally lower than copper against some diseases) and has fewer health and environmental effects than copper.

[0049] According to the present invention, when the metal is copper(II), the at least one inorganic metal source is copper(II) hydroxide (Cu(OH)2). According to this embodiment, preferably, the at least one inorganic copper(II) source consists essentially of copper(II) hydroxide (or Cu(OH)2). More preferably, compound (A) consists essentially of copper(II) hydroxide (meaning that no other inorganic sources of copper(II) are present / added in the composition, except for impurities that may be present in the starting materials).

[0050] According to the present invention, when the metal is zinc(II), the at least one inorganic metal source is zinc(II) oxide (ZnO). According to this embodiment, preferably, the at least one inorganic zinc(II) source essentially consists of zinc(II) oxide (ZnO). More preferably, compound (A) essentially consists of zinc(II) oxide (meaning that no other inorganic sources of zinc(II) are present / added in the composition, except for impurities that may be present in the starting materials).

[0051] According to yet another embodiment of the present invention, compound (A) comprises copper(II) hydroxide and zinc(II) oxide. More preferably, compound (A) consists essentially of copper(II) hydroxide and zinc(II) oxide (meaning that no other zinc(II) and copper(II) inorganic sources are present / added in the composition, except for impurities that may be present in the starting materials). The presence of both a copper(II) source and a zinc(II) source can synergistically enhance biocidal activity, since less metal (total amount of copper+zinc) is required to achieve the same biocidal activity / efficacy than when one of these metals is used alone.

[0052] When compound (A) comprises at least one source of inorganic zinc(II) and at least one source of inorganic copper(II), the ratio of copper:zinc in the composition is preferably about 2:1, alternatively about 1:2.

[0053] The compounds (B) according to the invention are carboxylic acids having at least two carboxyl groups and optionally at least one hydroxyl group.

[0054] Examples of carboxylic acids according to embodiments of the present invention are provided in the table below.

[0055] [Table 1]

[0056] Preferably, compound (B) is a carboxylic acid having at least three carboxyl groups and, optionally, at least one hydroxyl group.

[0057] In a more preferred embodiment, compound (B) is trans-aconitic acid, tricarballylic acid or citric acid.

[0058] In the most preferred embodiment, compound (B) is citric acid. Citric acid is a carboxylic acid with three carboxyl groups and one hydroxyl group. For example, compound (B) is anhydrous citric acid or citric acid monohydrate. Citric acid is advantageous in the present invention because it is inexpensive, has good chelating power for copper (II) or zinc (II), and has low (phyto) toxicity. Moreover, above all, citric acid has been proven to allow the use of copper (II) and zinc (II) in the specific stoichiometry (metal / acid molar ratio) of the present invention to produce compounds / complexes with low (phyto) toxicity that are insoluble or slightly soluble during (1) aqueous solutions (thereby dissolving insoluble inorganic copper or zinc sources) and (2) crystallization / precipitation (e.g., by evaporation of water).

[0059] In the composition according to the invention, the molar ratio of metal / acid is between 1 and 2. For clarity, this molar ratio is obtained by dividing the number of moles of metal from the inorganic metal source by the number of moles of carboxylic acid molecules. This range of molar ratio, in combination with other characteristics of the composition, makes it possible to reach the objectives of the invention, in particular to reach a solid composition capable of forming a solution in water and which irreversibly forms an insoluble or slightly soluble compound upon evaporation of the water and / or precipitation / crystallization.

[0060] In advantageous embodiments, the metal / acid molar ratio is 1.9; 1.8; 1.7; 1.6 or less than 1.5.

[0061] In other advantageous embodiments, the metal / acid molar ratio is 1.05; 1.1; 1.2; 1.3 or 1.4 or higher.

[0062] These upper and lower molar ratio limits allow the present invention to approach the identified optimum stoichiometry, i.e., metal:acid stoichiometry of 3:2 and / or 2:1. Small deviations from this 3:2 or 2:1 stoichiometry do not prevent the invention from being achieved, but it is better to approach 1.5 or 1.67 (aiming for a mixture of 3:2 and 2:1 stoichiometry), or even closer to 2.

[0063] Also preferably, the molar ratio of metal / acid is 1.1-2, more preferably 1.2-2, further preferably 1.3-2, and further preferably 1.4-2.

[0064] According to a highly preferred embodiment, the metal / acid molar ratio is about 1.5.

[0065] According to another highly preferred embodiment, the metal / acid molar ratio is about 2.

[0066] According to yet another highly preferred embodiment, the metal / acid molar ratio is about 1.67.

[0067] According to one embodiment, the composition of the invention is soluble in water (i.e., solubility >1 g / L at 20° C.). In particular, the composition according to the invention has a water solubility of at least 30 g / L, at least 40 g / L, at least 50 g / L, or preferably at least 60 g / L, or even at least 70 g / L, more preferably at least 80 g / L at 20° C.

[0068] According to one embodiment, the composition of the invention is in the form of a powder, granules or tablets. If in the form of a powder, it is preferably in the form of a free-flowing powder.

[0069] The composition of the present invention may also comprise other ingredients / additives next to compound (A) and compound (B) without departing from the present invention. For example, the composition of the present invention may comprise at least one additive selected from the list comprising pH adjusters, film formers, anti-caking agents, surfactants, wetting agents, defoamers, anti-drift agents, adhesives, thickeners, foaming agents, solidifying agents, other biocides, fertilizers and stabilizers.

[0070] According to the present invention, the method for preparing a biocidal solution comprises combining a solid composition with a solvent, said solvent comprising water. Preferably, said solvent is essentially water. This is advantageous because the biocidal solution is obtained by simply dissolving the solid composition, especially in water. The composition of the present invention as a precursor of a biocidal solution makes it possible to avoid the problems exposed above (clogging, settling or need for regular mixing, insufficient coverage of plants, etc.) associated with the use of suspensions.

[0071] Additives may also be used and may be added either pre-added to the solvent, added to the solution after preparation, or added together when the solid composition and the solvent are combined. Examples of additives include pH adjusters, film formers, anti-caking agents, surfactants, wetting agents, defoamers, anti-drift agents, adhesives, thickeners, foaming agents, solidifying agents, other biocides, fertilizers, stabilizers, etc.

[0072] Preferably, the amounts of solid composition and solvent are such that the resulting solution has an M metal concentration of 0.01 g / L to 5 g / L, preferably 0.05 g / L to 3 g / L. More preferably, the amounts of solid composition and solvent are such that the resulting solution has an M metal concentration of 0.1 g / L to 2 g / L.

[0073] According to the present invention, a method for preventing or inhibiting the growth of live pathogenic organisms on plants, plant products, seeds, tubers and / or fruits comprises, in order, the steps of: a) preparing a biocidal solution by combining the composition of the present invention with a solvent, the solvent comprising water; and b) applying said solution to plants, plant products, seeds, tubers and / or fruits.

[0074] FIG. 1 is a flow chart showing steps (a) and (b) of a method for preventing or suppressing the growth of live pathogenic organisms on plants, plant products, seeds, tubers and / or fruits according to the present invention.

[0075] According to one embodiment, the applying step is carried out by spraying or milling or dipping or watering or coating.

[0076] According to another embodiment, the amount of metal applied on said plants, plant products, seeds, tubers and / or fruits is less than 4000 g / ha (maximum registered dose) upon application, preferably less than 3000 g / ha, more preferably less than 2000 g / ha, even less than 1000 g / ha or less than 500 g / ha. For clarity, the amount of metal according to this embodiment is determined / calculated based on the molar mass of the metallic elements Cu and / or Zn.

[0077] According to yet another embodiment, the method for preventing or suppressing the growth of live pathogenic organisms on plants, plant products, seeds, tubers and / or fruits comprises, after application step b), a step c) of crystallizing and / or precipitating a slightly water-soluble to insoluble solid compound (C) on the plants, plant products, seeds, tubers and / or fruits. For example, this crystallization and / or precipitation step c) is carried out by evaporation of the solvent, for example natural water evaporation (due to ambient temperature, wind, etc.). Through step c) according to the invention, the solid compound (C) is formed on the plants, plant products, seeds, tubers and / or fruits in the form of an amorphous precipitate or in the form of crystals or in the form of a mixture thereof.

[0078] In particular, when compound (B) is citric acid, the solid compound (C) has a concentration ranging from 0, i.e. (C6H8O7), to -4, i.e. (C6H4O7) 4- The complexes include those with citrate having ionization states up to

[0079] In one embodiment, when compound (B) is citric acid, the solid compound (C) in the present invention is represented by the formula Cu w Zinc x (C6H y O7) z and / or a hydrate thereof, wherein 0≦w≦3; 0≦x≦3; 1≦(w+x)≦3; 4≦y≦8; 1 ≤ z ≤ 2; 1≦(w+x) / z≦2 (for the sake of clarity, (w+x) / z corresponds to the metal / acid molar ratio according to the invention).

[0080] In an advantageous embodiment, when compound (B) is citric acid, the solid compound (C) comprises (i) copper citrate of formula Cu3(C6H5O7)2 or Cu2(C6H4O7), or (ii) zinc citrate of formula Zn3(C6H5O7)2, or (iii) a zinc-copper citrate mixture of formula ZnCu2(C6H5O7)2, or (iv) a zinc-copper citrate mixture of formula Zn2Cu(C6H5O7)2, or (v) a hydrate of (i) or (ii) or (iii) or (iv), or a mixture thereof.

[0081] The solid compound (C) may also contain other compounds, soluble or insoluble, next to the copper citrate and / or zinc citrate(s) without departing from the scope of the present invention. For example, the solid compound (C) may contain "free" citric acid (e.g., when it is present in excess in the solid composition of the present invention compared to the targeted stoichiometry of the insoluble metal citrate).

[0082] Preferably, when compound (B) is citric acid, said solid compound (C) consists essentially of (i) copper citrate of formula Cu3(C6H5O7)2 or Cu2(C6H4O7), or (ii) zinc citrate of formula Zn3(C6H5O7)2, or (iii) a zinc-copper citrate mixture of formula ZnCu2(C6H5O7)2, or (iv) a zinc-copper citrate mixture of formula Zn2Cu(C6H5O7)2, or (v) a hydrate of (i) or (ii) or (iii) or (iv), or a mixture thereof.

[0083] In particular, copper citrate, especially of the formula Cu3(C6H5O7)2 and its hydrates, or of the formula Cu2C6H4O7 and its hydrates (e.g., Cu2(C6H4O7)·H2O), has the advantage of being highly biocidal, yet highly persistent due to its low solubility, and is not toxic to fish, birds, mammals, or bees (see especially Fishel (2011) “Pesticide Toxicity Profile: Copper-based Pesticides”, Pesticide Information Office, Florida Cooperative Extension Service, Institute of Food and Agricultural Sciences, University of Florida).

[0084] Zinc citrate, especially its formula Zn3(C6H5O7)2 and its hydrates, is known as a "generally recognized as safe" food ingredient, because of its low solubility, which allows it to retain a very good biocidal activity while also increasing its residual potential. In fact, in Europe, zinc citrate is included in the positive list of Regulation (EC) No. 1925 / 2006 on food fortification. It is also listed as a vitamin and mineral substance that may be used in the manufacture of food supplements in Directive 2002 / 46 / EC of the European Parliament and of the Council on food supplements. Furthermore, it is listed as a mineral salt in EU Regulation (EC) No. 609 / 2013 on foods for infants and young children, foods for special medical purposes and total diet replacement for weight control. Secondly, in the United States, zinc citrate is considered to be a substance classified as a dietary ingredients according to § 201(ff) of the FDC Act. In oral care, zinc citrate preparations are classified as class I active ingredients with regard to safety and class III active ingredients with regard to efficacy. Since 2009, zinc citrate is fully compliant with the U.S. Food, Drug, and Cosmetic Act and is "Generally Recognized as Safe" (self-affirmed GRAS).

[0085] Advantageously, the solubility of compound (C) is 1 g / L or less. Preferably, it is 0.8 g / L or less. Also preferably, the solubility of compound (C) is 0.1 g / L or more, preferably 0.2 g / L or more, even 0.3 g / L or more, and even more preferably 0.5 g / L or more.

[0086] This is advantageous for reaching good copper(II) bioavailability and a balance between high dissolution and high retention, especially compared to the very low solubility of copper hydroxide.

[0087] According to the invention, the solid composition is used as a biocide, in particular as a fungicide and / or bactericide, in the following fields: i) In agriculture, including field crops, horticulture, arboriculture and viticulture, as pre- and / or post-harvest treatments; ii) lawn and garden (including professional lawns); iii) forestry; and iv) Disinfection in general.

[0088] In the field of disinfection generally, solid compositions are advantageous in many applications such as medical, veterinary, household and industrial, including but not limited to, as disinfectants for fluids (water, air, etc.) and surfaces (floors, work surfaces, toilets, medical instruments, prostheses, etc.).

[0089] In particular, the solid compositions according to the invention are used as biocides in: i) In agriculture, including field crops, horticulture, arboriculture and viticulture, as pre- and / or post-harvest treatments; ii) lawns and gardens (including professional lawns); and iii) Forestry.

[0090] The composition of the present invention is advantageously used as a biocide to treat various bacterial and fungal diseases in various plants, plant products, seeds, tubers and / or fruits.In particular, the composition of the present invention is advantageously used as a fungicide, for example, but not limited to, to treat fungal diseases such as grape downy mildew (Plasmopara viticola), potato late blight (Phytophtora infestans) and gray mold (Botrytis cinerea) in grapevines and many other crops.

[0091] Preferably, in the use according to the invention, the solid composition according to the invention is used in an aqueous solution, optionally together with at least one additive selected from the list comprising pH adjusters, film formers, anti-caking agents, surfactants, wetting agents, anti-foaming agents, anti-drift agents, thickeners, foaming agents, solidifying agents, other biocides, fertilizers and stabilizers.

[0092] The composition of the present invention is also advantageous in promoting plant growth, and therefore can be used as fertilizer (e.g., foliar fertilizer).In fact, zinc and copper are essential elements for plant growth.For example, zinc is important for root development and crop germination due to its role in the synthesis of growth hormone, and copper improves photosynthesis, enzyme activity, and plays an important role in cell wall lignin formation. [Brief description of the drawings]

[0093] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0094] Next, the embodiments of the present invention will be further described by way of examples, together with comparative examples not according to the present invention. The following examples are provided for illustrative purposes and are not intended to limit the scope of the present invention. EXAMPLES

[0095] 1) Preparation of the solid composition according to the present invention

[0096] The preparation of the compositions according to the invention was carried out in a continuous process using a Thermo Electron EuroLab XL16 40 L / D high torque twin screw extruder equipped with three Brabender DDW-MD2-DDSR20N gravimetric dosing of the starting materials.

[0097] The TSE (Twin Screw Extruder) has two intermeshing co-rotating screws (200-400 rpm) mounted on splined shafts within a temperature-controlled, sealed barrel. The designed screws are stiff and self-wiping, eliminating stagnation zones throughout the entire length of the process section. The result is a homogenous mixture, forming a free-flowing powder.

[0098] Each of the solid compositions (1 to 5) was analyzed by powder X-ray diffraction. The measurement was performed for one hour per sample using Kα1 radiation supplied from a Johansson spectrometer by the Bragg-Brentano method.

[0099] (Composition 1)

[0100] Anhydrous citric acid and copper(II) hydroxide were mixed at a rate of 10 Kg / h with a copper:acid molar ratio of 3:2 as follows:

[0101] [Table 2]

[0102] XRD analysis of the resulting solid composition showed a binary mixture of two compounds, anhydrous citric acid and copper hydroxide (overlay of the respective XRD patterns).

[0103] Composition 1 contains 28.16 mass % copper (Cu).

[0104] (Composition 2)

[0105] Anhydrous citric acid and zinc (II) oxide were mixed at a rate of 10 Kg / h with a zinc:acid molar ratio of 3:2 as follows:

[0106] [Table 3]

[0107] XRD analysis of the resulting solid composition showed a binary mixture of two compounds, anhydrous citric acid and zinc oxide (overlay of the respective XRD patterns).

[0108] Composition 2 contains 31.23 mass % of metallic zinc (Zn).

[0109] (Composition 3)

[0110] Anhydrous citric acid, copper (II) hydroxide and zinc (II) oxide were mixed at a rate of 10 Kg / h in a molar ratio of copper:zinc:acid of 2:1:2 as follows:

[0111] [Table 4]

[0112] XRD analysis of the resulting solid composition showed a ternary mixture of three compounds, anhydrous citric acid, copper hydroxide, and zinc oxide (overlay of the respective XRD patterns).

[0113] Composition 3 contained 19.23 mass % metallic copper (Cu) and 9.90 mass % metallic zinc (Zn).

[0114] (Composition 4)

[0115] Anhydrous citric acid (2 moles), copper(II) hydroxide (1 mole) and zinc(II) oxide (2 moles) were mixed at a rate of 10 Kg / h in a molar ratio of copper:zinc:acid of 1:2:2 as follows:

[0116] [Table 5]

[0117] XRD analysis of the resulting solid composition indicated a ternary mixture of three compounds, anhydrous citric acid, copper hydroxide, and zinc oxide. This is evident from FIG. 2, which shows the XRD patterns of (b) solid composition 4, (c) copper hydroxide, (d) zinc oxide, and (e) anhydrous citric acid. Pattern (b) is an overlay of the respective XRD patterns (c), (d), and (e).

[0118] Composition 4 contained 9.86 mass % metallic copper (Cu) and 20.30 mass % metallic zinc (Zn).

[0119] (Composition 5)

[0120] Anhydrous citric acid (1 mole) and copper (II) hydroxide (2 moles) were mixed at a rate of 10 Kg / h with a copper:acid molar ratio of 2:1 as follows:

[0121] [Table 6]

[0122] XRD analysis showed a binary mixture of two compounds, anhydrous citric acid and copper hydroxide (overlay of the respective XRD patterns).

[0123] Composition 5 contains 32.82 mass % of metallic copper (Cu).

[0124] 2) Preparation of the biocidal solution

[0125] (Solution from composition 1)

[0126] Different amounts of solid composition 1 were added to water at room temperature under gentle stirring at 500 RPM using a Velp Scientifica magnetic stirrer equipped with a PTFE plain stir bar (Solution 1a: 0.67 g / L; Solution 1b: 1.34 g / L; Solution 1c: 2.68 g / L; Solution 1d: 4.03 g / L). Clear solutions were obtained after 1-5 minutes.

[0127] (Solution from composition 2)

[0128] Different amounts of solid composition 2 were added to water at room temperature under gentle stirring at 500 RPM using a Velp Scientifica magnetic stirrer equipped with a PTFE plain stir bar (Solution 1a: 0.61 g / L; Solution 1b: 1.21 g / L; Solution 1c: 2.42 g / L; Solution 1d: 3.63 g / L). Clear solutions were obtained after 1-5 minutes.

[0129] (Solution from composition 3)

[0130] Different amounts of solid composition 3 were added to water at room temperature (0.025 g / L to 3 g / L) under gentle stirring at 500 RPM using a Velp Scientifica magnetic stirrer equipped with a PTFE plain stir bar. A clear solution was obtained after 1 to 5 minutes.

[0131] (Solution from composition 4)

[0132] Different amounts of solid composition 4 were added to water at room temperature (0.025 g / L to 3 g / L) under gentle stirring at 500 RPM using a Velp Scientifica magnetic stirrer equipped with a PTFE plain stir bar. A clear solution was obtained after 1 to 5 minutes.

[0133] (Solution from composition 5)

[0134] Different amounts of Solid Composition 5 were added to water at room temperature (0.025 g / L to 3 g / L) under gentle stirring at 500 RPM using a Velp Scientifica magnetic stirrer equipped with a PTFE plain stir bar. A clear solution was obtained after 1 to 5 minutes.

[0135] 3) Crystallization results

[0136] Each of compositions 1 to 5 was dissolved in water at a concentration of 60 g / L. The resulting transparent solution was then placed in a glass petri dish and left at room temperature and atmospheric pressure for 24 hours. The resulting solid compound (compound (C) according to the present invention) was filtered, dried, and finally analyzed by powder X-ray diffraction. The measurement was performed for one hour per sample using Kα1 radiation supplied from a Johansson type spectrometer by the Bragg-Brentano method.

[0137] Crystallized Compounds (C) Obtained from Compositions 1-3: XRD analysis of each of the compounds obtained by crystallization of aqueous solutions of Compositions 1-3 showed patterns inconsistent with those of Compounds (A) and (B) (i.e., anhydrous citric acid and copper hydroxide and / or zinc oxide) present in the starting solid Compositions 1-3.

[0138] Crystallized compound (C) obtained from composition 4: FIG. 2(a) shows the XRD pattern of solid compound (C) obtained by crystallization of an aqueous solution of composition 4, which does not match the XRD patterns of compounds (A) and (B) (i.e., anhydrous citric acid, copper hydroxide, and zinc oxide) present in the starting solid composition 4. For comparison, FIG. 2 also shows the patterns of (b) solid composition 4 before solubilization, (c) copper hydroxide, (d) zinc oxide, and (e) anhydrous citric acid. The solid compound (C) obtained after crystallization of the solubilized solution of composition 4 is expected to be a mixed zinc citrate complex of the general formula Zn2Cu(C6H5O7)2·xH2O.

[0139] Crystallized compound (C) obtained from composition 5: Figure 3(b) shows the XRD pattern of the solid compound (C) obtained by crystallization of an aqueous solution of composition 5. A structure search in ICSD returns a hit (CIF ICSD 251344) corresponding to Cu2(C6H4O7)·H2O. The theoretical XRD pattern of Cu2(C6H4O7)·H2O (CIF ICSD 251344) is shown in Figure 3(a). This result proves that dissolving composition 5 in water and crystallizing it resulted in a nearly pure phase of the copper citrate compound.

[0140] 4) Solubility results

[0141] Solid compositions 1-5: These compositions are completely soluble in water at room temperature, with solubilities higher than 80 g / L, each of which gives a clear / transparent solution after a maximum of a few minutes under classical stirring conditions.

[0142] For comparison, the solubility of Cu(OH)2 is 0.003 g / L and the solubility of ZnO is 0.004 g / L.

[0143] Compound (C): The solid precipitates obtained from the solutions of compositions 1-5 in 3) above were suspended in water at room temperature at a concentration of 10 g / L and mixed for 5 minutes (at 500 RPM using a Velp Scientifica magnetic stirrer equipped with a PTFE plain stir bar). After centrifugation (Hettich Roto Silenta 630 RS set at 3000 RPM-2224RCF), the supernatant was analyzed by the enzyme-certified dosing procedures (Agroscope STS0223 13.5.07.ME.023 and 13.5.07.ME.074) for copper and citrate to determine solubility.

[0144] The solid compounds (C) obtained from the solutions of compositions 1 to 5 all exhibit solubilities of 0.5 to 1 g / L, meaning that they are slightly soluble, and therefore represent a good compromise between weak to moderate leachability and long-term persistence.

[0145] 5) Comparison between homogeneous mixtures and simple mixtures

[0146] The solubility of the compositions according to the invention, i.e. homogeneous mixtures, was compared with a standard high speed simple mixture of the corresponding citric acid, copper hydroxide and / or zinc oxide in the same proportions.

[0147] Quantitative analysis of metals (zinc and / or copper) in the solution (dissolved) was carried out using a highly sensitive emission spectrometer (ICP MP-AES 4210, manufactured by Agilent).

[0148] A relatively simple high speed mix was prepared using a standard high speed powder mixer, an Alfa Laval Vortex Shear-Mixer.

[0149] The tests were carried out by adding 10 grams of each composition (inventive and comparative) to distilled water at room temperature (beaker equipped with magnetic mixer fingers rotating at 500 rpm) and then measuring the metal concentration in the solution by ICP.

[0150] For a mixture of 61.15% by mass of anhydrous citric acid and 38.852% by mass of zinc oxide

[0151] [Table 7]

[0152] For a mixture of 59.61% anhydrous citric acid, 15.14% copper hydroxide, and 25.25% zinc oxide

[0153] [Table 8]

[0154] (Consideration)

[0155] Under the test conditions, it was observed that the solubility of the compositions according to the invention (homogeneous mixtures) was virtually complete (almost all of the metal amount was in solution), whereas the corresponding simple mixtures showed only very moderate solubility of the metals, meaning that a significant portion of the metal sources (zinc oxide and / or copper hydroxide) remained insoluble, illustrating the drawbacks arising in the context of the present invention.

[0156] 6) Fungicidal activity results (laboratory test)

[0157] Bioassay of Efficacy of Composition 1 Against P. viticola on Grape Leaf Discs

[0158] (method)

[0159] Composition 1 for preventive protection against grape powdery mildew was compared with the commercial product Kocide® Opti TMA comparative test was carried out using a suspension of 1 × 10 sucrose (copper hydroxide, insoluble) as a standard. Both were standardized with a minimum test dose of 300 g metallic copper per hectare. The range of test concentrations (aqueous solutions) was 1, 2, 4 and 6 times higher than the registered dose of Kocide® Opti (solutions 1a, b, c and d). Solutions 1a-d of Composition 1 and a suspension of Kocide® Opti were applied with a Potter spray tower to a Petri dish containing 10 leaf discs (cultivar Cabernet Sauvignon) on water-soaked filter paper. After application, the leaf discs were allowed to dry slowly under a laminar flow hood. Inoculation was carried out with a suspension of sporangia (1 × 10 5 sporangia · ml -1 ) 24 hours after treatment / spraying. The boxes were sealed and placed in an incubator (constant 22°C, high humidity ensured by water-soaked filter paper, natural photoperiod). Disease severity was assessed 7 days after inoculation by estimating the percentage of the disk surface that showed sporulation.

[0160] (result)

[0161] The infection rate was satisfactory (78% in untreated controls).

[0162] FIG. 4 shows the severity (%) of powdery mildew on leaf discs using a suspension of Kocide® Opti at the registered dosage concentration (0.19 g / L) and solution 1 according to the invention at different metallic copper concentrations (0.19, 0.38, 0.76 and 1.13 g / L).

[0163] Severity data were subjected to analysis of variance with comparative mean tests (Tukey test: R2 = 0.968; Pr>F: < 0.0001, threshold P = 0.05). Data were arcsine transformed before analysis. The same letters indicate no significant differences between modalities (treatments / concentrations).

[0164] These results show that composition 1 according to the invention has similar biocidal activity as Kocide® Opti at the registered dose of metallic copper (0.19 g / L).

[0165] Furthermore, at the high concentration of composition 1 (solution 1d), only slight phytotoxic symptoms were observed in the form of small necrotic spots.

[0166] This shows that composition 1 according to the invention is a suitable precursor for preparing biocidal solutions that, in addition to being easy to apply due to its solubility, have very good biocidal activity (comparable to copper hydroxide) and very low phytotoxicity.

[0167] From these bioassay results, it is expected that copper and citric acid based composition 1 will result in the formation of a slightly soluble compound of formula Cu3(C6H5O7)2·xH2O and will not show toxic effects on fish, birds, mammals or bees.

[0168] Bioassay of Efficacy of Composition 2 Against P. viticola on Grape Leaf Discs

[0169] (method)

[0170] Composition 2, for preventative protection against grape powdery mildew, is compared with the commercial product Kocide® Opti TM A comparative test was carried out with a suspension of 1 × 10 sucrose (copper hydroxide, insoluble) as a standard. Both were standardized with a minimum test dose of 300 g metallic copper per hectare. The range of test concentrations was ... 5 sporangia · ml -1) 24 hours after treatment / spraying. The boxes were sealed and placed in an incubator (constant 22°C, high humidity ensured by water-soaked filter paper, natural photoperiod). Disease severity was assessed 7 days after inoculation by estimating the percentage of the disk surface that showed sporulation.

[0171] (result)

[0172] The infection rate was satisfactory (78% in untreated controls).

[0173] FIG. 5 shows the severity (%) of powdery mildew on leaf discs using a suspension of Kocide® Opti at the registered dosage concentration (0.19 g / L) and composition 2 according to the invention at different metallic zinc concentrations (0.19, 0.38, 0.76 and 1.13 g / L).

[0174] Severity data were subjected to analysis of variance with comparative mean test (Tukey test: R2 = 0.881, Pr>F: < 0.0001, threshold P = 0.05). Data were arcsine transformed before analysis. Different letters on the graphs indicate statistically significant differences between treatments / concentrations.

[0175] These results show that composition 2 according to the invention has a satisfactory biocidal activity, similar to Kocide® Opti at high concentrations, the lowest concentration showing 81% efficacy, although less active than the copper benchmark.

[0176] Furthermore, no phytotoxic symptoms were observed at the high concentration of Composition 2 (Solution 2d).

[0177] This shows that composition 2 according to the invention is a suitable precursor for preparing biocidal solutions that, in addition to being easy to apply due to its solubility, are non-phytotoxic and have good biocidal activity (even if lower than that of copper hydroxide).

[0178] Finally, composition 2, based on zinc and citric acid, is expected to result in the formation of a slightly soluble compound of formula Zn3(C6H5O7)2·xH2O, which is non-toxic and "generally recognized as safe".

[0179] [Bioassay (in vitro test) of the effectiveness of compositions 1 and 2 against Botrytis cinerea]

[0180] (method)

[0181] Compositions 1 and 2 were tested in vitro for preventative protection against Botrytis cinerea.

[0182] The determination of the minimum inhibitory concentration (MIC) was performed in 24-well plates based on the in vitro poisoned food method. First, compositions 1 and 2 were dissolved in liquid medium (PDB, potato dextrose broth, Difco) in the desired concentration range and dispensed in triplicate into 24-well plates. The positive control consisted of pure culture medium, while the negative control consisted of the addition of a registered dose of a fungicide switch (cyprodinil + fludioxonil, Syngenta, Switzerland) to the medium. Nutrient agar medium (PDA, potato dextrose agar, Difco) maintained at 45°C was added to a final concentration of 30% by volume to solidify the nutrient medium. The inoculum was prepared by suspending conidia from 10-day-old colonies in sterile water (10 5 ~10 6 The concentration of the medium was 1 / ml, and 50 μl was placed per well. The plates were incubated at 22°C under a natural light cycle. Fungal growth was evaluated 7, 14, and 25 days after inoculation to determine fungal toxicity.

[0183] (result)

[0184] As expected, mycelial growth was recorded in the positive control and inhibited in the negative control.

[0185] For Composition 1, the MIC was >5 g / L at 7 days post inoculation (dpi) but increased to 10–20 g / L at 25 dpi, indicating that the pathogen can tolerate this concentration but is blocked at 20 g / L.

[0186] Composition 2 showed excellent effect in controlling Botrytis, with a low MIC of 5 to 10 g / L.

[0187] Bioassay of Efficacy of Compositions 3 and 4 Against P. viticola on Grape Leaf Discs

[0188] (method)

[0189] Compositions 3 and 4 for preventive protection against grape powdery mildew were compared with the commercial product Kocide® Opti TM A comparative test was conducted using a suspension of (copper hydroxide, insoluble) as the standard.

[0190] The 50% inhibitory concentration (IC 50 ) was calculated according to the powdery mildew severity assessment using the XLSTAT software (45-parameter logistic regression module). For that purpose, tests were carried out at concentrations ranging from 0.025 to 3 g composition / L (aqueous solution).

[0191] Solutions of compositions 3-4 and a Kocide® Opti suspension were sprayed with a Potter spray tower onto a Petri dish containing 10 leaf disks (cultivar Cabernet Sauvignon) on water-soaked filter paper. After spraying, the leaf disks were allowed to dry slowly under a laminar flow hood. Inoculation was performed with a suspension of sporangia (1 × 10 5 sporangia · ml -1 ) 24 hours after treatment / spraying. The boxes were sealed and placed in an incubator (constant 22°C, high humidity ensured by water-soaked filter paper, natural photoperiod). Disease severity was assessed 7 days after inoculation by estimating the percentage of the disk surface that showed sporulation.

[0192] (result)

[0193] The infection rate was satisfactory (77% in the untreated control) and no sporulation was observed by the above criteria.

[0194] Composition 4 showed better IC than composition 3 at concentrations of 0.025 g / L and 0.070 g / L in water, respectively. 50 By extrapolation, IC 99 (theoretical doses capable of completely controlling the disease) can be determined to be 0.532 g / L for composition 3 and 0.106 g / L for composition 4.

[0195] Additionally, phytotoxic symptoms were observed for Compositions 3 and 4 at the highest tested concentrations.

[0196] [Comparative bioassay results of compositions 1 to 4]

[0197] The following table summarizes the results obtained in the bioassays carried out with compositions 1 to 4 according to the invention against P. viticola, and the values ​​for the commercial Kocide® Opti based on the registered dose.

[0198] The table lists the mass percentage of metal (copper and / or zinc) and IC for each of Compositions 1-4 and the Kocide® Opti product. 99 The measured value (g / L) of IC 99 The values ​​of and the required metal amounts (g / ha) taking into account the application of an aqueous solution of 400 L / ha (standard value) are also shown.

[0199] [Table 9] * Registered dose

[0200] From these results, we can see that: · Composition 1 is significantly more effective than Kocide® Opti (3 times less copper per season); · Even though composition 2 (zinc only) is less effective than composition 1 (copper only), it is close to Kocide® Opti (and has other advantages over Kocide® Opti); · The combination of copper and zinc in a solid composition allows a reduction in the amount of metal required / applied compared to a copper-only (or zinc-only) solid composition; The combination of copper and zinc in the solid composition allows a significant reduction in the amount of metal required / applied compared to Kocide® Opti (up to 20 times less for composition 4).

[0201] [Bactericidal activity results (laboratory test)]

[0202] (method)

[0203] Compositions 1-4 were tested in aqueous solution against several bacteria, namely Escherichia coli, Staphylococcus aureus, Pseudomonas Aerginosa, and Enterococcus hirae.

[0204] Their minimum inhibitory concentrations (MIC), i.e. the lowest product test concentration sufficient to completely inhibit the growth of the microorganisms, were determined.

[0205] The tests were performed according to the ISO 20776-1:2007 standard: Culture medium: Mueller-Hinton Broth (MHB) Inoculum: 5~8×10 5 CFU / mL (colony forming units per mL of suspension) Temperature: 37℃ Incubation time: 18±2 hours Antibiotics Verified: Tetracycline

[0206] (result)

[0207] The results obtained are shown in the table below.

[0208] [Table 10]

[0209] The MIC values ​​obtained indicated moderate to good efficacy against the human pathogenic bacteria tested.

Claims

1. A solid composition comprising a homogeneous mixture of solid compound (A) and solid compound (B), The compound (A) is at least one inorganic metal source, and the metal is copper(II) or zinc(II). The compound (B) is a carboxylic acid having at least two carboxyl groups, In a composition characterized by a metal / acid molar ratio of 1 to 2, When the metal is copper(II), the at least one inorganic metal source is copper(II) hydroxide. A composition in which, when the metal is zinc(II), the at least one inorganic metal source is zinc(II) oxide.

2. The composition according to claim 1, characterized in that the molar ratio of the metal to the acid is about 1.5, about 1.67, or about 2.

3. The composition according to claim 2, characterized in that the compound (B) is a carboxylic acid having at least three carboxyl groups.

4. The composition according to claim 3, characterized in that the compound (B) is trans-aconitic acid, tricarbaryl acid, or citric acid.

5. The composition according to claim 4, characterized in that the compound (B) is citric acid.

6. The composition according to any one of claims 1 to 5, characterized in that the compound (A) comprises copper(II) hydroxide and zinc(II) oxide.

7. The composition according to any one of claims 1 to 5, characterized in that it has a water solubility of at least 60 g / L at 20°C.

8. The composition according to any one of claims 1 to 5, characterized in that it is in the form of a powder, granules, or tablets.

9. The composition according to any one of claims 1 to 5, characterized by comprising at least one additive selected from the list consisting of pH adjusters, film-forming agents, anti-caking agents, surfactants, wetting agents, defoaming agents, anti-drift agents, adhesives, thickeners, foaming agents, solidifying agents, other biocides, fertilizers, and stabilizers.

10. A method for preparing the composition according to any one of claims 1 to 5, characterized by comprising the step of mixing solid compound (A) and solid compound (B) by applying a mechanical action to obtain a homogeneous mixture.

11. The method according to claim 10, characterized in that the mixing is carried out by ball milling or twin-screw extrusion.

12. A method for preparing a biocide solution, comprising the step of combining a solid composition according to claims 1 to 5 with a solvent, wherein the solvent is water.

13. The method according to claim 12, characterized in that the solvent is essentially water.

14. The method according to claim 12, characterized in that the amounts of the composition and the solvent are such that the solution has a metal M concentration of 0.01 g / L to 5 g / L, preferably 0.1 g / L to 2 g / L.

15. a) A step of preparing the biocide solution according to claim 12, b) A step of applying the solution to plants, plant products, seeds, tubers and / or fruits, A method for preventing or suppressing the proliferation of live pathogenic organisms on plants, plant products, seeds, tubers and / or fruits, characterized by comprising the following in order.

16. The method according to claim 15, characterized in that the application step is carried out by spraying, crushing, immersion, irrigation, or coating.

17. The method according to claim 15, characterized in that, after step b), it includes step c) crystallizing and / or precipitating a solid compound (C) that is slightly soluble to insoluble in water on a plant, plant product, seed, tuber and / or fruit.

18. When compound (B) is citric acid, the solid compound (C) is of the formula Cu ｗ Zn ｘ (C ６ H ｙ O ７ ) ｚ The method according to claim 17, characterized by comprising at least one citrate and / or hydrate represented by (however, 0 ≤ ≤ 3; 0 ≤ x ≤ 3; 1≦(w+x)≦3; 4 ≤ y ≤ 8; 1 ≤ z ≤ 2; 1 ≤ (w + x) / z ≤ 2 (for simplicity, (w + x) / z corresponds to the metal / acid molar ratio according to the present invention).

19. The following uses of the compositions described in claims 1 to 5 as biocides: i) Agriculture, including field crops, horticulture, tree cultivation, and viticulture, as pre-harvest and / or post-harvest treatments; ii) Lawns and gardens, including professional turf; iii) forestry; iv) All aspects of disinfection.

20. The use according to claim 19 as a fungicide and / or bactericide, preferably as a fungicide.

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