Novel formulation of copper-based fungicides and bactericide

Abstract

This invention relates to a novel composition comprising a) a buffer system; b) tannins; and c) a copper-based fungicide. This invention also relates to a method for reducing phytotoxicity by applying a composition comprising: a) a buffer system; b) tannins; and c) a copper-based fungicide to a site. This invention further relates to the use of the buffer system for stabilizing a liquid composition of a copper-based fungicide.

Description

[Technical Field]

[0001] This invention relates to a unique formulation of fungicides and bactericides containing a copper-based fungicide, tannic acid, and a buffer system as active ingredients. [Previous Technology]

[0002] Copper-based insecticides are widely used in agricultural chemical products to control a wide range of fungi, bacteria, and other pests. Copper was one of the earliest elements used as a plant fungicide, and its discovery can be traced back to the famous Bordeaux mixture, which contained a mixture of copper sulfate (CuSO4) and quicklime, and was used in French vineyards to control downy mildew.

[0003] Copper-based fungicides are divided into highly water-soluble compounds such as copper acetate, copper chloride and copper chlorate, copper formate, copper hexafluorosilate, copper nitrate, copper chromate, copper sulfate pentahydrate and Baudouin mixed solution; and compounds such as copper hydroxide, copper oxychloride sulfate (COCS) and ternary copper sulfate (copper sulfate, copper hydroxide, hemihydrate), which are also called "mixed" copper and have relatively low solubility in water.

[0004] Copper-based fungicides are important due to their low cost, protective / preventive properties, and ability to inhibit fungal spore germination and hyphal penetration. When copper particles come into contact with water, they slowly dissolve, releasing Cu+ ions to provide fungal control.

[0005] Copper particles adhere to the leaf surface and act as an ion reservoir, continuously releasing Cu+2 ions and forming a protective layer to prevent infection. The Cu+2 ion release efficiency of copper fungicide formulations varies depending on the source of copper. Furthermore, the concentration of copper ions on leaves depends on the balance between copper complexes and soluble forms (Menkissoglu and Lindow 1991).

[0006] Therefore, the efficacy of the formulation is highly dependent on the technology used to generate stable complexes, allowing for moderate and sustained copper ion release.

[0007] It is known that copper is toxic when it penetrates plant tissues in a dissolved form. Generally, when applying copper-based fungicides, spray additives such as foliar nutrients and any surfactants with penetrating properties should be avoided.

[0008] It is also known that certain commercially available copper-based fungicides are associated with high levels of eye irritation and aquatic toxicity.

[0009] Currently, there are several solid formulations of copper-based fungicides on the market, such as Kocide (DuPont), BORDELES RSR DISPERSS (UPL), Champ® WG (Nufarm), etc.; Suspension concentrate (SC) formulations have many advantages due to their low cost, lower skin penetration and easier handling by farmers; therefore, effective copper-based SC formulations are very suitable for agricultural fields.

[0010] US 4544666 and US 4673687 disclose SC compositions containing a tannate complex of copper sulfate pentahydrate and ammonium magnesium formate. These compositions contain picric acid, which has many disadvantages and is known to be an explosive compound and should be handled with extreme care.

[0011] Therefore, there is a need for copper-based fungicide compositions that contain low amounts of copper-based fungicides, are easy to handle, are safer for users, and are more environmentally friendly.

[0012] Surprisingly, it has been found that the composition of the present invention containing a water-soluble copper-based fungicide is less harmful to plants than commercially known formulations.

[0013] The present invention provides a novel, improved, safer and greener copper-based fungicide composition with low copper content and no added unwanted surfactants.

[0014] Compared to other conventional copper-based products, the composition of the present invention exhibits high bioavailability of long-lasting copper when diluted in water, and shows effective prevention and control of fungal infections in cultures.

[0015] Surprisingly, it has been found that the composition of the present invention reduces eye irritation. [Summary of the Invention]

[0016] Therefore, the present invention provides an agricultural chemical composition comprising a) a buffer system; b) tannic acid and c) a copper-based fungicide.

[0017] The present invention also provides a method for reducing plant toxicity by applying a composition comprising a) a buffer system; b) tannic acid and c) a copper-based fungicide to a site.

[0018] The present invention also provides the use of a buffer system for stabilizing the liquid composition of a copper-based fungicide.

[0019] Furthermore, the present invention provides a method for reducing eye irritation and aquatic toxicity by applying the disclosed composition.

Implementation Method

[0021] Definition

[0022] Before detailing the subject matter of this invention, it may be helpful to provide definitions of certain terms intended to be used herein. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this subject matter pertains. For clarity, the following definitions are provided.

[0023] The term “a” or “one” as used herein includes both the singular and the plural, unless otherwise specified. Therefore, the terms “a,” “one,” or “at least one” are used interchangeably in this application.

[0024] As used herein, the verb “comprising” as used in this description and the scope of the patent application and its variations is used in its non-limiting sense to mean that the item following the word is included, but does not exclude items not specifically mentioned.

[0025] As used herein, when used in conjunction with numerical values, the term "about" includes ±10% of the indicated value. Furthermore, all ranges herein for the same component or property include endpoints, can be independently combined, and include all intermediate points and ranges. It should be understood that when providing a parameter range, the invention also provides all integers within that range and their tenths.

[0026] As used herein, the term "effective amount" means the amount of an active ingredient commercially recommended for the control and / or prevention of pests. The commercially recommended amount of each active ingredient is usually specified as the application rate of a commercially available formulation and can be found on the label accompanying the commercially available formulation. The commercially recommended application rate of a commercially available formulation may vary depending on factors such as the plant species and the pest to be controlled.

[0027] As used herein, the term “pest” includes, but is not limited to, unwanted plant pathogenic fungi, unwanted insects, unwanted nematodes and weeds.

[0028] As used herein, the term "pesticide" refers to any agent that can be used to prevent, control, and / or kill pests. This term should be understood to include, but is not limited to, fungicides, insecticides, nematicides, herbicides, acaricides, parasiteicides, or other control agents. For details on chemical categories and application, and specific compounds within each category, see "The Pesticide Manual Thirteenth Edition" (British Crop Protection Council, Hampshire, UK, 2003) and "The e-Pesticide Manual, Version 3" (British Crop Protection Council, Hampshire, UK, 2003-04), the contents of which are incorporated herein by reference in their entirety.

[0029] As used herein, the term "locus" includes not only areas where pests may have developed, but also areas where pests have not yet appeared, and also areas under cultivation. Locus includes plants or crops and the propagation material of plants or crops. Locus also includes the area surrounding plants or crops and the growth medium of plants or crops, such as soil and the crop site.

[0030] As used herein, the terms "plant" or "crop" include the whole plant, plant organs (such as leaves, stems, branches, roots, trunks, crowns, twigs, fruits, etc.), plant cells, or plant seeds. This term also includes plant crops, such as fruits, spores, bulbs, rhizomes, bud bases, stolons and buds, and other parts of plants (including seedlings and young plants) that are transplanted after germination or emergence.

[0031] As used herein, the term "ha" means hectare.

[0032] The term "copper dosage" represents the amount of active ingredient provided by the formulation.

[0033] The present invention provides a fungicide composition comprising a) a buffer system; b) tannic acid and c) a copper-based fungicide.

[0034] In some embodiments, the buffer system is a combination of carboxylic acid and base.

[0035] In some embodiments, the carboxylic acid is selected from acetic acid, formic acid, citric acid, propionic acid, butyric acid, and / or any combination thereof. In a preferred embodiment, the carboxylic acid is acetic acid.

[0036] In some embodiments, the amount of carboxylic acid is from about 22% to about 38% by weight, based on the total weight of the composition. In a preferred embodiment, the amount of carboxylic acid is from about 25% to about 30% by weight, based on the total weight of the composition.

[0037] In some embodiments, the base is ammonium hydroxide.

[0038] In some embodiments, the amount of alkali is from about 19% to about 24% by weight, based on the total weight of the composition. In a preferred embodiment, the amount of alkali is from about 20% to about 21% by weight, based on the total weight of the composition.

[0039] In some embodiments, an excess of carboxylic acid is added relative to the base.

[0040] In some embodiments, the weight ratio of carboxylic acid to base is from about 0.9:1 to about 1.8:1. In a preferred embodiment, the weight ratio of carboxylic acid to base is from about 1.2:1 to about 1.4:1.

[0041] In some embodiments, the amount of tannic acid in the composition is from about 0.49% by weight to about 0.51% by weight, based on the total weight of the composition. In a preferred embodiment, the amount of tannic acid in the composition is about 0.5% by weight, based on the total weight of the composition.

[0042] In some embodiments, the copper-based fungicide is selected from copper acetate, copper chloride, copper chlorate, copper formate, copper hexafluorosilate, copper nitrate, copper chromate, copper sulfate pentahydrate, Baudouinsky mixture, copper hydroxide, copper oxychloride sulfate (COCS), ternary copper sulfate (such as copper sulfate), copper hydroxide, hemihydrate, and / or any combination thereof. In a preferred embodiment, the copper-based fungicide is selected from copper acetate, copper chloride, copper chlorate, copper formate, copper hexafluorosilate, copper nitrate, copper chromate, copper sulfate pentahydrate, Baudouinsky mixture, and any combination thereof. In a more preferred embodiment, the copper-based fungicide is selected from copper sulfate pentahydrate, Baudouinsky mixture, and / or any combination thereof.

[0043] In some embodiments, the amount of the copper-based fungicide is from about 16% to about 24% by weight, based on the total weight of the composition. In a preferred embodiment, the amount of the copper-based fungicide is from about 18% to 22% by weight, based on the total weight of the composition.

[0044] In some embodiments, the composition of the present invention comprises a) a buffer system, which is a combination of carboxylic acid and base; b) tannic acid and c) a copper-based fungicide. In some embodiments, the composition of the present invention comprises a) a buffer system, which is a combination of acetic acid and ammonium hydroxide; b) tannic acid and c) a bromide mixture as a copper-based fungicide.

[0045] In some embodiments, the copper content of the copper-based fungicide is from about 40 g / L to about 500 g / L. In a preferred embodiment, the copper content is from about 50 g / L to about 300 g / L. In a more preferred embodiment, the copper content is from about 50 g / L to about 100 g / L. In a particular preferred embodiment, the copper content is about 66 g / L.

[0046] In some embodiments, the molar ratio between the carboxylic acid and the copper-based fungicide is from about 3.5:1 to about 25:1. In a preferred embodiment, the molar ratio between the carboxylic acid and the copper-based fungicide is from about 10:1 to about 18:1. In a preferred embodiment, the molar ratio between the carboxylic acid and the copper-based fungicide is from about 15:1 to about 18:1.

[0047] In some embodiments, the molar ratio between the alkali and the copper-based fungicide is from about 3.7:1 to about 17:1. In a preferred embodiment, the molar ratio between the alkali and the copper-based fungicide is from about 10:1 to about 16:1. In a preferred embodiment, the molar ratio between the alkali and the copper-based fungicide is from about 11:1 to about 15:1.

[0048] In some embodiments, the composition of the present invention further includes a stabilizer.

[0049] In some embodiments, the stabilizer is selected from salts of propionic acid, sodium salts of butyric acid, sodium salts of valeric acid, and any combination thereof. In a preferred embodiment, the stabilizer is a salt of propionic acid.

[0050] In some embodiments, the salt may be sourced from sodium, calcium, magnesium, potassium, lithium, and / or any combination thereof. In a preferred embodiment, the salt is sourced from sodium.

[0051] In a preferred embodiment, the stabilizer is a sodium salt of propionic acid.

[0052] In some embodiments, the amount of stabilizer is from about 0.8% by weight to about 1.0% by weight, based on the total weight of the composition. In a preferred embodiment, the amount of stabilizer is about 0.9% by weight, based on the total weight of the composition.

[0053] In some embodiments, the composition of the present invention comprises a) a buffer system, which is a combination of acetic acid and ammonium hydroxide; b) tannic acid; c) a mixture of copper-based fungicides and a stabilizer. In some embodiments, the composition of the present invention comprises a) a buffer system, which is a combination of acetic acid and ammonium hydroxide; b) tannic acid; c) a mixture of copper-based fungicides and a sodium salt of propionic acid as a stabilizer.

[0054] In some embodiments, the composition of the present invention further comprises additives. Non-limiting examples include antifreeze, defoamers, thickeners, rheology modifiers, and any other additional additives known in formulation industry practices, and any combination thereof. In some preferred embodiments, the additives are selected from thickeners and rheology modifiers. In some embodiments, the rheology modifier is xanthan gum.

[0055] In some embodiments, the composition of the present invention comprises a) a buffer system, which is a combination of acetic acid and ammonium hydroxide; b) tannic acid; c) a mixture of copper-based fungicides, a stabilizer, and an additive. In some embodiments, the composition of the present invention comprises a) a buffer system, which is a combination of acetic acid and ammonium hydroxide; b) tannic acid; c) a mixture of copper-based fungicides, a sodium salt of propionic acid as a stabilizer, and a rheology modifier as an additive. In some embodiments, the composition of the present invention comprises a) a buffer system, which is a combination of acetic acid and ammonium hydroxide; b) tannic acid; c) a mixture of copper-based fungicides, a sodium salt of propionic acid as a stabilizer, and xanthan gum as a rheology modifier.

[0056] In some embodiments, the composition of the present invention comprises a) about 28% by weight of acetic acid and about 20% by weight of ammonium hydroxide, based on the total weight of the composition; b) about 0.5% by weight of tannic acid, based on the total weight of the composition; c) about 18% by weight of Porto mixture, based on the total weight of the composition; about 0.9% by weight of sodium propionic acid, based on the total weight of the composition; and about 0.3% by weight of xanthan gum, based on the total weight of the composition.

[0057] In some embodiments, the dosage of the composition of the present invention is from about 0.4 L / ha to about 5 L / ha. In some embodiments, the dosage of the composition of the present invention is from about 1 L / ha to about 4 L / ha. In some embodiments, the dosage of the composition of the present invention is from about 2.5 L / ha to about 3.5 L / ha.

[0058] The copper fungicide, carboxylic acid, alkali and tannic acid composition of the present invention obtained by the integrated manufacturing process can produce a supersaturated solution that is stable during preparation and is best suited for the following crop protection: (a) the carboxylic acid is prepared together with a salt formed from the same acid to form a buffer system that keeps it stable when diluted by acid buffering of the dilution medium and ensures better application to plants, and (b) a rheology modifier is used to ensure the stability of the concentrate during its half-life, but no dispersant is required.

[0059] The composition of the present invention is designed to achieve a special interaction of components without the use of a dispersant. This interaction initially occurs during the formulation of the components (copper interaction rather than dispersion) and is subsequently diluted with water.

[0060] The components of the present invention are prepared in the following order of addition: a) buffer system; b) tannic acid and c) copper-based fungicide.

[0061] The present invention also provides a method for controlling plant pathogenic fungi and / or bacteria in a crop field, comprising applying an effective amount of the composition disclosed herein to the crop field to control plant pathogenic fungi and / or bacteria in the crop field.

[0062] In some embodiments, the crop line is selected from the group consisting of cotton, grapevines, fruits, and vegetables, such as Rosaceae sp. (e.g., pome fruits, such as apples and pears, and drupes such as apricots, cherries, almonds, and peaches, and berries such as strawberries), Ribesioidae sp., Juglandaceae sp., Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp., Actinidaceae sp., Lauraceae sp., Musaceae sp. (e.g., banana trees and banana plantations), Rubiaceae sp. (e.g., coffee), Theaceae sp., Sterculiaceae sp., Rutaceae sp. (e.g., lemon and grapefruit); Solanaceae sp. (e.g., tomato), Liliaceae sp., Asteraceae sp. (e.g., lettuce), Umbelliferae sp., Cruciferae sp., Chenopodiaceae sp., Cucurbitaceae sp. (e.g., cucumber), Allium sp. (e.g., leek, onion), Papilionaceae sp. (e.g., pea); major crop plants, such as Gramineae sp. (e.g., corn, turf, cereals such as wheat, rye, rice, barley, oats, sorghum / millet and black wheat), Asteraceae sp. (e.g., sunflower), Brassicaceae (e.g., white cabbage, red cabbage, broccoli, cauliflower, Brussels sprouts, bok choy, kohlrabi, radish and rapeseed, mustard, wasabi and watercress), Fabaceae (e.g., green beans, peanuts), Papilionaceae (e.g., soybeans), Solanaceae (e.g., potatoes), Chenopodiaceae (e.g., sugar beets, fodder beets, flame beets, beetroot); sugarcane, poppies, olives, coconuts, cocoa, tobacco and useful and ornamental plants from gardens and woodlands; and their respective genetically modified varieties, and their seeds. In a preferred embodiment, the crop is selected from the group consisting of fruit trees, grapevines and vegetables.In a preferred embodiment, the crop is selected from the group consisting of: pome fruits, such as apples and pears; drupes, such as peaches, apricots and almonds; tree nuts, such as walnuts and hazelnuts; grapevines, such as grapes, kiwis and hops; other tree crops, such as olives, citrus fruits, and avocados; fruits and vegetables, such as tomatoes, peppers, and cucumbers; root and tuber crops, such as potatoes and carrots; leafy vegetables, such as lettuce and cabbage; oil crops, such as sunflowers and rapeseed; cereals, such as wheat, rye, barley and rice; small fruits, such as blackberries and blueberries; ornamental plants, such as roses and azaleas; and herbs, such as mint and basil.

[0063] Non-limiting examples of fungal pathogens that can be treated according to the present invention include: diseases caused by powdery mildew pathogens, such as Blumeria species [e.g., Blumeria graminis], Podosphaera species [e.g., Podosphaera leucotricha], Sphaerotheca species [e.g., Sphaerotheca fuliginea], Uncinula species [e.g., Uncinula necator], and Erysiphe species; diseases caused by rust pathogens, such as Gymnosporangium species [e.g., Gymnosporangium sabinae]; and Hemileia species [e.g., Hemileia rust]. Vastatrix; Phakpsora species [e.g., Phakpsora pachyrhizi or Phakpsora meibomiae], Puccinia species [e.g., Puccinia recondita, Puccinia graminis, or Puccinia strii formis], Uromyces species [e.g., Uromyces appendiculatus], diseases caused by pathogens from the Oomycetes group, such as Albugo species [e.g., Algubo Candida], Bremia species [e.g., Bremia laciucaer], Peronospora species (e.g., pea downy mildew (Peronospora pisi) or cabbage downy mildew (P. brassicaer)), Phytophthora species (e.g., pathogenic Phytophthora infestans)), Plasmopara species (e.g., grape downy mildew (Plasmopara))Leaf spot and leaf blight caused by the following fungi include: *Pseudoperonospora* species (e.g., *Pseudoperonospora humuli* or *Pseudoperonospora cubensis*), *Pythium* species (e.g., *Pythium ultimum*), *Alternaria* species (e.g., *Alternaria solani*), *Cercospora* species (e.g., *Cercospora beticola*), *Cladiosporum* species (e.g., *Cladiosporium cucumerinur*), and *Cochliobolus* species (e.g., *Cochliobolus gracilis*). [sativus] (Conidial form: Drechslera, synonyms: Helminthosporium or Cochliobolus miyabeanus)], Colletotrichum species [e.g. Colletotrichum lindemuthianum], Corynespora species [e.g. Corynespora cassiicola], Cycloconium species [e.g. Cycloconium oleaginunv], Diaporthe species [e.g. Diaporthe citrv], Elsinoe species [e.g. Elsinoe f.] Gloeosporium species (e.g., *Gloeosporium laeticolor*), Glomerella species (e.g., *Glomerella cingulata*), Guignardia species (e.g., *Guignardia bidwellv*), and Leptosphaeria speciesspecies [e.g., *Leptosphaeria maculans*], *Magnaporthe* species [e.g., *Magnaporthe grisea*], *Microdochium* species [e.g., *Microdochium nivaler*], *Mycosphaerella* species [e.g., *Mycosphaerella graminicola* (also known as *Septoria tritici*)], *Mycosphaerella arachidicola* or *Mycosphaerella fi jiens*], *Phaeosphaeria* species [e.g., *Phaeosphaeria nodorunr*], *Pyrenophora* species [e.g., *Pyrenophora*]. The fungi causing wheat leaf blight include *Pyrenophora tritici repenth*, *Ramularia* species (e.g., *Ramularia collo-cygni* or *Ramularia areola*), *Rhynchosporium* species (e.g., *Rhynchosporium secalis*), *Septoria* species (e.g., *Septoria apii* or *Septoria lycopersici*), *Stagonospora* species (e.g., *Stagonospora nodorum*), *Typhula* species (e.g., *Typhula incarnate*), and *Venturia* species (e.g., *Venturia aubergine*). [inaequalis], root and stem diseases caused by the following, for example, Corticium species [such as Corticium solani], Fusarium species [such as Fusarium oxysporum], and Gramineae.The following species (e.g., *Gaeumannomyces graminis*), *Plasmodiophora* species (e.g., *Plasmodiophora brassica*), *Rhizoctonia* species (e.g., *Rhizoctonia solani*), *Sarocladium* species (e.g., *Sarocladium oryzae*), *Sclerotium* species (e.g., *Sclerotium oryzae*), *Tapesia* species (e.g., *Tapesia acuformis*), and *Thielaviopsis* species (e.g., *Thielaviopsis basicola*) cause ear and inflorescence diseases (including corn cob diseases), for example, *Alternaria* species. species (e.g., *Alternaria* spp.); *Aspergillus* species (e.g., *Aspergillus flavus*), *Cladosporium* species (e.g., *Cladosporium cladosporioides*), *Claviceps* species (e.g., *Claviceps purpurea*), *Fusarium* species (e.g., *Fusarium culmorunr*), *Gibberella* species (e.g., *Gibberella zeae*), *Monographella* species (e.g., *Monographella nivalis*), *Stagonospora* species (e.g., *Stagonospora* glume). [nodorunr] refers to diseases caused by smut fungi, such as *Sphacelotheca* species (e.g., *Sphacelotheca reiliana*), *Tilletia* species (e.g., *Tilletia caries* or *Tilletia dwarf*).The following fungi cause fruit rot: *Urocystis* species (e.g., *Urocystis occulta*), *Ustilago* species (e.g., *Ustilago nuda*), *Aspergillus* species (e.g., *Aspergillus flavus*), *Botrytis* species (e.g., *Botrytis cinerea*), *Monilinia* species (e.g., *Monilinia laxa*), *Penicillium* species (e.g., *Penicillium expansum* or *Penicillium purpurogenum*), *Rhizopus* species (e.g., *Rhizopus stolonifer*), and *Sclerotinia*. Seed and soil rot and blight, as well as seedling diseases, caused by the following species (e.g., *Sclerotinia sclerotiorum*), *Verticilium* species (e.g., *Verticilium albo-atrum*), etc.): *Alternaria* species (e.g., *Alternaria brassicicola*), *Aphanomyces* species (e.g., *Aphanomyces euteiches*), *Ascochyta* species (e.g., *Ascochyta lends*), *Aspergillus* species (e.g., *Aspergillus flavus*), *Cladosporium* species (e.g., *Cladosporium herbarum*), *Cochliobolus*. species) [such as Cochliobolus sativus] (conidia: Drechslera, Bipolaris, synonym: Helminthosp orium) , Colletotrichumspecies (e.g., *Colletotrichum coccodes*), *Fusarium* species (e.g., *Fusarium culmorum*), *Gibberella* species (e.g., *Gibberella zeae*), *Macrophomina* species (e.g., *Macrophomina phaseolina*), *Microdochium* species (e.g., *Microdochium nivale*), *Monographella* species (e.g., *Monographella nivalis*), *Penicillium* species (e.g., *Penicillium expansum*), *Phoma* species (e.g., *Phoma lingam*), *Phomopsis* species (e.g., *Phomopsis so ae* of soybean), *Phytophthora* species (e.g., *Phytophthora cactorum*), *Pyrenophora* species (e.g., *Pyrenophora graminea* of barley), *Pyricularia* species (e.g., *Pyricularia oryzae* of rice), *Pythium* species (e.g., *Pythium ultimum*), *Rhizoctonia* species (e.g., *Rhizoctonia solani* of standing blight), *Rhizopus* species (e.g., *Rhizopus oryzae* of rice); *Sclerotium* species (e.g., *Sclerotium rolfsii* of white rot), *Septoria* species (e.g., *Septoria nodorum*), *Typhula* species (e.g., *Typhula incarnata*), *Verticillium* species (e.g., *Verticillium dahliae*)[dahliae], cankers, galls, and leaf clusters caused by the following, for example, *Nectria* species [e.g., *Nectria galligena*]; wilt caused by the following, for example, *Verticillium* species [e.g., *Verticillium longisporum*], *Fusarium* species [e.g., *Fusarium oxysporum*]; deformities of leaves, flowers, and fruits caused by the following, for example, *Exobasidium* species [e.g., *Exobasidium vexans*], *Taphrina* species [e.g., *Taphrina deformans*]; degenerative diseases of woody plants caused by the following, for example, *Esca* species [e.g., *Phaeomoniella*]. Diseases affecting plant tubers caused by fungi such as *Chlamydospora*, *Phaeoacremonium aleophilum*, or *Fomitiporia mediterranean*, and *Ganoderma* species (e.g., *Ganoderma boninense*), such as *Rhizoctonia* species (e.g., *Rhizoctonia solani*) and *Helminthosporium* species (e.g., *Helminthosporium solani*), such as diseases caused by bacterial pathogens such as *Xanthomonas* species (e.g., *Xanthomonas campestris* pv. oryzae*) and *Pseudomonas* species (e.g., *Pseudomonas syringae*). pv. lachrymans), *Erwinia* species [e.g., *Erwinia amylovora*], *Liberibacter* species [e.g., *Liberibacter asiaticus*], *Xylella* species [e.g., *Xylella* var. *leaves scorch*]Soybean diseases include fungal diseases affecting leaves, stems, pods, and seeds caused by the following fungi: Alternaria spec atrans tenuissima leaf spot, Colletotrichum gloesporioides dematium var. truncatum, and Septoria spp. (e.g., Solanaceae Ralstonia solanacearum), Dickeya species (e.g., Dickeya solanv), Clavibacter species (e.g., Clavibacter michiganensis), and Streptomyces species (e.g., Streptomyces scabies). Cercospora kikuchii leaf spot and wilt, Choanephora infundibulifera trispora leaf blight, Dactuliophora glycines leaf spot, Peronospora manshurica downy mildew, Drechslera glycini blight, Cercospora sojina leaf spot, and Leptosphaerulina leaf spot. Trifolii, Phyllostica leaf spot [Phyllosticta sojaecola], Phomopsis sojae, Microsphaera diffusa, PyrenochaetaFungal diseases affecting the roots and stem base, including: * *Rhizoctonia solani* (aerial root, leaf, and vein wilt), *Phakopsora pachyrhizi* (soybean rust), *Phakopsora meibomiae* (layer rust), *Sphaceloma glycines* (canker spot), *Stemphylium botryosum* (leaf blight), *Fusarium virguliforme* (sudden death), and *Corynespora cassiicola* (target spot); and fungal diseases of the roots and stem base caused by the following fungi, such as: black root rot (*Calonectria crotalariae*), and anthracnose (*Macrophomina* (bean damping-off). Fusarium wilt or wilting, root rot and pod and neck rot [Fusarium oxysporum, Fusarium orthoceras, Fusarium semitectum, Fusarium equiseti], root rot of Mycoleptodiscus [Mycoleptodiscus terrestris], Neocosmospora [Neocosmospora vasinfecta], pod and stem wilt [Diaporthe phaseolorum], stem canker (Diaporthe phaseolorum var. caulivora)], Phytophthora rot [Phytophthora davidii] [megasperma], brown stem rot [Phialophora gregata], pythium rot [Pythium aphanidermatum, Pythium irregulare, Pythium debaryanum, Pythium myriotylum, Pythium ultimum], rhizoctonia root rot, stem rot and damping-off [Rhizoctonia solani]Sunflower sclerotinia stem rot, Sclerotinia rolfsii white rot, Thieviopsis basicola root rot.

[0064] In some embodiments, the plant pathogenic harmful fungi are selected from the genera *Taphrina* spp., *Monilia* spp., *Venturia* spp., *Stemphylium* spp., *Alternaria* spp., *Sphaerotheca* spp., *Podosphaera* spp., *Glomerella* spp., *Xanthomonas* spp., *Pseudomonas* spp., *Erwinia* spp., *Botryosphaeria* spp., *Plasmopara* spp., and *Pseudoperonospora*. spp.), Peronospora spp., Bremia spp., Phytophthora spp., Pythium spp., Sclerotinia spp., Septoria spp., Uncinula spp., Puccinia spp., Pyricularia spp., Elsinoe spp., Kuehneola spp., Phakopsora spp., Colletotrichum spp., Cladosporium spp., Corynespora spp.

[0065] In a different state, the present invention relates to the use of a buffer system for stabilizing the liquid composition of a copper-based fungicide.

[0066] In some embodiments, the buffer system stabilizes the liquid composition of the copper-based fungicide and tannic acid.

[0067] In some embodiments, the liquid composition is in the form of a suspension concentrate.

[0068] In some embodiments, the buffer system is a combination of carboxylic acid and base.

[0069] In some embodiments, the carboxylic acid is selected from acetic acid, formic acid, citric acid, propionic acid, butyric acid, and / or any combination thereof. In a preferred embodiment, the carboxylic acid is acetic acid.

[0070] In some embodiments, the amount of carboxylic acid is from about 22% to about 38% by weight, based on the total weight of the composition. In a preferred embodiment, the amount of carboxylic acid is from about 25% to about 30% by weight, based on the total weight of the composition.

[0071] In some embodiments, the base is ammonium hydroxide.

[0072] In some embodiments, the amount of alkali is from about 19% to about 24% by weight, based on the total weight of the composition. In a preferred embodiment, the amount of alkali is from about 20% to about 21% by weight, based on the total weight of the composition.

[0073] In some embodiments, an excess of carboxylic acid is added relative to the base.

[0074] In some embodiments, the weight ratio of carboxylic acid to base is from about 0.9:1 to about 1.8:1. In a preferred embodiment, the weight ratio of carboxylic acid to base is from about 1.2:1 to about 1.4:1.

[0075] In some embodiments, the copper-based fungicide is selected from copper acetate, copper chloride, copper chlorate, copper formate, copper hexafluorosilate, copper nitrate, copper chromate, copper sulfate pentahydrate, Baudouinsky mixture, copper hydroxide, copper oxychloride sulfate (COCS), copper oxide, ternary copper sulfate (such as copper sulfate), copper hydroxide, hemihydrate, and / or any combination thereof. In a preferred embodiment, the copper-based fungicide is selected from copper acetate, copper chloride, copper chlorate, copper formate, copper hexafluorosilate, copper nitrate, copper chromate, copper sulfate pentahydrate, Baudouinsky mixture, and / or any combination thereof. In a more preferred embodiment, the copper-based fungicide is selected from copper sulfate pentahydrate, Baudouinsky mixture, and any combination thereof.

[0076] In some embodiments, the amount of the copper-based fungicide is from about 16% to about 24% by weight, based on the total weight of the composition. In a preferred embodiment, the amount of the copper-based fungicide is from about 18% to 22% by weight, based on the total weight of the composition.

[0077] In some embodiments, the molar ratio between the carboxylic acid and the copper-based fungicide is about 3.5:1 to about 18:1. In a preferred embodiment, the molar ratio between the carboxylic acid and the copper-based fungicide is about 10:1 to about 18:1. In a preferred embodiment, the molar ratio between the carboxylic acid and the copper-based fungicide is about 15:1 to about 18:1.

[0078] In some embodiments, the molar ratio between the alkali and the copper-based fungicide is from about 3.7:1 to about 17:1. In a preferred embodiment, the molar ratio between the alkali and the copper-based fungicide is from about 10:1 to about 16:1. In a preferred embodiment, the molar ratio between the alkali and the copper-based fungicide is from about 11:1 to about 15:1.

[0079] In some embodiments, the buffer system stabilizing the copper-based liquid composition further comprises tannic acid.

[0080] In some embodiments, the amount of tannic acid in the composition is from about 0.49% by weight to about 0.51% by weight, based on the total weight of the composition. In a preferred embodiment, the amount of tannic acid in the composition is about 0.5% by weight, based on the total weight of the composition.

[0081] In some embodiments, the composition of the present invention further includes a stabilizer.

[0082] In some embodiments, the stabilizer is selected from salts of propionic acid, sodium salts of butyric acid, sodium salts of valerate, and / or any combination thereof. In a preferred embodiment, the stabilizer is a salt of propionic acid.

[0083] In some embodiments, the salt may be sourced from sodium, calcium, magnesium, potassium, lithium, and / or any combination thereof. In a preferred embodiment, the salt is sourced from sodium.

[0084] In a preferred embodiment, the stabilizer is a sodium salt of propionic acid.

[0085] In some embodiments, the amount of stabilizer is from about 0.8% by weight to about 1.0% by weight, based on the total weight of the composition. In a preferred embodiment, the amount of stabilizer is about 0.9% by weight, based on the total weight of the composition.

[0086] In some embodiments, the composition of the present invention further comprises additives. Non-limiting examples include antifreeze, defoamers, thickeners, rheology modifiers, and any other additional additives known in formulation industry practices, and any combination thereof. In some preferred embodiments, the additives are selected from thickeners and rheology modifiers. In some embodiments, the rheology modifier is xanthan gum.

[0087] In some embodiments, the dosage of the composition of the present invention is from about 0.4 L / ha to about 5 L / ha. In some embodiments, the dosage of the composition of the present invention is from about 1 L / ha to about 4 L / ha. In some embodiments, the dosage of the composition of the present invention is from about 2.5 L / ha to about 3.5 L / ha.

[0088] In a different embodiment, the present invention relates to a method for reducing phytotoxicity by applying a composition comprising: a) a buffer system; b) tannic acid and c) a copper-based fungicide to a site.

[0089] In some embodiments, the buffer system is a combination of carboxylic acid and base.

[0090] In some embodiments, the carboxylic acid is selected from acetic acid, formic acid, citric acid, propionic acid, butyric acid, and / or any combination thereof. In a preferred embodiment, the carboxylic acid is acetic acid.

[0091] In some embodiments, the amount of carboxylic acid is from about 22% to about 38% by weight, based on the total weight of the composition. In a preferred embodiment, the amount of carboxylic acid is from about 25% to about 30% by weight, based on the total weight of the composition.

[0092] In some embodiments, the base is ammonium hydroxide.

[0093] In some embodiments, the amount of alkali is from about 19% to about 24% by weight, based on the total weight of the composition. In a preferred embodiment, the amount of alkali is from about 20% to about 21% by weight, based on the total weight of the composition.

[0094] In some embodiments, an excess of carboxylic acid is added relative to the base.

[0095] In some embodiments, the weight ratio of carboxylic acid to base is from about 0.9:1 to about 1.8:1. In a preferred embodiment, the weight ratio of carboxylic acid to base is from about 1.2:1 to about 1.4:1.

[0096] In some embodiments, the amount of tannic acid in the composition is from about 0.49% by weight to about 0.51% by weight, based on the total weight of the composition. In a preferred embodiment, the amount of tannic acid in the composition is about 0.5% by weight, based on the total weight of the composition.

[0097] In some embodiments, the copper-based fungicide is selected from copper acetate, copper chloride, copper chlorate, copper formate, copper hexafluorosilate, copper nitrate, copper chromate, copper sulfate pentahydrate, Baudouin mixed solution, copper hydroxide, copper oxychloride sulfate (COCS), copper oxide, ternary copper sulfate (such as copper sulfate), copper trihydrate, hemihydrate, and / or any combination thereof. In a preferred embodiment, the copper-based fungicide is selected from copper acetate, copper chloride, copper chlorate, copper formate, copper hexafluorosilate, copper nitrate, copper chromate, copper sulfate pentahydrate, Baudouin mixed solution, and any combination thereof. In a more preferred embodiment, the copper-based fungicide is selected from copper sulfate pentahydrate, Baudouin mixed solution, and / or any combination thereof.

[0098] In some embodiments, the amount of the copper-based fungicide is from about 16% to about 24% by weight, based on the total weight of the composition. In a preferred embodiment, the amount of the copper-based fungicide is from about 18% to 22% by weight, based on the total weight of the composition.

[0099] In some embodiments, the composition of the present invention comprises a) a buffer system, which is a combination of carboxylic acid and base; b) tannic acid and c) a copper-based fungicide. In some embodiments, the composition of the present invention comprises a) a buffer system, which is a combination of acetic acid and ammonium hydroxide; b) tannic acid and c) a bromide mixture as a copper-based fungicide.

[0100] In some embodiments, the copper content of the copper-based fungicide is from about 40 g / L to about 500 g / L. In a preferred embodiment, the copper content is from about 50 g / L to about 300 g / L. In a more preferred embodiment, the copper content is from about 50 g / L to about 100 g / L. In a particular preferred embodiment, the copper content is about 66 g / L.

[0101] In some embodiments, the molar ratio between the carboxylic acid and the copper-based fungicide is from about 3.5:1 to about 18:1. In a preferred embodiment, the molar ratio between the carboxylic acid and the copper-based fungicide is from about 10:1 to about 18:1. In a preferred embodiment, the molar ratio between the carboxylic acid and the copper-based fungicide is from about 15:1 to about 18:1.

[0102] In some embodiments, the molar ratio between the alkali and the copper-based fungicide is from about 3.7:1 to about 17:1. In a preferred embodiment, the molar ratio between the alkali and the copper-based fungicide is from about 10:1 to about 16:1. In a preferred embodiment, the molar ratio between the alkali and the copper-based fungicide is from about 11:1 to about 15:1.

[0103] In some embodiments, the composition of the present invention further includes a stabilizer.

[0104] In some embodiments, the stabilizer is selected from salts of propionic acid, sodium salts of butyric acid, sodium salts of valerate, and any combination thereof. In a preferred embodiment, the stabilizer is a salt of propionic acid.

[0105] In some embodiments, the salt may be sourced from sodium, calcium, magnesium, potassium, lithium, or any combination thereof. In a preferred embodiment, the salt is sourced from sodium.

[0106] In a preferred embodiment, the stabilizer is a sodium salt of propionic acid.

[0107] In some embodiments, the composition of the present invention comprises a) a buffer system, which is a combination of acetic acid and ammonium hydroxide; b) tannic acid; c) a mixture of copper-based fungicides and a stabilizer. In some embodiments, the composition of the present invention comprises a) a buffer system, which is a combination of acetic acid and ammonium hydroxide; b) tannic acid; c) a mixture of copper-based fungicides and a sodium salt of propionic acid as a stabilizer.

[0108] In some embodiments, the amount of stabilizer is from about 0.8% by weight to about 1.0% by weight, based on the total weight of the composition. In a preferred embodiment, the amount of stabilizer is about 0.9% by weight, based on the total weight of the composition.

[0109] In some embodiments, the composition of the present invention further comprises additives. Non-limiting examples include antifreeze, defoamers, thickeners, rheology modifiers, and any other additional additives known in formulation industry practices, and any combination thereof. In some preferred embodiments, the additives are selected from thickeners and rheology modifiers. In some embodiments, the rheology modifier is xanthan gum.

[0110] In some embodiments, the composition of the present invention comprises a) a buffer system, which is a combination of acetic acid and ammonium hydroxide; b) tannic acid; c) a mixture of copper-based fungicides, a stabilizer, and an additive. In some embodiments, the composition of the present invention comprises a) a buffer system, which is a combination of acetic acid and ammonium hydroxide; b) tannic acid; c) a mixture of copper-based fungicides, a sodium salt of propionic acid as a stabilizer, and a rheology modifier as an additive. In some embodiments, the composition of the present invention comprises a) a buffer system, which is a combination of acetic acid and ammonium hydroxide; b) tannic acid; c) a mixture of copper-based fungicides, a sodium salt of propionic acid as a stabilizer, and xanthan gum as a rheology modifier.

[0111] In some embodiments, the composition of the present invention comprises a) about 28% by weight of acetic acid and about 20% by weight of ammonium hydroxide, based on the total weight of the composition; b) about 0.5% by weight of tannic acid, based on the total weight of the composition; c) about 18% by weight of Porto mixture, based on the total weight of the composition; about 0.9% by weight of sodium propionic acid, based on the total weight of the composition; and about 0.3% by weight of xanthan gum, based on the total weight of the composition.

[0112] In some embodiments, the dosage of the composition of the present invention is from about 0.4 L / ha to about 5 L / ha. In some embodiments, the dosage of the composition of the present invention is from about 1 L / ha to about 4 L / ha. In some embodiments, the dosage of the composition of the present invention is from about 2.5 L / ha to about 3.5 L / ha.

[0113] In some embodiments, the present invention also provides a method for reducing eye irritation by applying the disclosed composition.

[0114] In some embodiments, the present invention also provides a method for reducing aquatic toxicity by applying the disclosed composition.

[0115] All components of the present invention are formulated into a suspension concentrate (SC).

[0116] More particularly, the formulation of the present invention provides a stable copper fungicide SC formulation, which may be combined with further active ingredients, preferably selected from fungicides, to treat plants.

[0117] All components and / or combinations of the present invention may further comprise one or more active antifungal, antibacterial, insecticidal, or herbicidal ingredients. Preferably, the components of the present invention comprise one or more active insecticidal, antibacterial, or antifungal ingredients, more preferably one or more active antifungal or antibacterial ingredients, and even more preferably one or more active antifungal ingredients.

[0118] Non-limited examples of active fungicidal mixture partners include metalaxyl, zoxamide, fluopicolide, ametoctradin, amisulbrom, cymoxanil, mandipropamid, dimethomorph, captan, folpet, mancozeb, difenoconazole, metconazole, tebuconazole, azoxystrobin, picoxystrobin, trifloxystrobin, pydiflumetofen, fluxapyroxad, fluopyram, and any combination thereof.

[0119] The present invention also provides a suspension obtained by mixing water with the liquid composition of the present invention. The mixing ratio of water to the suspension concentrate can be in the range of 1500:1 to 1:1, preferably in the range of 500:1 to 10:1.

[0120] Dilution is achieved by pouring the concentrate of the present invention into water. For rapid mixing of the concentrate and water, stirring is typically used. However, stirring is usually unnecessary. Although the temperature used for dilution is not a critical factor, dilution is generally carried out at 0°C to 50°C, particularly in the temperature range of 5°C to 40°C, or at ambient temperature.

[0121] The water used for dilution is typically tap water. However, the water may already contain water-soluble or finely dispersed compounds used for crop protection, such as nutrients, fertilizers, or pesticides. Various oils, wetting agents, adjuvants, buffers, fertilizers or micronutrients, and further pesticides (such as herbicides, insecticides, fungicides, growth regulators, safeners, inducers) may be added to the suspension of the present invention in a premixed form or, as needed, shortly before use (bucket mixing). They may be added to the composition of the present invention at a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.

[0122] Users typically apply the composition of this invention using pre-dose systems, backpack sprayers, spray cans, spray aircraft, drones, or irrigation systems; the composition of this invention is typically diluted with water, buffers, and / or other adjuvants to the desired concentration, providing the ready-to-use spray solution or agricultural chemical composition of this invention. Typically, 20 to 2000 liters, preferably 50 to 1000 liters, of ready-to-use spray solution are prepared per hectare of applicable agricultural area.

[0123] The general diluted components of the present invention are mainly applied by spraying, especially by spraying leaves. Application can be carried out by spraying techniques known to those skilled in the art, such as using water as a carrier, and the amount of spray liquid is about 50 to 1000 liters per hectare, such as 100 to 200 liters per hectare.

[0124] The present invention is illustrated by the following examples, but is not limited thereto. Example 1 – Blend A Components weight% Porto Mixture 18.2 ammonium hydroxide 20.0 Acetic acid 27.9 Tannic acid 0.5 Sodium propionic acid 0.9 Propylene glycol 8.0 Polydimethylsiloxane, methyl-terminated 0.04 Xanthan Gum 0.3 water 24.16 Preparation method:

[0125] 1.1. Initially, 20 parts of ammonium hydroxide were loaded into a laboratory reactor and cooled at about 6°C.

[0126] 1.2. Then, add 10.7 parts water and mix until homogeneous.

[0127] 1.3. While the mixture is still cold, slowly add 27.9 parts of acetic acid at a controlled temperature (6 to 15°C).

[0128] 1.4. Add tannic acid (0.5 parts) and dilute it thoroughly in the system.

[0129] 1.5. Before adding 18.2 parts of the Porto mixture, heat the mixture to a temperature range of 65 to 68°C and mix vigorously for 1 hour.

[0130] 1.6. After stirring, add polydimethylsiloxane, methyl-terminated (0.008 parts), and heat the mixture to 50°C.

[0131] 1.7. Grind the mixture in a horizontal mill (Mini Lab II NETZSCH) and then dilute it with 8 parts of propylene glycol at a maximum temperature of 52°C before adding 0.9 parts of sodium propionate.

[0132] 1.8. Finally, xanthan gum is hydrated with the remaining water and then added to the mixture.

[0133] 1.9. The product was kept at 43°C with stirring for 3 hours, and the remaining polydimethylsiloxane was added 30 minutes before the end of stirring.

[0134] 1.10. Bring the final mixture to a temperature of 32°C. Example 2 – Phytotoxicity in grapes:

[0135] The purpose of this experiment is to evaluate the phytotoxicity and selectivity of formulation A and Phyton 27 relative to commercially available standard products in the control of powdery mildew in grapes.

[0136] This experiment was conducted on a sensitive wine grape variety in Ribadumia, a municipality in Spain. Method

[0137] Apply eight times as a preventative measure, following local practices, from pre-flowering until fruit development (when most berries are in contact with each other). The application interval is 7 to 14 days, depending on weather conditions and local copper compound practices. Water volume: 1000 L / ha. Efficacy and selectivity in leaves and berries were evaluated. Results

[0138] Starting from the third application, some treatments showed that phytotoxicity caused changes in leaf color: Table 1. serial number deal with Application rate (L or Kg / Ha) Application (gr Cu / Ha) Phytotoxicity (%) after one application Phytotoxicity (%) after two applications Phytotoxicity (%) after 3 applications Phytotoxicity (%) after 4 applications Phytotoxicity (%) after 5 applications 1 Untreated inspection 0 0 0 0 0 2 Blend A 1.5 99 0 0 0 1.3 7.5 3 PHYTON 27 1.5 97.5 0 0 0 11.3 20

[0139] In formulation A, applied 1 to 4 times, 1.5 L / Ha (99 gCu / Ha) did not appear to show any or obvious phytotoxicity symptoms; however, the Phyton 27 formulation showed greater phytotoxicity. Example 3 – Apple fruit browning and roughening test setup and protocol:

[0140] Between 2018 and 2019, six field trials were conducted in EU countries to verify the effect of formulation A on browning and roughening of apple fruit in apple varieties known to be sensitive to different copper fungicides. The treated apple plants were grown according to best practices and were in full production at the time of the trials.

[0141] In accordance with the EPPO guidelines, the experiment was conducted using an RCB (randomized block design). As shown in the table below, the experimental protocol included a multi-product spraying program (up to 8 or more applications) throughout the crop growth cycle, with intervals of 7 to 10 days depending on local weather conditions. Mixture A was applied at 2.5 L / ha, 3 L / ha, 3.5 L / ha, and 4 L / ha, accompanied by various commercially available products based on Bordo mixtures (in France: Bouille Bodelaise RSR Disperss; in Italy: Poltiglia Disperss; in Portugal: Caldo Bordoles RSR Disperss) at a rate of 6 kg / ha as reference standards.

[0142] At harvest or when the fruit is fully developed, the presence of brown roughness on the peel is visually assessed, and the fruit is divided into three categories (A: no brown roughness observed, B: brown roughness present but commercially acceptable, C: severe brown roughness, fruit devalued or commercially unacceptable). Experimental protocol: Crop: Apple Processing Number Processing Name Application rate per hectare (L or kg) Number of applications time 1 Unprocessed - 4 Blend A 2.5 L 8 to 10 times 7 to 10 days 5 Blend A 3 L 6 Blend A 3.5 L 7 Blend A 4 L 8 Standard products (mainly based on Porto mixture) 6 kg result

[0143] As shown in the table below, when formulation A was applied at the highest application rates (3, 5, and 4 L / ha), the incidence of brown roughness in apple fruits was lower compared to the commercially available reference product. This lower incidence of brown roughness compared to the commercially available reference product can be seen as a reduction in the incidence of brown roughness in individual fruit categories and a trend towards higher-priced commercially available fruit categories.

[0144] Results Table. Data are expressed as a percentage (%) of the harvested fruit and are divided into three categories, A, B, and C, corresponding to different degrees of browning and roughening on the fruit. Table 2. Test ID and Variety Fruit varieties (%) fruit Product Name Blend A Blend A Blend A Blend A Standard products Unprocessed category* Product application rate / ha 2.5 L / ha 3 L / ha 3.5 L / ha 4 L / ha 6 kg / ha Cu application rate (g / ha)* 165 198 231 264 1200 FR18FEMABSD403A A 16 20 8 8 2 84 Golden B 19 12 9 14 4 2 C 64 69 83 78 95 14 FR18FEMABSD403B A 7 3 4 2 3 8 Gold B 40 45 45 39 20 76 C 53 52 51 59 77 16 IT18FEMABSD334B A 89 90 83 82 79 100 Gold B 9 7 10 12 11 0 C 2 4 7 6 10 0 FR19FEMABSD460A A 69 50 26 36 15 98 Gold B 11 9 13 3 7 1 C 20 41 61 62 79 2 PT18FEMABSD361A A twenty two 20 18 17 18 29 Gala (Royal Gala) B 44 48 50 48 63 55 C 34 32 32 35 19 16 IT19FEMABSD346A A 95 90 85 80 80 100 Fuji B 5 10 10 10 5 0 C 0 0 5 10 15 0 * A: No browning roughness observed; B: Browning roughness present, but commercially acceptable; C: Severe browning roughness, fruit is devalued or commercially unacceptable. Example 4 – Test setup and protocol for the efficacy of grapevines against grape downy mildew (P. viticola).

[0145] In 2021, a commercial vineyard in Italy conducted a trial to compare the efficacy of formulation A with other commercially available products with similar properties against powdery mildew [grape downy mildew (Plasmopara viticola)]. Following EPPO guidelines, the trial was conducted using an RCB (randomized block design). As shown in the table below, the trial protocol included a spraying schedule throughout the crop growing season (up to 10 applications), spaced approximately 7 days apart depending on local weather conditions. Formulation A was applied at 3.5 L / ha and 4 L / ha, while Bordoflow new was applied at 2.6 L / ha and 5 L / ha. Formulation A and the standard Bordoflow new were tested at additionally lower rates of copper delivery per hectare, in addition to their recommended labeled application rates.

[0146] Assess the presence of powdery mildew on leaves and foliage, and calculate efficacy according to EPPO guidelines. Experimental protocol deal with Types of ingredients Application rate per hectare (L or kg) Number of applications time Untreated inspection Blend A (231 gCu / ha) SC 3.5 L 10 times 7 days Blend A (264 gCu / ha) SC 4 L BORDOFLOW NEW SC 2.6 L BORDOFLOW NEW SC 5 L Table 3. deal with Application rate [l / ha] Severity [Efficacy %] Leaf severity [efficacy %] Untreated inspection 0 (d) 0 (e) Blend A (231 gCu / ha) 3.5 91.2 (ab) 85.7 (a) Blend A (264 gCu / ha) 4.0 92.9 (ab) 88.2 (a) Bordoflow new (322 gCu / ha) 2.6 81.4 (c) 46.0 (d) Bordoflow new (620 gCu / ha) 5.0 91.7 (ab) 70.1 (c) result

[0147] Table 3 confirms that formulation A showed better efficacy than the commercially available product Bordoflow new (SC formulation) on both clumps and leaves. The results showed that even at lower copper dosages and lower application rates, formulation A achieved better efficacy than Bordoflow new. [Simplified Explanation of the Diagram]

[0020] Figure 1. Phytotoxicity level (%) of leaves after foliar application.

Claims

1. A composition comprising: a) a buffer system; b) tannic acid and c) a copper-based fungicide, in the form of a suspension concentrate, wherein the buffer system is a combination of a carboxylic acid and a base, and the carboxylic acid is selected from any combination of acetic acid, citric acid, propionic acid, butyric acid and / or the like, the weight ratio of the carboxylic acid to the base is from 1.2:1 to 1.4:1 and the molar ratio of the base to the copper-based fungicide is from 10:1 to 16:

1.

2. The composition of claim 1, wherein the copper-based fungicide is selected from copper sulfate pentahydrate, bromosulfate mixture and / or any combination thereof.

3. The composition of claim 1 or 2, wherein the base is ammonium hydroxide.

4. The composition of claim 1 or 2, wherein the molar ratio between the carboxylic acid and the copper-based fungicide is 3.5:1 to 18:

1.

5. The composition of claim 1 or 2, wherein the amount of carboxylic acid is 22% to 38% by weight based on the total weight of the composition.

6. The composition of claim 1 or 2, wherein the amount of alkali is 19% to 24% by weight based on the total weight of the composition.

7. The composition of claim 1 or 2, wherein the amount of tannic acid in the composition is from 0.49% to 0.51% by weight, based on the total weight of the composition.

8. The composition of claim 1 or 2, wherein the amount of the copper-based fungicide is 16% to 24% by weight based on the total weight of the composition.

9. The composition of claim 1 or 2, wherein the copper content of the copper-based fungicide is 66 g / l.

10. The composition of claim 1 or 2 further comprises a stabilizer selected from salts of propionic acid, salts of butyric acid, salts of valeric acid and / or any combination thereof.

11. The composition of claim 10, wherein the amount of the stabilizer is from 0.8% to 1.0% by weight based on the total weight of the composition.

12. The composition of claim 1 or 2, wherein the composition is applied in an amount of 0.4 L / ha to 5 L / ha.

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