EP4213629A1

EP4213629A1 - Formulation of copper-based fungicides and bactericide

Info

Publication number: EP4213629A1
Application number: EP21802018.8A
Authority: EP
Inventors: Pedro Gonzalez; Juan Daniel DZUL PUC
Original assignee: Adama Makhteshim Ltd
Current assignee: Adama Makhteshim Ltd
Priority date: 2020-09-16
Filing date: 2021-09-13
Publication date: 2023-07-26
Also published as: CN116347986A; MX2023002963A; TW202226948A; WO2022059002A1

Abstract

The invention relates to novel composition comprising a) a buffering system; b) tannic acid and c) a copper-based fungicide. The invention also relates to a method for reducing phytotoxicity by applying a composition comprising: a) a buffering system; b) tannic acid and c) a copper-based fungicide to a locus. The invention further relates to the use of a buffering system for stabilizing liquid composition of a copper-based fungicide.

Description

TITLE:

FORMULATION OF COPPER-BASED FUNGICIDES AND BACTERICIDE

TECHNICAL FIELD OF THE INVENTION

The present invention concerns a unique fungicide and bactericide formulation which contain copperbased fungicide as active ingredient, tannic acid and a buffering system.

BACKGROUND OF THE INVENTION

Copper-based pesticides are widely used in agrochemical products to control a wide range of fungal, bacterial, and other pests. Copper was one of the first elements used as a plant fungicide and its discovery can be traced back to the famous origin of bordeaux mixture, containing a mixture of copper sulfate (CuSO4) and slaked lime, used for downy mildew control in French vineyards.

Copper-based fungicides are divided into compounds that are highly soluble in water such as cupric acetate, cupric chloride and cupric chlorate, cupric formate, cupric hexafluorosilicate, cupric nitrate, cupric chromate, copper sulfate pentahydrate and bordeaux mixture; and compounds such as copper hydroxide, copper oxychloride sulfate (COCS), and tribasic copper sulfate (cupric sulfate, tricupric hydroxide, hemihydrate) which also known as "fixed" coppers that are relatively less soluble in water.

Copper-based fungicides are important, due to their low costs and their protectant/preventative characteristics and abilities to inhibit fungal spore germination and hyphal penetration. The fungal control is provided when the copper particles slowly dissolve in contact with water releasing Cu+2 ions.

The copper particles adhere to the leaf surface and act as ion reservoirs, continuously releasing Cu+2 ions and forming a protective layer which prevent infection. Copper fungicides formulations vary in the efficiency of Cu+2 ion release which is dependent upon the copper source. Moreover, the concentration of copper ions on the leaves depends on the equilibrium established with the complexed and soluble forms of copper (Menkissoglu and Lindow 1991).

The performance of the formulation is therefore highly dependent on its technology for generating a stable complex allowing moderate and long-lasting effect of release of copper ions. It is known that copper is toxic when the dissolved form penetrates into plant tissue. In general, the use of spray additives such as foliar nutrients, and any surfactants with penetrating characteristics should be avoided when applying copper-based fungicides.

It is also known that certain copper-based fungicides available in the market are associated with high eye irritancy and aquatic toxicity.

Currently in the market there are several solid formulations of copper-based fungicide such as Kocide (DuPont), BORDELES RSR DISPERSS (UPL), Champ® WG (Nufarm) and etc.; Suspension concentrate (SC) formulations have many advantages due to their low cost, lower skin penetration and easier handling by the farmer; therefore effective copper-based SC formulation can be very useful in the agriculture filed.

SC compositions containing copper sulphate pentahydrate and tannate complex of picro ammonium formate were disclosed in US 4544666 and US 4673687. These compositions contain picric acid which has many disadvantages and is known as an explosive compound that should be handled very carefully.

Therefore, there is a need for copper-based fungicide compositions comprising reduce quantities of copper-based fungicides, that are easy to handle, safer for the user and greener for the environment.

It was surprisingly been found that the compositions of the present invention comprising water soluble copper-based fungicide cause less plant injury than known formulations in the market.

The invention provides novel, improved safer and greener copper-based fungicide compositions which have low copper content and does not use the addition of unwanted surfactants.

The compositions of the invention show high bioavailability of long-acting copper when diluted in water and shows an effective control against fungal-infected cultures compared to other traditional copperbased products.

It has surprisingly been found that the compositions of the present invention reduce eye irritancy.

SUMMARY

The present invention therefore provides an agrochemical composition comprising a) a buffering system; b) tannic acid and c) a copper-based fungicide. The invention also provides a method for reducing phytotoxicity by applying a composition comprising a) a buffering system; b) tannic acid and c) a copper-based fungicide to a locus.

The present invention also provides the use of a buffering system for stabilizing liquid compositions of a copper-based fungicide.

Furthermore, the present invention provides methods for reducing eye irritancy and aquatic toxicity by applying the disclosed compositions.

BRIEF DESCRIPTION OF THE FIGURE

Figure 1. Leaf Phytotoxicity level (%) after foliar applications.

DETAILED DESCRIPTION OF THE PREFERED EMBODIMENTS

Definitions

Prior to setting forth the present subject matter in detail, it may be helpful to provide definitions of certain terms to be used herein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art to which this subject matter pertains. The following definitions are provided for clarity.

The term "a" or "an" as used herein includes the singular and the plural, unless specifically stated otherwise. Therefore, the terms "a," "an," or "at least one" can be used interchangeably in this application.

As used herein, the verb "comprise" as is used in this description and in the claims and its conjugations are used in its non-limiting sense to mean that items following the word are included, but items not specifically mentioned are not excluded.

As used herein, the term "about" when used in connection with a numerical value includes ±10% from the indicated value. In addition, all ranges directed to the same component or property herein are inclusive of the endpoints, are independently combinable, and include all intermediate points and ranges. It is understood that where a parameter range is provided, all integers within that range, and tenths thereof, are also provided by the invention. As used herein, the term "effective amount" refers to an amount of the active component that is commercially recommended for use to control and/or prevent pest. The commercially recommended amount for each active component, often specified as application rates of the commercial formulation, may be found on the label accompanying the commercial formulation. The commercially recommended application rates of the commercial formulation may vary depending on factors such as the plant species and the pest to be controlled.

As used herein, the term "pest" includes, but is not limited to, unwanted phytopathogenic harmful fungi, unwanted insect, unwanted nematode, and weed.

As used herein, the term "pesticide" broadly refers to an agent that can be used to prevent, control and/or kill a pest. The term is understood to include but is not limited to fungicides, insecticides, nematicides, herbicides, acaricides, parasiticides or other control agents. For chemical classes and applications, as well as specific compounds of each class, see "The Pesticide Manual Thirteenth Edition" (British Crop Protection Council, Hampshire, UK, 2003), as well as "The e-Pesticide Manual, Version 3" (British Crop Protection Council, Hampshire, UK, 2003-04), the contents of each of which are incorporated herein by reference in their entirety.

As used herein, the term "locus" includes not only areas where the pest may already be developed, but also areas where pests have yet to emerge, and also to areas under cultivation. Locus includes the plant or crop and propagation material of the plant or crop. Locus also includes the area surrounding the plant or crop and the growing media of the plant or crop, such as soil and crop field.

As used herein the term "plant" or "crop" includes reference to whole plants, plant organs (e.g. leaves, stems, twigs, roots, trunks, limbs, shoots, fruits etc.), plant cells, or plant seeds. This term also encompasses plant crops such as fruits, spores, corms, bulbs, rhizomes, sprouts basal shoots, stolons, and buds and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil.

As used herein the term "ha" refers to hectare.

The term "Copper dose" represents the quantity of active ingredient provided by the formulation. The present invention provides a fungicide composition comprising a) a buffering system; b) tannic acid and c) a copper-based fungicide.

In some embodiments, the buffering system is a combination of a carboxylic acid and a base.

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.

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

In some embodiments, the base is ammonium hydroxide.

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

In some embodiments the carboxylic acid is added in excess with respect to the base.

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

In some embodiments, the amount of tannic acid in the composition is of about 0.49 % 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 of about 0.5% by weight, based on the total weight of the composition.

In some embodiments, the copper-based fungicide is selected from cupric acetate, cupric chloride, cupric chlorate, cupric formate, cupric hexafluorosilicate, cupric nitrate, cupric chromate, copper sulfate pentahydrate, bordeaux mixture, copper hydroxide, copper oxychloride sulfate (COCS), tribasic copper sulfate such as cupric sulfate, tricupric hydroxide, hemihydrate and/or any combination thereof. In a preferred embodiment, the copper-based fungicide is selected from cupric acetate, cupric chloride, cupric chlorate, cupric formate, cupric hexafluorosilicate, cupric nitrate, cupric chromate, copper sulfate pentahydrate, bordeaux mixture and any combination thereof. In more preferred embodiment, the copper-based fungicide is selected from copper sulfate pentahydrate, bordeaux mixture and/or any combination thereof.

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

In some embodiments, the compositions of the invention comprising a) a buffering system which is a combination of a carboxylic acid and a base; b) tannic acid and c) a copper-based fungicide. In some embodiments, the compositions of the invention comprising a) a buffering system which is a combination of acetic acid and ammonium hydroxide; b) tannic acid and c) bordeaux mixture as a copper-based fungicide.

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 particularly preferred embodiment, the copper content is about 66 g/l.

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

In some embodiments, the molar ratio between the base to copper-based fungicide is of about 3.7:1 to about 17:1. In a preferred embodiment, the molar ratio between the base to copper-based fungicide is of about 10:1 to about 16:1. In a preferred embodiment, the molar ratio between the base to copperbased fungicide is of about 11:1 to about 15:1.

In some embodiments, the composition of the present invention is further comprising stabilizers.

In some embodiments, the stabilizers are selected from the salts of propionic acid, sodium salt of butyric acid, sodium salt of valeric acid and any combination thereof. In a preferred embodiment the stabilizer is the salt of propionic acid. In some embodiments the origin of the salt is may be selected from sodium, calcium, magnesium, potassium, lithium and/or any combination thereof. In a preferred embodiment the origin of the salt is sodium.

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

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

In some embodiments, the compositions of the invention comprising a) a buffering system which is a combination of acetic acid and ammonium hydroxide; b) tannic acid; c) bordeaux mixture as a copperbased fungicide and a stabilizer. In some embodiments, the compositions of the invention comprising a) a buffering system which is a combination of acetic acid and ammonium hydroxide; b) tannic acid; c) bordeaux mixture as a copper-based fungicide and sodium salt of propionic acid as the stabilizer.

In some embodiments, the composition of the present invention further comprising additives. Non limiting examples are anti-freezing agents, anti-foaming agents, thickening agent, rheological agent, and any other additional additive which is known from common practice in the formulation industry and any combination thereof. In some preferred embodiment the additive is selected from thickening agent and rheological agent. In some embodiments the rheological agent is Xanthan Gum.

In some embodiments, the compositions of the invention comprising a) a buffering system which is a combination of acetic acid and ammonium hydroxide; b) tannic acid; c) bordeaux mixture as a copperbased fungicide, a stabilizer and an additive. In some embodiments, the compositions of the invention comprising a) a buffering system which is a combination of acetic acid and ammonium hydroxide; b) tannic acid; c) bordeaux mixture as a copper-based fungicide, sodium salt of propionic acid as the stabilizer and rheological agent as an additive. In some embodiments, the compositions of the invention comprising a) a buffering system which is a combination of acetic acid and ammonium hydroxide; b) tannic acid; c) bordeaux mixture as a copper-based fungicide, sodium salt of propionic acid as the stabilizer and Xanthan Gum as the rheological agent. In some embodiments, the compositions of the invention comprising a) acetic acid in amount of about 28% and ammonium hydroxide in amount of about 20%, by weight, based on the total weight of the composition; b) tannic acid in amount of about 0.5% by weight, based on the total weight of the composition; c) bordeaux mixture in amount of about 18% by weight, based on the total weight of the composition; sodium salt of propionic acid in amount of about 0.9% by weight, based on the total weight of the composition and Xanthan Gum in amount of about 0.3% by weight, based on the total weight of the composition.

In some embodiments, the composition of the present invention is applied in an amount from about 0.4 L/ha to about 5 L/ha. In some embodiments, the composition of the present invention is applied in an amount from about 1 L/ha to about 4 L/ha. In some embodiments, the composition of the present invention is applied in an amount from about 2.5 L/ha to about 3.5 L/ha.

The compositions of the invention copper fungicide, carboxylic acid, base and tannic acid obtained through an integrated manufacturing process generating a supersaturated solution that is stabilized during its preparation for optimal use in crop protection with : (a) carboxylic acid that together with the salt formed from the same acid, which creates a buffering system that allows it to remain stable in dilution by acid buffering of the dilution medium and ensure better application to the plant and (b) with a rheological agent to ensure stability as a concentrated product during its half-life but no dispersant agent required.

The compositions of the present invention are designed to make a special interaction of the ingredients without the use of dispersants. The interaction is created initially during formulation (copper interaction instead of dispersion) with the ingredients and then with the water under dilution.

The compositions of the invention are prepared by the following addition order: a) buffering system; b) tannic acid and c) a copper-based fungicide.

The present invention also provides a method of controlling phytopathogenic harmful fungi and/or bacteria in a field of crop comprising applying an effective amount of the compositions disclosed herein to a field of crop so as to thereby control the phytopathogenic harmful fungi and/or bacteria in the field of crop. In some embodiments, the crop is selected from the group consisting of cotton, grapevines, fruit, vegetables, such as Rosaceae sp. (for example pome fruit such as apples and pears, but also stone fruit such as apricots, cherries, almonds and peaches, and berry fruits such as strawberries), Ribesioidae sp., Juglandaceae sp., Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp., Actinidaceae sp., Lauraceae sp., Musaceae sp. (for example banana trees and plantations), Rubiaceae sp. (for example coffee), Theaceae sp., Sterculiceae sp., Rutaceae sp. (for example lemons and grapefruit); Solanaceae sp. (for example tomatoes), Liliaceae sp., Asteraceae sp. (for example lettuce), Umbelliferae sp., Cruciferae sp., Chenopodiaceae sp., Cucurbitaceae sp. (for example cucumbers), Alliaceae sp. (for example leeks, onions), Papilionaceae sp. (for example peas); main crop plants such as Gramineae sp. (for example maize, turfgrass, cereals such as wheat, rye, rice, barley, oats, sorghum/millet and triticale), Asteraceae sp. (for example sunflowers), Brassicaceae sp. (for example white cabbage, red cabbage, broccoli, cauliflower, Brussels sprouts, Pak Choi, kohlrabi, radishes, and rapeseed, mustard, horseradish and cress), Fabaceae sp. (for example beans, peanuts), Papilionaceae sp. (for example soya beans), Solanaceae sp. (for example potatoes), Chenopodiaceae sp. (for example sugar beet, fodder beet, chard, beetroot); sugarcane, poppies, olives, coconuts, cocoa, tobacco and useful plants and ornamental plants in gardens and forests; and genetically modified varieties of each of these plants, and the seeds of these plants. In a preferred embodiment, the crop is selected from the group consisting of Fruit trees, vines and Vegetables. In a more preferred embodiment, the crop is selected from the group consisting of Pome fruits such as apple and pear; Stone Fruits such as Peach, apricot and almond; Tree nuts such as Walnut, hazelnut; Vines such as Grapes, Kiwi and Hop, other tree crops such as olive, citrus, avocado; Fruiting vegetables such as Tomato, Pepper and cucumber; Root & tuber such as Potato and Carrot; Leafy Vegetables such as Lettuce and Cabbage; Oil crops such as sunflower and oil Seed Rape; Cereals such as Wheat, Rye, Barely and Rice; Small fruits like blackberry and blueberry; Ornamentals like roses and Azalea and Herbs like mint and basil.

Non-limiting examples of pathogens of fungal diseases which may be treated in accordance with the invention include: diseases caused by powdery mildew pathogens, for example Blumeria species, for example Blumeria graminis, Podosphaera species, for example Podosphaera leucotricha, Sphaerotheca species, for example Sphaerotheca fuliginea, Uncinula species, for example Uncinula necator, for example Erysiphe species; diseases caused by rust disease pathogens, for example Gymnosporangium species, for example Gymnosporangium sabinae ; Hemileia species, for example Hemileia vastatrix; Phakopsora species, for example Phakopsora pachyrhizi or Phakopsora meibomiae Puccinia species, for example Puccinia recondita, Puccinia graminis oder Puccinia striif ormis, Uromyces species, for example Uromyces app endiculatus, diseases caused by pathogens from the group of the Oomycetes, for example Albugo species, for example Albugo Candida , Bremia species, for example Bremia laciucaer, Peronospora species, for example Peronospora pisi or P. brassicaer, Phytophthora species, for example Phytophthora infestans, Plasmopara species, for example Plasmopara viticola, Pseudoperonospora species, for example Pseudoperonospora humuli or Pseudoperonospora cubensis, Pythium species, for example Pythium ultimum, leaf blotch diseases and leaf wilt diseases caused, for example, by Alternaria species, for example Alternaria solani, Cercospora species, for example Cercospora beticola, Cladosporium species, for example Cladosporium cucumerinunr, Cochliobolus species, for example Cochliobolus sativus (conidial form: Drechslera, syn: Helminthosporium) or Cochliobolus miyabeanus, Colletotrichum species, for example Colletotrichum lindemuthianum, Corynespora species, for example Corynespora cassiicola, Cycloconium species, or example Cycloconium oleaginunv, Diaporthe species, for example Diaporthe citrv, Elsinoe species, for example Elsinoe f awcettii, Gloeosporium species, for example Gloeosporium laeticolor, Glomerella species, for example Glomerella cingulata, Guignardia species, for example Guignardia bidwellv, Leptosphaeria species, for example Leptosphaeria maculans, Magnaporthe species, for example Magnaporthe grisea, Microdochium species, for example Microdochium nivaler, Mycosphaerella species, for example Mycosphaerella graminicola (also known as Septoria tritici), Mycosphaerella arachidicola or Mycosphaerella fi j iens , Phaeosphaeria species, for example Phaeosphaeria nodorunr, Pyrenophora species, for example Pyrenophora teres or Pyrenophora tritici rep enth , Ramularia species, for example Ramularia collo-cygni or Ramularia areola, Rhynchosporium species, for example Rhynchosporium secalis, Septoria species, for example Septoria apii or Septoria lycopersici, Stagonospora species, for example Stagonospora nodorum, Typhula species, for example Typhula incarnata, Venturia species, for example Venturia inaequalis, root and stem diseases caused, for example, by Corticium species, for example Corticium solani, Fusarium species, for example Fusarium oxysporum\ graminearum species, for example Gaeumannomyces graminis, Plasmodiophora species, for example Plasmodiophora brassica, Rhizoctonia species, for example Rhizoctonia solani, Sarocladium species, for example Sarocladium oryzae; Sclerotium species, for example Sclerotium oryzae, Tapesia species, for example Tapesia acuformis, Thielaviopsis species, for example Thielaviopsis basicola, ear and panicle diseases (including com cobs) caused, for example, by Alternaria species, for example Alternaria spp.; Aspergillus species, for example Aspergillus flavus, Cladosporium species, for example Cladosporium cladosporioides, Claviceps species, for example Claviceps purpurea, Fusarium species, for example Fusarium culmorunr, Gibberella species, for example Gibberella zeae Monographella species, for example Monographella nivalis, Stagnospora species, for example Stagnospora nodorunr, diseases caused by smut fungi, for example Sphacelotheca species, for example Sphacelotheca reiliana, Tilletia species, for example Tilletia caries or Tilletia controversy, Urocystis species, for example Urocystis occulta, Ustilago species, for example Ustilago nuda, fruit rot caused, for example, by Aspergillus species, for example Aspergillus flavus, Botrytis species, for example Botrytis cinerea, Monilinia species, for example Monilinia lotxot, Penicillium species, for example Penicillium expansum or Penicillium purpurogenum, Rhizopus species, for example Rhizopus stolonifer, Sclerotinia species, for example Sclerotinia sclerotiorum, Verticillium species, for example Verticillium albo-atrum, seed- and soil-borne rot and wilt diseases, and also diseases of seedlings, caused, for example, by Alternaria species, for example Alternaria brassicicola, Aphanomyces species, for example Aphanomyces euteiches, Ascochyta species, for example Ascochyta lends, Aspergillus species, or example Aspergillus flavus, Cladosporium species, for example Cladosporium herbarum, Cochliobolus species, for example Cochliobolus sativus (conidial form: Drechslera, Bipolaris Syn: Helminthosp orium), Colletotrichum species, for example Colletotrichum coccodes, Fusarium species, for example Fusarium culmorum, Gibberella species, for example Gibberella zeae, Macrophomina species, for example Macrophomina phaseolina, Microdochium species, for example Microdochium nivale , Monographella species, for example Monographella nivalis, Penicillium species, for example Penicillium expansum, Phoma species, for example Phoma lingam, Phomopsis species, for example Phomopsis so ae Phytophthora species, for example Phytophthora cactorum, Pyrenophora species, for example Pyrenophora graminea, Pyricularia species, for example Pyricularia oryzae, Pythium species, for example Pythium ultimum, Rhizoctonia species, for example Rhizoctonia solani, Rhizopus species, for example Rhizopus oryzae; Sclerotium species, for example Sclerotium rolfsii, Septoria species, for example Septoria nodorum, Typhula species, for example Typhula incarnata, Verticillium species, for example Verticillium dahliae, canckers, galls and witches' broom caused, for example, by Nectria species, for example Nectria galligena, wilt diseases caused, for example, by Verticillium species, for example Verticillium longisporum, Fusarium species, for example Fusarium oxysporum, deformations of leaves, flowers and fruits caused, for example, by Exobasidium species, for example Exobasidium vexans, Taphrina species, for example Taphrina deformans, degenerative diseases in woody plants, caused, for example, by Esca species, for example Phaeomoniella chlamydospora, Phaeoacremonium aleophilum or Fomitiporia mediterranean Ganoderma species, for example Ganoderma boninense, diseases of plant tubers caused, for example, by Rhizoctonia species, for example Rhizoctonia solani, Helminthosporium species, for example Helminthosporium solani, diseases caused by bacterial pathogens, for example Xanthomonas species, for example Xanthomonas campestris pv. oryzae, Pseudomonas species, for example Pseudomonas syringae pv. lachrymans, Erwinia species, for example Erwinia amylovora, Liberibacter species, for example Liberibacter asiaticus, Xylella species, for example Xylella fastidiosa, Ralstonia species, for example Ralstonia solanacearum, Dickeya species, for example Dickeya solanv, Clavibacter species, for example Clavibacter michiganensis, Streptomyces species, for example Streptomyces scabies, diseases of soya beans: fungal diseases on leaves, stems, pods and seeds caused, for example, by Alternaria leaf spot (Alternaria spec atrans tenuissima), Anthracnose (Colletotrichum gloesporioides dematium var. truncatum), brown spot (Septoria glycines), Cercospora leaf spot and blight (Cercospora kikuchii), choanephora leaf blight (Choanephora infundibulifera trispora (Syn.j), dactuliophora leaf spot (Dactuliophora glycines), downy mildew (Peronospora manshurica), Drechslera blight (Drechslera glycini), frogeye leaf spot (Cercospora sojina), leptosphaerulina leaf spot (Leptosphaerulina trifolii), phyllostica leaf spot (Phyllosticta sojaecola), pod and stem blight (Phomopsis sojae), powdery mildew (Microsphaera diffusa), pyrenochaeta leaf spot (Pyrenochaeta glycines), rhizoctonia aerial, foliage, and web blight (Rhizoctonia solani), rust (Phakopsora pachyrhizi, Phakopsora meibomiae), scab (Sphaceloma glycines), Stemphylium leaf blight (Stemphylium botryosum), sudden death syndrome (Fusarium virguliforme), target spot (Corynespora cassiicola). Fungal diseases on roots and the stem base caused, for example, by black root rot (Calonectria crotalariae), charcoal rot (Macrophomina phaseolina), fusarium blight or wilt, root rot, and pod and collar rot (Fusarium oxysporum, Fusarium orthoceras, Fusarium semitectum, Fusarium equiseti), mycoleptodiscus root rot (Mycoleptodiscus terrestris), neocosmospora (Neocosmospora vasinfecta), pod and stem blight (Diaporthe phaseolorum), stem canker (Diaporthe phaseolorum var. caulivora), phytophthora rot (Phytophthora megasperma), brown stem rot (Phialophora gregata), pythiumrot (Pythium aphanidermatum, Pythium irregulare, Pythium debaryanum, Pythium myriotylum, Pythium ultimum), rhizoctonia root rot, stem decay, and damping-off (Rhizoctonia solani), sclerotinia stem decay (Sclerotinia sclerotiorum), sclerotinia southern blight (Sclerotinia rolfsii), thielaviopsis root rot (Thielaviopsis basicola).

In some embodiments, the phytopathogenic harmful fungi is selected from 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., 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.

In a different aspect the present invention relates to the use of a buffering system for stabilizing liquid composition of a copper-based fungicide.

In some embodiments, the buffering system stabilize liquid composition of copper-based fungicides and tannic acid.

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

In some embodiments, the base is ammonium hydroxide. In some embodiments, the amount of the base is of about 19% to about 24 % by weight, based on the total weight of the composition. In a preferred embodiment, the amount of the base is of about 20% to about 21% by weight, based on the total weight of the composition.

In some embodiments, the copper-based fungicide is selected from cupric acetate, cupric chloride, cupric chlorate, cupric formate, cupric hexafluorosilicate, cupric nitrate, cupric chromate, copper sulfate pentahydrate, bordeaux mixture, copper hydroxide, copper oxychloride sulfate (COCS), copper oxide, tribasic copper sulfate such as cupric sulfate, tricupric hydroxide, hemihydrate and/or any combination thereof. In a preferred embodiment, the copper-based fungicide is selected from cupric acetate, cupric chloride, cupric chlorate, cupric formate, cupric hexafluorosilicate, cupric nitrate, cupric chromate, copper sulfate pentahydrate, bordeaux mixture and/or any combination thereof. In more preferred embodiment, the copper-based fungicide is selected from copper sulfate pentahydrate, bordeaux mixture and any combination thereof.

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

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

In some embodiments, the molar ratio between the base to copper-based fungicide is of about 3.7:1 to about 17:1. In a preferred embodiment, the molar ratio between the base to copper-based fungicide is of about 10:1 to about 16:1. In a preferred embodiment, the molar ratio between the base to copperbased fungicide is of about 11:1 to about 15:1. In some embodiments, the buffering system stabilize the liquid composition of copper-based further comprising tannic acid.

In some embodiments, the amount of tannic acid in the composition is of about 0.49 % 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 of about 0.5% by weight, based on the total weight of the composition.

In some embodiments, the composition of the present invention further comprising stabilizers.

In some embodiments, the stabilizers are selected from the salts of propionic acid, sodium salt of butyric acid, sodium salt of valeric acid and/or any combination thereof. In a preferred embodiment the stabilizer is the salt of propionic acid.

In some embodiments the origin of salt may be selected from sodium, calcium, magnesium, potassium, lithium and/or any combination thereof. In a preferred embodiment the origin of the salt is sodium.

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

In a different aspect, the invention relates to a method for reducing phytotoxicity by applying a composition comprising: a) a buffering system; b) tannic acid and c) a copper-based fungicide to a locus. In some embodiments, the buffering system is a combination of a carboxylic acid and a base.

In some embodiments, the base is ammonium hydroxide.

In some embodiments, the copper-based fungicide is selected from cupric acetate, cupric chloride, cupric chlorate, cupric formate, cupric hexafluorosilicate, cupric nitrate, cupric chromate, copper sulfate pentahydrate, bordeaux mixture, copper hydroxide, copper oxychloride sulfate (COCS), copper oxide, tribasic copper sulfate such as cupric sulfate, tricupric hydroxide, hemihydrate and/or any combination thereof. In a preferred embodiment, the copper-based fungicide is selected from cupric acetate, cupric chloride, cupric chlorate, cupric formate, cupric hexafluorosilicate, cupric nitrate, cupric chromate, copper sulfate pentahydrate, bordeaux mixture and any combination thereof. In more preferred embodiment, the copper-based fungicide is selected from copper sulfate pentahydrate, bordeaux mixture and/or any combination thereof.

In some embodiments, the stabilizers are selected from the salts of propionic acid, sodium salt of butyric acid, sodium salt of valeric acid and any combination thereof. In a preferred embodiment the stabilizer is the salt of propionic acid. In some embodiments the origin of salt may be selected from sodium, calcium, magnesium, potassium, lithium and any combination thereof. In a preferred embodiment the origin of the salt is sodium.

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

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

In some embodiments, the compositions of the invention comprising a) a buffering system which is a combination of acetic acid and ammonium hydroxide; b) tannic acid; c) bordeaux mixture as a copperbased fungicide, a stabilizer and an additive. In some embodiments, the compositions of the invention comprising a) a buffering system which is a combination of acetic acid and ammonium hydroxide; b) tannic acid; c) bordeaux mixture as a copper-based fungicide, sodium salt of propionic acid as the stabilizer and rheological agent as an additive. In some embodiments, the compositions of the invention comprising a) a buffering system which is a combination of acetic acid and ammonium hydroxide; b) tannic acid; c) bordeaux mixture as a copper-based fungicide, sodium salt of propionic acid as the stabilizer and Xanthan Gum as the rheological agent.

In some embodiments, the compositions of the invention comprising a) acetic acid in amount of about 28% and ammonium hydroxide in amount of about 20%, by weight, based on the total weight of the composition; b) tannic acid in amount of about 0.5% by weight, based on the total weight of the composition; c) bordeaux mixture in amount of about 18% by weight, based on the total weight of the composition; sodium salt of propionic acid in amount of about 0.9% by weight, based on the total weight of the composition and Xanthan Gum in amount of about 0.3% by weight, based on the total weight of the composition.

In some embodiments, the present invention also provides a method for reducing eye irritancy by applying the disclosed composition.

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

All the compositions of the present invention are formulated as suspension concentrate (SC).

More particularly, the formulations of the invention provide stable SC formulations of copper fungicide, optionally in combination with further active ingredients, preferably selected from fungicides, for treatment of plants.

All the compositions and/or combinations of the invention may comprise further one or more active fungicidal, bactericidal, insecticidal or herbicidal ingredients. Preferably, the compositions of the invention comprise one or more active insecticidal, bactericidal or fungicidal ingredients, more preferably one or more active fungicidal or bactericidal ingredients, more preferably one or more active fungicidal ingredients.

Non limiting examples of active fungicidal mixing partners are metalaxyl, zoxamide, fluopicolide, ametoctradin, amisulbrom, cymoxanil, mandipropamid, dimethomorph, captan, folpet, mancozeb, difenoconazole, metconazole, tebuconazole, azoxystrobin, picoxystrobin, trifloxystrobin, pydiflumetofen, fluxapyroxad, fluopyram and any combination thereof. The present invention likewise provides a suspension obtainable by mixing water with the liquid compositions of the invention. The mixing ratio of water to suspension concentrate may be in the range from 1500:1 to 1:1, preferably 500:1 to 10:1.

The dilution is achieved by pouring the concentrates of the invention into the water. For rapid mixing of the concentrate with water, it is customary to use agitation, for example stirring. However, agitation is generally unnecessary. Even though the temperature for the dilution operation is an uncritical factor, dilutions are typically conducted at temperatures in the range from 00°C to 50°C, especially at 5 °C to 40 °C or at ambient temperature.

The water used for dilution is generally tap water. The water may, however, already contain water soluble or finely dispersed compounds which are used in crop protection, for instance nutrients, fertilizers or pesticides. It is possible to add various kinds of oils, wetting agents, adjuvants, buffers, fertilizers or micronutrients and further pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners, elicitors) to the suspension of the invention in the form of a premix or, if appropriate, not until shortly before use (tank-mix). These may be added to the compositions of the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.

The user will apply the compositions of the invention typically from a pre-dosing system, a backpack sprayer, a spraying tank, a spraying aircraft, drone or an irrigation system; the compositions of the invention is typically diluted to the desired deployment concentration with water, buffer and/or further auxiliaries, which affords the ready-to-use spray liquid or agrochemical composition of the invention. Typically, 20 to 2000 liters, preferably 50 to 1000 liters, of the ready-to-use spray liquid are deployed per hectare of useful agricultural area.

The generally diluted compositions of the invention are applied mainly by spraying, especially spraying of the leaves. Application can be conducted by spraying techniques known to those skilled in the art, for example using water as carrier and amounts of spray liquid of about 50 to 1000 liters per hectare, for example from 100 to 200 liters per hectare.

The invention is illustrated by the following examples without limiting it thereby. EXAMPLES

Example 1 - formulation A

Method of preparation:

1.1. Initially, 20 parts of ammonium hydroxide was charged into the lab reactor and cooled at about 6 ° C.

1.2. Then 10.7 parts of water was added and mixed until homogenization.

1.3. With the mixture still cold, 27.9 parts of acetic acid were slowly added under controlled temperature (6 - 15 ° C).

1.4. Tannic acid was further added (0.5 parts) and well diluted in the system.

1.5. The mixture was heated to a range of temperature between 65 to 68 ° C previous the addition of 18.2 parts of Bordeaux Mixture and strongly mixed for 1 hour.

1.6. Polydimethyl siloxane, methyl end blocked (0.008 parts) was added after agitation and the mixture was allowed to warm up to a temperature of 50 ° C.

1.7. The mixture was milled in a Horizontal Mill (Mini Lab II NETZSCH) and then 0.9 parts of propionic acid sodium salt was added previous dilution in 8 parts of propylene glycol at a maximum temperature of 52°C.

1.8. Finally the xanthan gum was hydrated with the remaining water and then added to the mixture 1.9. The product was hold under agitation for 3 hours at a temperature of 43°C and, 30 minutes before the end of agitation, the remaining Polydimethyl siloxane was added.

1.10. Final mixture was allowed to reach a temperature of 32°C.

Example 2 -Phytotoxicity in grapes:

The objective of the trial was to evaluate the phytotoxicity and selectivity of formulation A and Phyton 27 vs market standards in the control of downy mildew in grape.

The trial was carried out in on a susceptible variety of wine grape, in the municipality of Ribadumia, Spain.

Method

Eight applications were done in a preventive way according to local practices, from pre-flowering and up to fruit development when majority of the berries touching each other. The interval between applications was 7-14 days according to weather conditions and local practices for copper compounds. Water Volume: 1000 L/ha. Efficacy and selectivity assessed on leaves and berries.

Results

From the 3^rd applications some treatments showed leaf color changing by phytotoxicity:

Table 1. It appears that in application 1-4 of formulation A, in 1.5L/Ha (99 gCu/Ha) did not show any or significant phytotoxicity symptoms; however, Phyton 27 formulation showed greater phytotoxicity. The results are also presented graphically in a form of bar diagram of figure 1.

Example 3 - apple fruit russeting

Trials setup and protocols:

During the years 2018 and 2019 6 field trials were carried out in various Eu countries to verify the influence of the formulation A on apple fruit russeting in different varieties known to be sensitive to copper fungicides. Were treated apple plants grown according to best farming practice and already in fully productive age at the time of the trials. The trial was set up as RGB (randomized block design) according to EPPO guidelines. As indicated in the table below, trial protocol included a multiple product spray plan (up to 8 or more applications) throughout the crop growth cycle, 7-10 days apart according to local weather conditions, of the formulation A at 2,5 L/ha, 3 L/ha, 3,5 l/ha and 4 L/ha, with various Bordeaux mix based commercial products (for France: Bouille Bodelaise RSR Disperss, for Italy: Poltiglia Disperss, for Portugal: Caldo Bordoles RSR Disperss) applied at 6 kg/ha as reference standard. The presence of russeting on fruit skin was visually assessed at harvest time or when fruits were fully developed, classifying fruits in 3 classes (A: no visible russeting, B: russeting present but commercially acceptable, C: heavy russeting, fruit depreciated or not commercially acceptable).

Trial protocol: Results

As shown in the table below the formulation A when applied at its highest rates (3,5 and 4 L/ha) showed a lower incidence of apple fruit russeting compared to the commercial reference. The lower russeting incidence can be seen both as reduced incidence per single fruit class affected by russeting, as well as tendency toward more commercially priced fruit classes compared to the commercial reference.

Table of results. Data are expressed as % of harvested fruits divided into the three classes A, B, C, corresponding to different severity of russeting on fruit.

Table 2.

*A: no visible russeting, B: russeting present but commercially acceptable, C: heavy russeting, fruit depreciated or not commercially acceptable

Example 4 - Efficacy on grapevine against P. viticola

Trail setup and protocols

A filed trail was set up on 2021 in a commercial vineyard located in Italy with the aim to compare the efficacy of the Formulation A and other commercial products with similar characteristics against downy mildew (Plasmopara viticola). The trial was set up as RGB (randomized block design) according to EPPO guidelines. As indicated in the table below, trial protocol included a spray plan with up to 10 applications throughout the crop growth cycle, about 7 days apart according to local weather conditions, of Formulation A at 3,5 L/ha and 4 L/ha and Bordoflow new at 2,6 L/ha and 5 L/ha. Formulation A and the standard Bordoflow new, in addition to their recommended label rate, were tested at additional lower rate in terms of metallic copper delivered per ha.

The presence of the downy mildew disease was assessed on leaves and bunches and the efficacy was calculated according to EPPO guidelines.

Trial protocol Table 3.

Results

Table 3 demonstrate that formulation A shows better efficacy than the commercial product Bordoflow new (SC formulation) on both bunch and leaf. It is shown that formulation A achieves better efficacy than bordoflow new even in lower Copper dose and in lower application rates.

Claims

27 Claims:

1. A composition comprising: a) a buffering system; b) tannic acid and c) a copper-based fungicide.

2. The composition according to claim 1, wherein the buffering system is a combination of a carboxylic acid and a base.

3. The composition according to claim 2, wherein the carboxylic acid is selected from acetic acid, formic acid, citric acid, propionic acid, butyric acid and/or any combination thereof.

4. The composition according to claim 3, wherein the amount of the carboxylic acid is of about 22% to about 38% by weight, based on the total weight of the composition.

5. The composition according to claim 4, wherein the amount of the carboxylic acid is of about 25% to about 28% by weight, based on the total weight of the composition.

6. The composition according to claim 2, wherein the base is ammonium hydroxide.

7. The composition according to claim 6, wherein the amount of the base is of about 19% to about 24 % by weight, based on the total weight of the composition.

8. The composition according to claim 7, wherein the amount of the base is of about 20% to about 21% by weight, based on the total weight of the composition.

9. The composition according to any one of the preceding claims, wherein the weight ratio between the carboxylic acid and the base is of about 0.9:1 to about 1.8:1.

10. The composition according to claim 9, wherein the weight ratio between the carboxylic acid and the base is of about 1.2:1 to about 1.4:1.

11. The composition according to any one of the preceding claims, wherein the amount of tannic acid in the composition is of about 0.49 % to about 0.51 % by weight, based on the total weight of the composition.

12. The composition according to claim 11, wherein the amount of tannic acid in the composition is of about 0.5 % by weight, based on the total weight of the composition.

13. The composition according to any one of the preceding claims, wherein the copper-based fungicide is selected from copper sulfate pentahydrate, bordeaux mixture and/or any combination thereof.

14. The composition according to claim 13, wherein the amount of the copper-based fungicide is of about 16 % to about 24 % by weight, based on the total weight of the composition. The composition according to claim 14, wherein the amount of copper-based fungicide is of about 18% to 22% by weight, based on the total weight of the composition. The composition according to any one of the proceeding claims, wherein the copper content of the copper-based fungicide is from about 40 to about 500 g/l. The composition according to claim 16, wherein the copper content of the copper-based fungicide is from about 50 to about 300 g/l. The composition according to claim 17, wherein the copper content of the copper-based fungicide is of about 66 g/l. The composition according to any one of the preceding claims, wherein the molar ratio between the carboxylic acid to the copper-based fungicide is of about 3.5:1 to about 18:1. The composition according to any one of the preceding claims, wherein the molar ratio between the base to copper-based fungicide is of about 3.7:1 to about 17:1. The composition according to any one of the proceeding claims, further comprising stabilizers. The composition according to claim 21, wherein the stabilizers are selected from the salts of propionic acid, butyric acid, valeric acid and/or any combination thereof. The composition according to claim 22, wherein the stabilizer is the salt of propionic acid. The composition according to claims 22 or 23, wherein the salt is sodium. The composition according to any one of claims 21-24, wherein the amount of the stabilizer is of about 0.8% to about 1.0% by weight, based on the total weight of the composition. The composition according to claim 25, wherein the amount of the stabilizer is of about 0.9% by weight, based on the total weight of the composition. The composition according to any one of the preceding claims, further comprising additives. The composition according to any one of the preceding claims, wherein the composition is applied in an amount from about 0.4 L/ha to about 5 L/ha. The composition according to claim 28, wherein the composition is applied in an amount from about 1 L/ha to about 4 L/ha. The composition according to claim 29, wherein the composition is applied in an amount from about

2.5 L/ha to about 3.5 L/ha. A method for reducing phytotoxicity by applying a composition comprising: a) a buffering system; b) tannic acid and c) a copper-based fungicide to a locus. The method according to claim 31, wherein the buffering system is a combination of a carboxylic acid and a base. The method according to claim 32, wherein the carboxylic acid is selected from acetic acid, formic acid, citric acid, propionic acid, butyric acid and/or any combination thereof. The method according to claim 33, wherein the amount of the carboxylic acid is of about 22% to about 38% by weight, based on the total weight of the composition. The method according to claim 32, wherein the base is ammonium hydroxide. The method according to claim 35, wherein the amount of the base is of about 19% to about 24 % by weight, based on the total weight of the composition. The method according to claim 36, wherein the amount of the base is of about 20% to about 21% by weight, based on the total weight of the composition. The method according to any one of claims 32-37, wherein the weight ratio between the carboxylic acid and the base is of about 0.9:1 to about 1.8:1. The method according to claim 38, wherein the weight ratio between the carboxylic acid and the base is of about 1.2:1 to about 1.4:1. The method according to any one of claims 31-39, wherein the amount of tannic acid in the composition is of about 0.49 % to about 0.51 % by weight, based on the total weight of the composition. The method according to claim 40, wherein the amount of tannic acid in the composition is of about 0.5 % by weight, based on the total weight of the composition. The method according to any one of claims 31-41, wherein the copper-based fungicide is selected from copper sulfate pentahydrate, bordeaux mixture and/or any combination thereof. The method according to claim 42, wherein the amount of the copper-based fungicide is of about 16 % to about 24 % by weight, based on the total weight of the composition. The method according to claim 43, wherein the amount of the copper-based fungicide is of about

18 % to about 22 % by weight, based on the total weight of the composition. The method according to any one of claims 32-44, wherein the copper content of the copper-based fungicide is from about 40 to about 500 g/l. The method according to claim 45, wherein the copper content of the copper-based fungicide is from about 50 to about 300 g/l. The method according to claim 46, wherein the copper of the copper-based fungicide content is of about 66 g/l. The method according to any one of claims 31-47, wherein the molar ratio between the carboxylic acid to the copper-based fungicide is of about 3.5:1 to about 18:1. The method according to claim 48, wherein the molar ratio between the base to copper-based fungicide is of about 3.7:1 to about 17:1. The method according to any one of claims 31-49, wherein the composition further comprising stabilizers. The method according to claim 50, wherein the stabilizers are selected from the salts of propionic acid, butyric acid, valeric acid and/or any combination thereof. The method according to claim 51, wherein the stabilizer is the salt of propionic acid. The method according to claims 51 or 52, wherein the salt is sodium. The method according to any one of claims 50-53, wherein the amount of stabilizer is of about 0.8% to about 1.0% by weight, based on the total weight of the composition. The method according to claim 54, wherein the amount of stabilizer is of about 0.9% by weight, based on the total weight of the composition. The method according to any one of claims 31-55, wherein the composition further comprising additives. The method according to any one of claims 31-56, wherein the composition is applied in an amount from about 0.4 L/ha to about 5 L/ha. The method according to claim 57, wherein the composition is applied in an amount from about 1 L/ha to about 4 L/ha. The method according to claim 58, wherein the composition is applied in an amount from about 2.5

L/ha to about 3.5 L/ha. 31 A method for reducing eye irritancy by applying the composition according to any one of claims 1- 30. A method for reducing aquatic toxicity by applying the composition according to any one of claims 1-30. Use of a buffering system for stabilizing liquid composition of a copper-based fungicide. The use according to claim 62, wherein the buffering system is a combination of a carboxylic acid and a base. The use according to claim 63, wherein the carboxylic acid is selected from acetic acid, formic acid, citric acid, propionic acid, butyric acid and/or any combination thereof. The use according to claim 64, wherein the carboxylic acid is acetic acid. The use according to any one of claims 63-65, wherein the amount of the carboxylic acid is of about 22% to about 38% by weight, based on the total weight of the composition. The use according to claim 66, wherein the amount of the carboxylic acid is of about 25% to about 30% by weight, based on the total weight of the composition. The use according to claim 63, wherein the base is ammonium hydroxide. The use according to claim 68, wherein the amount of the base is of about 19% to about 24 % by weight, based on the total weight of the composition. The use according to claim 69, wherein the amount of the base is of about 20% to about 21% by weight, based on the total weight of the composition. The use according to any one of claims 63-70, wherein the weight ratio between the carboxylic acid and the base is of about 0.9:1 to about 1.8:1. The use according to claim 71, wherein the weight ratio between the carboxylic acid and the base is of about 1.2:1 to about 1.4:1. The use according to any one of claims 62-72, wherein the copper-based fungicide is selected from copper sulfate pentahydrate, bordeaux mixture and/or any combination thereof. The use according to claim 73, wherein the amount of the copper-based fungicide is of about 16 % to about 24 % by weight, based on the total weight of the composition. The use according to claim 74, wherein the amount of copper-based fungicide is of about 18% to 22% by weight, based on the total weight of the composition. 32 The use according to any one of claims 62-75, wherein the molar ratio between the carboxylic acid to the copper-based fungicide is of about 3.5:1 to about 18:1. The use according to claim 76, wherein the molar ratio between the carboxylic acid to the copperbased fungicide is of about 10:1 to about 18:1. The use according to claim 77, wherein the molar ratio between the carboxylic acid to the copperbased fungicide is of about 15:1 to about 18:1. The use according to any one of claims 63-75, wherein the molar ratio between the base to copperbased fungicide is of about 3.7:1 to about 17:1. The use according to claim 79, wherein the molar ratio between the base to copper-based fungicide is of about 10:1 to about 16:1. The use according to claim 80, wherein the molar ratio between the base to copper-based fungicide is of about 11:1 to about 15:1. The use according to any one of claims 62-81, wherein the composition further comprising tannic acid. The use according to claim 82, wherein the amount of tannic acid in the composition is of about 0.49 % to about 0.51% by weight, based on the total weight of the composition. The use according to claim 83, wherein the amount of tannic acid in the composition is of about 0.5% by weight, based on the total weight of the composition. The use according to any one of claims 62-84, wherein the composition further comprising stabilizers. The use according to claim 85, wherein the stabilizers are selected from the salt of propionic acid, sodium salt of butyric acid, sodium salt of valeric acid and/or any combination thereof. The use according to claim 86, wherein the stabilizer is the salt of propionic acid. The use according to claim 87, wherein the origin of salt is selected from sodium, calcium and/or any combination thereof. The use according to claim 88, wherein the origin of the salt is sodium. The use according to any one of claims 87-89, wherein the stabilizer is sodium salt of propionic acid. The use of according to any one of claims 86-90, wherein the amount of stabilizer is of about 0.8% to about 1.0% by weight, based on the total weight of the composition. 33 The use according to claim 91, wherein the amount of stabilizer is of about 0.9% by weight, based on the total weight of the composition. The use according to claim 62 for stabilizing liquid composition of a copper-based fungicide containing tannic acid. The use according to claim 63 wherein the liquid composition is in the form of a suspension concentrate.