Azole fungicide compositions

Abstract

The present invention provides a combination comprising (1) an amount of an azole fungicide and (2) an amount of an additive (I) selected from the group consisting of thiourea-based compounds, sodium thiosulfate, alkylamines, thioamide-based compounds, and any combination thereof, which may be in the form of a barrel mixture or composition. The invention also provides methods of using the combinations and compositions disclosed herein and methods of making the compositions disclosed herein.

Description

[0001] Throughout this application, various publications are referenced. The disclosures of these documents are hereby incorporated by reference into this application in their entireties in order to more fully describe the state of the art to which this invention pertains. Technical Field

[0002] The present invention provides a combination comprising (1) an amount of an azole fungicide and (2) an amount of an additive (I) selected from the group consisting of: a thiourea-based compound, sodium thiosulfate, an alkylamine, a thioamide-based compound, and any combination thereof, which may be in the form of a mixture, including a tank mix, or a premix composition. The present invention also provides methods of using the combinations and compositions disclosed herein and methods of preparing the compositions disclosed herein. Background Art

[0003] Azole fungicides, such as prothioconazole and epoxiconazole, are considered effective fungicides for controlling a wide range of pathogens. However, negative effects (phytotoxicity) associated with the application of azole fungicides in susceptible crops are known and the severity depends on environmental conditions and / or composition.

[0004] This negative impact affects the application of azole fungicides in different aspects such as application rate, application time and number of repetitions. In addition, formulating azole fungicides in the presence of different pesticides is also found to be challenging. There is a need to find ways to improve the use of azole fungicides, including use in the presence of other pesticides.

[0005] Copper-based fungicides are well known, but their use is limited due to phytotoxicity to plants and toxicity to users.

[0006] The solubility of copper ions in water depends on the source of the copper ions. Copper-based fungicides such as copper acetate, copper chloride and copper chlorate, copper formate, copper hexafluorosilicate, copper nitrate, copper chromate and copper sulfate pentahydrate are highly soluble in water. Others such as copper hydroxide, copper oxychlorosulfate (COCS), copper oxychloride and tribasic copper sulfate (copper sulfate, tricopper hydroxide, hemihydrate), which is also known as "fixed" copper, are relatively less soluble in water. Solubility in water affects the amount of copper-based fungicides that can be applied and their toxicity level.

[0007] Copper particles adhere to the leaf surface and act as an ion reservoir, continuously releasing Cu2+ ions and forming a protective layer to prevent infection. The efficiency of Cu2+ ion release of copper fungicide formulations varies, depending on the copper source. In addition, the concentration of copper ions on the leaves depends on the equilibrium established with complexed and soluble forms of copper (Menkissoglu and Lindow 1991).

[0008] It is well known that copper is toxic when the dissolved form penetrates plant tissues. In general, the use of spray additives such as foliar nutrients and any surfactants with penetrating properties should be avoided when applying copper-based fungicides.

[0009] Suspension concentrate (SC) compositions containing a tannate complex of copper sulfate pentahydrate and picric ammonium formate are disclosed in US 4,544,666 and US 4,673,687. These compositions contain picric acid, which has a number of disadvantages. Picric acid is also known to be an explosive compound that should be handled with great caution.

[0010] Polyelectrolytes are known in the agricultural field as slow release imparting agents. WO2008 / 002623 describes the use of ion exchange polymers to provide slow release of charged pesticides. In addition, WO 2013 / 133705 and WO 2013 / 133706 describe the use of neutral, insoluble polyelectrolyte complexes generated by mixing solutions of polycations and polyanions. PCT / IB2020 / 055089 discloses the use of polycations to increase the biological effect of mancozeb. US2002 / 010099 discloses a combination of crop protection agents and anionic polymers.

[0011] There is a need to develop new compositions having improved properties. Summary of the invention

[0012] The present invention provides a combination comprising (1) an amount of an azole fungicide and (2) an amount of an additive (I). In some embodiments, the combination comprises (1) an amount of an azole fungicide and (2) an amount of an additive (I) selected from the group consisting of a thiourea-based compound, sodium thiosulfate, an alkylamine, a thioamide-based compound, and any combination thereof.

[0013] The present invention provides the use of an additive (I) selected from the group consisting of thiourea-based compounds, sodium thiosulfate, alkylamines, thioamide-based compounds and any combination thereof for reducing phytotoxicity associated with the application of azole fungicides.

[0014] The present invention provides use of an additive (I) selected from the group consisting of: thiourea-based compounds, sodium thiosulfate, alkylamines, thioamide-based compounds, and any combination thereof, for increasing the plant health of a plant when treated with an azole fungicide, wherein the plant health of a plant treated with an azole fungicide in the presence of additive (I) is increased compared to the plant health of a plant treated with the same amount of the same azole fungicide in the absence of additive (I).

[0015] The present invention provides the use of an additive (I) selected from the group consisting of thiourea-based compounds, sodium thiosulfate, alkylamines, thioamide-based compounds and any combination thereof for reducing or eliminating phytotoxicity associated with the application of azole fungicides, wherein the phytotoxic effect on plants treated with an azole fungicide in the presence of additive (I) is lower than the phytotoxic effect on plants treated with the same amount of the same azole fungicide in the absence of additive (I).

[0016] The present invention provides the use of an additive (I) selected from the group consisting of: thiourea-based compounds, sodium thiosulfate, alkylamines, thioamide-based compounds and any combination thereof for reducing or eliminating the phytotoxicity of azole fungicides, wherein the application rate and / or the extent of phytotoxic effects when the azole fungicide is applied in the presence of additive (I) is reduced compared to the application rate and / or the extent of phytotoxic effects when the azole fungicide is applied in the absence of additive (I).

[0017] The present invention provides a method for producing a composition comprising (1) an azole fungicide and (2) an additive (I) selected from the group consisting of: a thiourea-based compound, sodium thiosulfate, an alkylamine, a thioamide-based compound, and any combination thereof, the method comprising the steps of: (a) preparing an aqueous composition of the azole fungicide and (b) adding the additive (I) to the aqueous composition to obtain a composition comprising the azole fungicide and the additive (I).

[0018] The present invention also provides a composition produced using the method described herein.

[0019] The invention also provides a method of treating a plant or a locus thereof against pathogens comprising contacting the plant, a part of a plant, or the locus with any of the combinations or compositions described herein.

[0020] The present invention provides a method for controlling fungal diseases caused by undesirable pathogens, which comprises applying an effective amount of any of the combinations and / or compositions and / or diluted compositions described herein to plants, their loci, their propagation materials, or areas infected by undesirable pathogens, so as to thereby control the fungal diseases.

[0021] The present invention provides a method for increasing the application rate of an azole fungicide to a plant or a plant part and / or increasing the frequency of application of an azole fungicide to a plant or a plant part without causing increased phytotoxicity to the plant, wherein the method comprises applying to the plant or the plant part an azole fungicide in combination with an additive (I) selected from the group consisting of a thiourea-based compound, sodium thiosulfate, an alkylamine, a thioamide-based compound, and any combination thereof.

[0022] The present invention provides a method of improving pest control using azole fungicides without increasing phytotoxicity, wherein the method comprises applying a combination or composition of the present invention where pest control is desired.

[0023] The present invention provides a method for reducing and / or eliminating phytotoxicity to plants or plant parts caused by azole fungicides applied to plants or plant parts, wherein the method comprises applying an azole fungicide in combination with an additive (I) selected from the group consisting of thiourea-based compounds, sodium thiosulfate, alkylamines, thioamide-based compounds, and any combination thereof.

[0024] The present invention provides a method for improving plant tolerance to a certain amount of azole fungicides, which comprises applying the amount of azole fungicides in combination with an additive (I) selected from the group consisting of thiourea-based compounds, sodium thiosulfate, alkylamines, thioamide-based compounds and any combination thereof.

[0025] The present invention provides a method for treating plants or loci seriously infected with or susceptible to fungal diseases, which comprises applying to the plants, plant parts, or loci an amount of an azole fungicide in combination with an additive (I) selected from the group consisting of thiourea-based compounds, sodium thiosulfate, alkylamines, thioamide-based compounds, and any combination thereof. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 Showing the effect of thiourea on the phytotoxicity of prothioconazole SC compositions [thiourea combination as a tank mix; (+) with thiourea; (-) without thiourea]

[0027] Figure 2 The effect of thiourea on the phytotoxicity of a suspoemulsion composition comprising copper oxychloride, prothioconazole and picoxystrobin is shown. [Presence of thiourea in premix composition; (+) with thiourea; (-) without thiourea]

[0028] Figure 3 The effect of thiourea on the phytotoxicity of suspoemulsion and suspension concentrate compositions comprising cupric oxychloride, prothioconazole and picoxystrobin was compared.

[0029] Figure 4a -b shows the phytotoxicity of SE compositions 49T (without thiourea) and 47T and 50T (with thiourea).

[0030] Figure 5 Four new copper-fungicide prototype formulations obtained from AUDPC are shown: DT-CE-C4-345-08T DT-CE-C4-345-09T DT-CE-C4-345-10T DT-CE-C4-345-11T +0.05% Tween80 and copper oxychloride (Difere) +0.05% Tween 80 Dose-response curve against soybean rust (Phakopsora pachyrhizi) strain THAI1.

[0031] Figure 6 Four new copper-fungicide prototype formulations DT-CE-C4-345-08T are shown DT-CE-C4-345-09T DT-CE-C4-345-10T and DT-CE-C4-345-11T Kocide Opti and Kocide 2000 In-planta evaluation of potato late blight caused by Phytophthora infestans. Dose-effect curves (efficacy calculated via DSI values; %) at 7 dpi for whole potato plants treated prophylactically 24 h before inoculation with Phytophthora infestans are presented. For each condition, a minimum of 12 leaves were considered. The EC of each copper-based product was evaluated. 50 .

[0032] Figure 7 Improved rain resistance in soybeans was shown for DT-CE-C4-345-08T and DT-CE-C4-345-10T compared to other copper formulations.

[0033] Figure 8 DT-CE-C4-345-08T and DT-CE-C4-345-10T were shown to be non-phytotoxic to soybean (Glycine max Abelina). DETAILED DESCRIPTION

[0034] 4.1 Definition

[0035] Unless defined otherwise, 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 inventive subject matter belongs.

[0036] Unless otherwise specifically stated, the terms "a or an" as used herein include the singular and the plural. Therefore, the terms "a / an" or "at least one" are used interchangeably in this application.

[0037] As used herein, the term "about", when used in conjunction with a numerical value, includes ±10% of the indicated value. In addition, all ranges involving the same component or characteristic herein include endpoints, are independently combinable, and include all intermediate points and ranges. It should be understood that where a parameter range is provided, the present invention also provides all integers and tenths thereof within the range. For example, "30%-45%" includes 30%, 30.1%, 30.2%, etc. up to 45%.

[0038] As used herein, the term "crop" includes cereals, such as wheat, barley, rye, oats, sorghum and millet, rice, cassava and maize, and crops producing, for example, peanuts, sugar beets, cotton, soybeans, rapeseed, potatoes, tomatoes, peaches, and vegetables.

[0039] As used herein, the term "part of a plant" refers to a part of a plant, including but not limited to pollen, ovules, leaves, roots, flowers, fruits, stems, bulbs, grains, branches, and seeds.

[0040] As used herein, the term "combination" means a collection of the combination components for administration by simultaneous or contemporaneous administration.

[0041] As used herein, the term "simultaneously" when used in conjunction with the administration of components means that the components are administered as an admixture (e.g., a tank mix). For simultaneous administration, the combination can be an admixture or separate containers, each containing the combination components that are combined prior to administration.

[0042] The admixture or the individual components may be in any physical form, such as a blend, solution, suspension, dispersion, emulsion, admixture, and the like.

[0043] As used herein, the term "contemporaneous" when used in connection with the administration of components means that the individual components of the combination are administered separately at the same time or sufficiently close in time to the other component such that the desired effect of the combination is achieved.

[0044] As used herein, the term "premix" means a composition that can be applied directly to plants after dilution. A composition comprises the components in combination.

[0045] As used herein, the term "composition" includes at least one of the combinations or mixtures of the present invention and an agriculturally acceptable carrier.

[0046] In some embodiments, the terms "composition" and "formulation" are used interchangeably.

[0047] As used herein, the term "polyelectrolyte" refers to a molecule consisting of multiple functional, charged groups attached to a polymer backbone. In the context of the present application, the term "polycation" is interchangeable with the term "positively charged polyelectrolyte", while the term "polyanion" is interchangeable with the term "negatively charged polyelectrolyte". The terms polycation and polyanion refer to polymer molecules that are positively and negatively charged under neutral or acidic conditions, i.e., at pH 3-8, respectively.

[0048] As used herein, the term "polyelectrolyte complex" refers to a structure formed by the interaction of at least one polycation and at least one polyanion, i.e., a complex of oppositely charged polyelectrolytes (polyanions and polycations). The complex is a strong but reversible electrostatic connection, thereby avoiding the use of covalent crosslinkers. Polyelectrolyte complexes are described, for example, in WO 2013 / 133705 and WO 2013 / 133706, the contents of each of which are hereby incorporated by reference.

[0049] As used herein, the term "macromolecular complex" refers to a structure formed by non-covalent interactions of a copper-based fungicide with a polyelectrolyte, such as at least one polyanion or at least one polyelectrolyte complex. In such macromolecular complexes, the non-covalent interactions are preferably electrostatic interactions. The macromolecular complex thus avoids the use of covalent crosslinking agents and produces a matric-like physical structure.

[0050] As used herein, the term "electrostatic interaction" refers to the electric force between any two charged molecules and / or dipole molecules. The term "electrostatic interaction" includes ionic interactions, hydrogen bonds, and van der Waals forces, such as dipole-dipole interactions.

[0051] As used herein, the term "part of a plant" refers to a part of a plant, including but not limited to pollen, ovules, leaves, roots, flowers, fruits, stems, bulbs, grains, branches, and seeds.

[0052] The term "polyion" refers to a molecule consisting of multiple charged groups attached to a common backbone. In the context of the present application, the term "polycation" is interchangeable with the term "positively charged polyelectrolyte", and the term "polyanion" is interchangeable with the term "negatively charged polyelectrolyte".

[0053] As used herein, the term "suspension concentrate" refers to a suspension of solid particles in a liquid intended for dilution with water prior to use. In some embodiments, the suspension concentrate is an aqueous suspension concentrate.

[0054] As used herein, the term "dispersion concentrate" refers to a dispersion of solid particles in a liquid intended for dilution with water prior to use.

[0055] As used herein, the term "water-dispersible granules" refers to a formulation in the form of particles that can be dispersed in water to form a dispersion, such as a suspension or a solution.

[0056] As used herein, the term "wettable powder" refers to a powder formulation intended to be mixed with water or other liquids prior to use.

[0057] As used herein, the term "water-slurryable powder" refers to a powder formulation that is slurried in water prior to use.

[0058] Azole fungicides and additives (I)

[0059] Combining additive (I) with an azole fungicide reduces the phytotoxicity associated with the application of the azole fungicide.

[0060] combination

[0061] The present invention provides a combination comprising (1) a certain amount of an azole fungicide and (2) a certain amount of an additive (I).

[0062] The present invention provides a combination comprising (1) an amount of an azole fungicide and (2) an amount of an additive (I) selected from the group consisting of a thiourea-based compound, sodium thiosulfate, an alkylamine, a thioamide-based compound, and any combination thereof.

[0063] The present invention provides a combination comprising (1) an amount of an azole fungicide, (2) an amount of an additive (I) selected from the group consisting of a thiourea-based compound, sodium thiosulfate, an alkylamine, a thioamide-based compound, and any combination thereof, and (3) water.

[0064] The present invention provides a combination comprising (1) an amount of an azole fungicide and (2) an amount of an additive (I) selected from the group consisting of: a thiourea-based compound, sodium thiosulfate, an alkylamine, a thioamide-based compound, and any combination thereof, wherein the combination does not contain a copper-based fungicide.

[0065] The present invention provides a combination comprising (1) an amount of an azole fungicide, (2) an amount of an additive (I) selected from the group consisting of a thiourea-based compound, sodium thiosulfate, an alkylamine, a thioamide-based compound, and any combination thereof, and (3) water, wherein the combination does not contain a copper-based fungicide.

[0066] In some embodiments, the combination comprises (1) an amount of prothioconazole and (2) an amount of thiourea.

[0067] In some embodiments, additive (I) is thiourea.

[0068] In some embodiments, the additive (I) is selected from the group consisting of thiourea-based compounds, hexamethylenetetramine, sodium thiosulfate, ethylenediamine, and any combination thereof.

[0069] In some embodiments, the additive (I) is a mixture of two compounds selected from the group consisting of a thiourea-based compound, sodium thiosulfate, an alkylamine, and a thioamide-based compound.

[0070] In some embodiments, additive (I) is a mixture of two compounds selected from the group consisting of: a thiourea-based compound, hexamethylenetetramine, sodium thiosulfate, and ethylenediamine.

[0071] In some embodiments, additive (I) is a thiourea-based compound.

[0072] In some embodiments, the thiourea-based compound is thiourea.

[0073] In some embodiments, thiourea refers to a compound having the formula SC(NH2)2 and the structure H2N-C(=S)-NH2 (also known as thiourea material, CAS No.: 62-56-6).

[0074] The thiourea-based compound refers to a compound having a structure represented by the following formula:

[0075] R 1 NH-C(=S)-NHR 2

[0076] in,

[0077] (i)R 1 , R 2 All are H;

[0078] (ii) R 1 is H, and R 2 is an alkyl or alkenyl or alkynyl or aryl or heterocyclic group;

[0079] (iii) R 1 , R2 are each independently alkyl, alkenyl or alkynyl;

[0080] (iv) R 1 , R 2 are each independently aryl or heterocyclic;

[0081] (v)R 1 is alkyl or alkenyl or alkynyl, and R 2 is an aryl or heterocyclic group, or

[0082] (vi)R 1 and R 2 may be taken together with the nitrogen atom to which they are attached to form a ring containing 2 to 4 carbon atoms and optionally one additional nitrogen, sulfur or oxygen atom, which ring may be saturated or unsaturated and optionally substituted by 1 to 4 substituents selected from the group consisting of C1-C2 alkyl, halogen, CN, NO2 and C1-C2 alkoxy.

[0083] In some embodiments, the alkyl group (which may be optionally substituted) represents a straight chain or branched chain or cyclic hydrocarbon group containing n carbon atoms.

[0084] In some embodiments, alkyl represents a straight chain or branched chain or cyclic hydrocarbon group containing 1-16 carbon atoms, or 1-8 carbon atoms.

[0085] In some embodiments, alkenyl (which may be optionally substituted) represents a straight or branched chain or cyclic hydrocarbon group containing n carbon atoms and at least one double bond.

[0086] In some embodiments, alkynyl (which may be optionally substituted) represents a straight or branched hydrocarbon group containing n carbon atoms and at least one triple bond.

[0087] In some embodiments, alkenyl and alkynyl groups contain 2-8 carbon atoms.

[0088] In some embodiments, aryl (which may be optionally substituted) represents a carbocyclic aromatic group having 6 to 14 carbon atoms.

[0089] In some embodiments, heterocycle (which may be optionally substituted) represents a saturated, partially saturated, or fully unsaturated cyclic group containing 3 to 6 ring atoms, wherein 1 to 4 of the ring atoms are from the group consisting of oxygen, nitrogen, and sulfur.

[0090] In some embodiments, the thiourea-based compound is butylthiourea, methylpropylthiourea, phenylthiourea, ethylphenylthiourea, or diphenylthiourea.

[0091] In some embodiments, the thiourea-based compound is a cyclic thiourea.

[0092] In some embodiments, additive (I) is not a fungicidal active ingredient.

[0093] In some embodiments, additive (I) is selected from thiourea-based compounds having no pesticidal activity.

[0094] In some embodiments, the selected additive (I) is a thioamide-based compound.

[0095] In some embodiments, thioamide-based compounds may include, but are not limited to, thioacetamide, thiobenzamide, furanthioamide, pyridinethioamide, and polythioamide.

[0096] In some embodiments, the thioamide-based compound is selected from the group consisting of thioacetamide, thiobenzamide, furanthioamide, pyridinethioamide, and polythioamide.

[0097] In some embodiments, additive (I) is sodium thiosulfate.

[0098] In some embodiments, additive (I) is an alkylamine. In some embodiments, additive (I) comprises one or more alkylamines.

[0099] In some embodiments, the alkylamine includes one or more monoamines.

[0100] In some embodiments, the alkylamine is a monoamine.

[0101] In some embodiments, the alkylamine is a diamine.

[0102] In some embodiments, the alkylamine is a polyamine.

[0103] In some embodiments, the polyamine is hexamethylenetetramine.

[0104] In some embodiments, the diamine is ethylenediamine.

[0105] In some embodiments, the alkylamine is represented by structure A;

[0106]

[0107] in:

[0108] (i)R 1 is hydrogen, alkyl, aryl, alkenyl, alkynyl or heterocyclyl; R 2 is hydrogen, alkyl, aryl, alkenyl, alkynyl or heterocyclyl; and R 3 is hydrogen, alkyl, aryl, alkenyl, alkynyl, or heterocyclyl; and

[0109] (ii) R 1 , R 2 , and R3 At least one of the groups is an alkyl group, an aryl group, an alkenyl group, an alkynyl group or a heterocyclic group.

[0110] In some embodiments, the alkyl group (which may be optionally substituted) represents a straight chain or branched chain or cyclic hydrocarbon group containing n carbon atoms.

[0111] In some embodiments, alkenyl (which may be optionally substituted) represents a straight or branched chain or cyclic hydrocarbon group containing n carbon atoms and at least one double bond.

[0112] In some embodiments, alkynyl (which may be optionally substituted) represents a straight or branched chain hydrocarbon group containing n carbon atoms and at least one triple bond.

[0113] In some embodiments, aryl (which may be optionally substituted) represents a carbocyclic aromatic group having 6 to 14 carbon atoms.

[0114] In some embodiments, heterocycle (which may be optionally substituted) represents a saturated, partially saturated, or fully unsaturated cyclic group containing 3 to 6 ring atoms, wherein 1 to 4 of the ring atoms are from the group consisting of oxygen, nitrogen, and sulfur.

[0115] In some embodiments, substitution refers to a group (R 1 , R 2 and / or R 3 ) may or may not be replaced by one or more groups (such as C n Alkyl, aryl, halogen, hydroxy, thio, amino, cyano, oxo, nitro, acyl, amide, C 1-6 Alkoxy, C 1-6 Alkenyloxy, aryloxy, acyloxy, C 1-6 Alkylamino, arylamino, C 1-6 Alkylthio, arylthio, alkylsulfonyl, arylsulfonyl, alkylsulfinyl, arylsulfinyl, C 1-8 alkylamide and carboxyl).

[0116] In some embodiments, R 1 , R 2 , R 3 Two or more of are the same.

[0117] In some embodiments, R 1 , R 2 , R 3 Each is different.

[0118] In which R 1 , R 2 , R 3 In some embodiments where one or more of the alkyl groups is alkyl, one or more of the alkyl groups is linear.

[0119] In some embodiments, the alkyl group is cyclic.

[0120] In some embodiments, the alkyl group is an alkyl fatty chain.

[0121] In some embodiments, R 1 , R 2 and R 3 It's methyl.

[0122] In some embodiments, R 1 , R 2 and R 3 It is ethyl.

[0123] In some embodiments, R 1 and R 2 is H and R 3 It is C 12 alkyl.

[0124] In some embodiments, R 1 and R 2 is H and R 3 It is C 18 Alkenyl.

[0125] In some embodiments, the selected additive (I) is an alkylamine.

[0126] In some embodiments, the alkylamine is oleylamine.

[0127] In some embodiments, the alkylamine is dodecylamine.

[0128] In some embodiments, the alkylamine is benzylamine.

[0129] In some embodiments, additive (I) is hexamethylenetetramine.

[0130] In some embodiments, additive (I) is sodium thiosulfate.

[0131] In some embodiments, additive (I) is ethylenediamine.

[0132] In some embodiments, the alkylamine is butylamine.

[0133] In some embodiments, the alkylamine is diethylamine.

[0134] In some embodiments, the alkylamine is triethylamine.

[0135] In some embodiments, additive (I) comprises thiourea.

[0136] In some embodiments, additive (I) comprises a thioamide-based compound.

[0137] In some embodiments, additive (I) comprises sodium thiosulfate.

[0138] In some embodiments, additive (I) comprises an alkylamine

[0139] In some embodiments, additive (I) comprises ethylenediamine.

[0140] In some embodiments, the alkylamine comprises butylamine.

[0141] In some embodiments, the alkylamine comprises diethylamine.

[0142] In some embodiments, the alkylamine comprises triethylamine.

[0143] In some embodiments, the additive (I) is a mixture of two compounds selected from the group consisting of a thiourea-based compound, sodium thiosulfate, an alkylamine, and a thioamide-based compound, and a weight ratio therebetween is 10:1 to 1:10.

[0144] In some embodiments, additive (I) is a mixture of thiourea and sodium thiosulfate.

[0145] In some embodiments, the weight ratio between thiourea and sodium thiosulfate is 10:1 to 1:10.

[0146] In some embodiments, additive (I) is a mixture of hexamethylenetetramine and thiourea.

[0147] In some embodiments, the weight ratio between thiourea and hexamethylenetetramine is 10:1 to 1:10.

[0148] In some embodiments, additive (I) is a mixture of hexamethylenetetramine and sodium thiosulfate.

[0149] In some embodiments, the weight ratio between hexamethylenetetramine and sodium thiosulfate is 10:1 to 1:10.

[0150] In some embodiments, additive (I) is a mixture of sodium thiosulfate and ethylenediamine.

[0151] In some embodiments, the weight ratio between sodium thiosulfate and ethylenediamine is 10:1 to 1:10.

[0152] In some embodiments, additive (I) is a mixture of thiourea and ethylenediamine.

[0153] In some embodiments, the weight ratio between thiourea and ethylenediamine is 10:1 to 1:10.

[0154] In some embodiments, the azole fungicide is prothioconazole.

[0155] In some embodiments, the azole fungicide is prothioconazole and the additive (I) is thiourea.

[0156] In some embodiments, the present invention provides a combination comprising (1) prothioconazole, (2) an additive (I) selected from the group consisting of thiourea-based compounds, sodium thiosulfate, alkylamines, thioamide-based compounds, and any combination thereof, and (3) water.

[0157] In some embodiments, additive (I) is thiourea.

[0158] In some embodiments, the combination contains no copper-based fungicides. In some embodiments, when the combination is a composition, the combination contains no copper-based fungicides. In some embodiments, when the combination is a premix composition, the combination contains no copper-based fungicides. In some embodiments, when the combination is a water-dilutable composition, the combination contains no copper-based fungicides.

[0159] In some embodiments, the combination is a composition.

[0160] In some embodiments, the combination is a composition.

[0161] In some embodiments, the combination is a premix composition.

[0162] In some embodiments, the combination is a tank mix.

[0163] In some embodiments, the combination is a water-dilutable composition.

[0164] In some embodiments, the combination is formulated together as a premix composition.

[0165] In some embodiments, the composition is a water-based composition.

[0166] In some embodiments, the water-based composition is a suspension concentrate.

[0167] In some embodiments, the water-based composition is a suspoemulsion.

[0168] In some embodiments, the composition is a non-aqueous based composition.

[0169] In some embodiments, the non-aqueous based composition is an emulsifiable concentrate composition.

[0170] In some embodiments, the non-aqueous based composition is an oil dispersion.

[0171] In some embodiments, the composition is a solid composition.

[0172] In some embodiments, the compositions are free of copper-based fungicides.

[0173] In some embodiments, the combination is formulated as two compositions.

[0174] In some embodiments, when the azole fungicide and the additive (I) are formulated as a premix composition, the weight ratio between the azole fungicide and the additive (I) is between about 0.2: 1 and 600: 1. In some embodiments, when the azole fungicide and the additive (I) are formulated as a premix composition, the weight ratio between the azole fungicide and the additive (I) is between about 10: 1 and 20: 1. In some embodiments, when the azole fungicide and the additive (I) are formulated as a premix composition, the weight ratio between the azole fungicide and the additive (I) is 17: 1. In some embodiments, when the azole fungicide and the additive (I) are formulated as a premix composition, the weight ratio between the azole fungicide and the additive (I) is 11.7: 1.

[0175] In some embodiments, when prothioconazole and thiourea are formulated as a premix composition, the weight ratio between prothioconazole and thiourea is between about 0.2: 1 and 600: 1. In some embodiments, when prothioconazole and thiourea are formulated as a premix composition, the weight ratio between prothioconazole and thiourea is between about 10: 1 and 20: 1. In some embodiments, when prothioconazole and thiourea are formulated as a premix composition, the weight ratio between prothioconazole and thiourea is 17: 1. In some embodiments, when prothioconazole and thiourea are formulated as a premix composition, the weight ratio between prothioconazole and thiourea is 11.7: 1.

[0176] In some embodiments, when the azole fungicide and the additive (I) are combined as a tank mix, the weight ratio between the azole fungicide and the additive (I) is between about 1:60 and 60: 1. In some embodiments, when the azole fungicide and the additive (I) are combined as a tank mix, the weight ratio between the azole fungicide and the additive (I) is 7.1:1.

[0177] In some embodiments, when prothioconazole and thiourea are combined as a tank mix, the weight ratio between prothioconazole and thiourea is between about 1:60 and 60: 1. In some embodiments, when prothioconazole and thiourea are combined as a tank mix, the weight ratio between prothioconazole and thiourea is 7.1:1.

[0178] In some embodiments, the combination comprises (1) a composition comprising an azole fungicide and (2) thiourea.

[0179] The composition as part of the combination is in the form of a suspension concentrate (SC), suspoemulsion (SE), emulsion (EW), water dispersible granules (WG), wettable powder (WP), dispersion concentrate (DC), dry seed treatment (DS), water slurry powder (WS), or flowable seed treatment (FS). Preferred compositions are suspoemulsions (SE) and suspension concentrates (SC).

[0180] In some embodiments, the combination further comprises an additional pesticide, such as a fungicide.

[0181] In some embodiments, the combination further comprises an additional fungicide.

[0182] In some embodiments, the combination comprises more than one azole fungicide.

[0183] In some embodiments, the combination comprises an additional fungicide other than an azole fungicide.

[0184] In some embodiments, the additional fungicide is selected from the group consisting of strobilurin fungicides, benzamide fungicides, morpholines, QiI fungicides, SDHIs, and any combination thereof.

[0185] In some embodiments, the combination comprises more than one additional fungicide other than an azole fungicide.

[0186] In some embodiments, the additional fungicide is fluazinam.

[0187] In some embodiments, the additional fungicide is folpet.

[0188] In some embodiments, the additional fungicide is captan.

[0189] In some embodiments, the additional fungicide is flumetylsulforim (5-fluoro-4-imino-3-methyl-1-tosyl-3,4-dihydropyrimidin-2(1H)-one).

[0190] Composition

[0191] The present invention provides a composition comprising (1) an amount of an azole fungicide, (2) an amount of at least one additive (I) and (3) an agriculturally acceptable carrier.

[0192] The present invention provides a composition comprising (1) an amount of an azole fungicide, (2) an amount of an additive (I) selected from the group consisting of a thiourea-based compound, sodium thiosulfate, an alkylamine, a thioamide-based compound, and any combination thereof, and (3) an agriculturally acceptable carrier.

[0193] The present invention provides a composition comprising (1) an amount of an azole fungicide, (2) an amount of at least one additive (I), and (3) an agriculturally acceptable carrier, wherein the composition does not contain a copper-based fungicide.

[0194] The present invention provides a composition comprising (1) an amount of an azole fungicide, (2) an amount of an additive (I) selected from the group consisting of a thiourea-based compound, sodium thiosulfate, an alkylamine, a thioamide-based compound, and any combination thereof, and (3) an agriculturally acceptable carrier for reducing or eliminating phytotoxicity associated with the application of the azole fungicide.

[0195] The present invention provides a composition comprising (1) an amount of an azole fungicide, (2) an amount of an additive (I) selected from the group consisting of a thiourea-based compound, sodium thiosulfate, an alkylamine, a thioamide-based compound, and any combination thereof, and (3) an agriculturally acceptable carrier for reducing or eliminating phytotoxicity associated with the application of the azole fungicide, wherein the composition does not contain a copper-based fungicide.

[0196] In some embodiments, the additive (I) is selected from the group consisting of thiourea, sodium thiosulfate, alkylamines, and any combination thereof. In some embodiments, the additive (I) is thiourea.

[0197] In some embodiments, azole phytotoxicity is reduced by at least 5%, at least 10%, or at least 20% compared to a composition not comprising additive (I).

[0198] In some embodiments, the composition is a liquid.

[0199] In some embodiments, the composition is a water-based composition.

[0200] In some embodiments, the water-based composition is a suspension concentrate.

[0201] In some embodiments, the water-based composition is a suspoemulsion.

[0202] In some embodiments, the composition is a non-aqueous based composition.

[0203] In some embodiments, the non-aqueous based composition is an emulsifiable concentrate composition.

[0204] In some embodiments, the non-aqueous based composition is an oil dispersion.

[0205] In some embodiments, the composition is a solid composition.

[0206] In some embodiments, the azole fungicide is in its solid form in the composition.

[0207] In some embodiments, the azole fungicide is suspended in an agriculturally acceptable carrier.

[0208] In some embodiments, the azole fungicide is dissolved in an agriculturally acceptable carrier.

[0209] In some embodiments, the agriculturally acceptable carrier is water.

[0210] In some embodiments, the agriculturally acceptable carrier is an organic carrier.

[0211] In some embodiments, the organic vehicle is an oil.

[0212] In some embodiments, the organic carrier is a water-immiscible carrier.

[0213] In some embodiments, the weight ratio between the azole fungicide and the additive (I) in the composition is between about 0.2: 1 and 600: 1. In some embodiments, the weight ratio between the azole fungicide and the additive (I) in the composition is between about 10: 1 and 20: 1. In some embodiments, the weight ratio between the azole fungicide and the additive (I) in the composition is 17: 1. In some embodiments, the weight ratio between the azole fungicide and the additive (I) in the composition is 11.7: 1.

[0214] In some embodiments, the azole fungicide is prothioconazole.

[0215] In some embodiments, additive (I) is thiourea.

[0216] In some embodiments, the azole fungicide is prothioconazole and the additive (I) is thiourea.

[0217] In some embodiments, the composition comprises (1) an azole fungicide, (2) an additive (I) selected from the group consisting of thiourea-based compounds, sodium thiosulfate, alkylamines, thioamide-based compounds, and any combination thereof, and (3) a copper-based fungicide.

[0218] In some embodiments, the composition comprises (1) an azole fungicide, (2) an additive (I) selected from the group consisting of thiourea-based compounds, sodium thiosulfate, alkylamines, thioamide-based compounds, and any combination thereof, (3) a strobilurin fungicide, and (4) a copper-based fungicide.

[0219] In some embodiments, the composition comprises (1) an azole fungicide, (2) an additive (I) selected from the group consisting of thiourea-based compounds, sodium thiosulfate, alkylamines, thioamide-based compounds, and any combination thereof, (3) a copper-based fungicide, and (4) water.

[0220] In some embodiments, the composition comprises (1) an azole fungicide, (2) an additive (I) selected from the group consisting of thiourea-based compounds, sodium thiosulfate, alkylamines, thioamide-based compounds, and any combination thereof, (3) a copper-based fungicide, (4) a strobilurin fungicide, and (5) water.

[0221] In some embodiments, the composition comprises (1) an azole fungicide, (2) an additive (I) selected from the group consisting of thiourea-based compounds, sodium thiosulfate, alkylamines, thioamide-based compounds, and any combination thereof, and (3) water.

[0222] In some embodiments, the composition comprises (1) an azole fungicide, (2) an additive (I) selected from the group consisting of thiourea-based compounds, sodium thiosulfate, alkylamines, thioamide-based compounds, and any combination thereof, and (3) water, wherein the composition does not contain a copper-based fungicide.

[0223] The present invention provides a composition comprising (1) an azole fungicide in an amount of about 1-50 wt % by weight based on the total weight of the composition, and (2) at least one additive (I) in an amount of 0.1-5 wt % by weight based on the total weight of the composition.

[0224] The present invention provides a composition comprising (1) an azole fungicide in an amount of about 1-50 wt % by weight based on the total weight of the composition, and (2) an additive (I) selected from the group consisting of a thiourea-based compound, sodium thiosulfate, an alkylamine, a thioamide-based compound, and any combination thereof in an amount of about 0.1-5 wt % by weight based on the total weight of the composition.

[0225] In some embodiments, the additive (I) is selected from the group consisting of thiourea, sodium thiosulfate, alkylamines, and any combination thereof. In some embodiments, the additive (I) is thiourea.

[0226] In some embodiments, the compositions comprise more than one azole fungicide.

[0227] In some embodiments, the composition comprises an additional fungicide other than an azole fungicide.

[0228] In some embodiments, the composition comprises more than one additional fungicide other than an azole fungicide.

[0229] In some embodiments, the additional fungicide is a copper-based fungicide. In some embodiments, the additional fungicide is different from the copper-based fungicide.

[0230] In some embodiments, the compositions are free of copper-based fungicides.

[0231] In some embodiments, the additional fungicide is selected from the group consisting of strobilurin fungicides, benzamide fungicides, morpholines, QiI fungicides, SDHIs, and any combination thereof.

[0232] In some embodiments, the additional fungicide is flumetylsulforim (5-fluoro-4-imino-3-methyl-1-tosyl-3,4-dihydropyrimidin-2(1H)-one).

[0233] In some embodiments, the additional fungicide is fluazinam

[0234] In some embodiments, the additional fungicide is folpet

[0235] In some embodiments, the additional fungicide is captan.

[0236] In some embodiments, the additional fungicide is a strobilurin fungicide.

[0237] In some embodiments, the additional fungicide is a dithiocarbamate fungicide. In some embodiments, the dithiocarbamate fungicide is mancozeb.

[0238] In some embodiments, the composition comprises two additional fungicides other than the azole fungicide which are a strobilurin and a copper-based fungicide.

[0239] In some embodiments, the composition further comprises at least one agriculturally acceptable additive.

[0240] In some embodiments, the composition comprises (1) an azole fungicide and (2) an additive (I), wherein the additive (I) is a thiourea.

[0241] In some embodiments, the amount of azole fungicide in the composition is between 0.1% and 70% by weight based on the total weight of the composition.

[0242] In some embodiments, when the azole fungicide is prothioconazole, the amount of the azole fungicide in the composition is between 0.1% and 70% by weight based on the total weight of the composition.

[0243] In some embodiments, the amount of additive (I) in the composition is between 0.1% and 5% by weight based on the total weight of the composition.

[0244] In some embodiments, when additive (I) is thiourea, the amount of additive (I) in the composition is between 0.1% and 5% by weight based on the total weight of the composition.

[0245] In some embodiments, when additive (I) is used, phytotoxicity is reduced by at least 5% compared to when additive (I) is not used.

[0246] In some embodiments, the compositions comprise one or more additional fungicides.

[0247] In some embodiments, the composition further comprises a water-immiscible solvent.

[0248] In some embodiments, the present invention provides a composition comprising any of the combinations described herein and at least one acceptable additive.

[0249] In some embodiments, the agriculturally acceptable additive is an agriculturally acceptable carrier.

[0250] In some embodiments, the agriculturally acceptable carrier is water.

[0251] In some embodiments, the agriculturally acceptable carrier is an organic (non-aqueous) carrier.

[0252] In some embodiments, the organic carrier is a water-immiscible carrier.

[0253] In some embodiments, when the azole fungicide is in its solid form and suspended in the composition, the particle size distribution (d90) is 10 microns or less. In some embodiments, the composition comprises particles having a particle size distribution (d90) of 7 microns or less. In some embodiments, the composition comprises particles having a particle size distribution (d90) of 4 microns or less.

[0254] In some embodiments, the concentration of additive (I) in the composition is between 0.01% and 10% by weight based on the total weight of the composition. In some embodiments, the concentration of additive (I) in the composition is between 0.1% and 8% by weight based on the total weight of the composition. In some embodiments, the concentration of additive (I) in the composition is between 0.1% and 5% by weight based on the total weight of the composition.

[0255] In some embodiments, the concentration of the azole fungicide in the composition is between 1% and 95% by weight based on the total weight of the composition. In some embodiments, the concentration of the azole fungicide in the composition is between 1% and 15% by weight based on the total weight of the composition. In some embodiments, the concentration of the azole fungicide in the composition is between 2% and 8% by weight based on the total weight of the composition.

[0256] In some embodiments, the concentration of the additional fungicide in the composition is between 1% and 45% by weight based on the total weight of the composition. In some embodiments, the concentration of the additional fungicide in the composition is between 10% and 40% by weight based on the total weight of the composition. In some embodiments, the concentration of the additional fungicide in the composition is between 20% and 35% by weight based on the total weight of the composition.

[0257] In some embodiments, the composition comprises an additional fungicide which is a copper-based fungicide.

[0258] In some embodiments, the concentration of the copper-based fungicide is between 30%-40% by weight based on the total weight of the composition.

[0259] In some embodiments, the composition comprises an additional fungicide that is different from the copper-based fungicide.

[0260] In some embodiments, the compositions are free of copper-based fungicides.

[0261] The addition of additives affects the chemical and physical stability of the composition. The additives can, for example, improve the stability of the composition.

[0262] In some embodiments, agriculturally acceptable additives are selected from agriculturally acceptable carriers, buffers, acidulants, antifoams, antifreezes, solvents, cosolvents, light agents, UV absorbers, free radical scavengers and antioxidants, adhesives, neutralizers, thickeners, binders, chelating agents, biocides, drift retardants, surfactants, dispersants, pigments, wetting agents, safeners and preservatives. The additives include, but are not limited to, surfactants, pigments, wetting agents and safeners, or such preservatives as bacteriostats or bactericides.

[0263] In some embodiments, the agriculturally acceptable additive is an agriculturally acceptable carrier. In some embodiments, the composition comprises at least one agriculturally acceptable carrier.

[0264] Adding a small amount of one or more agriculturally acceptable additives may affect parameters such as stability, efficacy and / or fastness to rain washout of the composition according to the invention. Adding a small amount of one or more agriculturally acceptable carriers preferably increases the stability, efficacy and / or fastness to rain washout of the composition according to the invention.

[0265] In some embodiments, the agriculturally acceptable carrier is water.

[0266] In some embodiments, the composition comprises 30%-80% water by weight. In some embodiments, the composition comprises 40%-70% water by weight. In some embodiments, the composition comprises 40%-80% water by weight. In some embodiments, the composition comprises 50%-70% water by weight. In some embodiments, the composition comprises 50%-55% water by weight. In some embodiments, the composition comprises about 52% water by weight. In some embodiments, the composition comprises about 53% water by weight. In some embodiments, the composition comprises about 54% water by weight. In some embodiments, the composition comprises about 55% water by weight.

[0267] In some embodiments, the composition further comprises a polyelectrolyte as described in PCT / IB2021 / 061258 (the entire contents of which are hereby incorporated by reference into this application).

[0268] In some embodiments, the composition is a suspension concentrate.

[0269] In some embodiments, the composition is a suspension concentrate, wherein the composition comprises the azole fungicide in its solid form.

[0270] In some embodiments, the azole is in dissolved form.

[0271] In some embodiments, the composition is a water-based composition.

[0272] In some embodiments, the water-based composition is a suspension concentrate.

[0273] In some embodiments, the water-based composition is a suspoemulsion.

[0274] In some embodiments, the composition is a non-aqueous based composition.

[0275] In some embodiments, the non-aqueous based composition is an emulsifiable concentrate composition.

[0276] In some embodiments, the non-aqueous based composition is an oil dispersion.

[0277] In some embodiments, the composition is a solid composition.

[0278] In some embodiments, when the composition comprises an additional pesticide, the composition is a suspoemulsion, wherein the composition comprises at least two carriers: (1) water and (2) a water-immiscible carrier.

[0279] In some embodiments, the azole fungicide is dissolved in a water-immiscible carrier.

[0280] In some embodiments, the additional fungicide is selected from the group consisting of strobilurin fungicides, benzamide fungicides, morpholines, QiI fungicides, SDHIs, and any combination thereof.

[0281] In some embodiments, the additional fungicide is flumetylsulforim (5-fluoro-4-imino-3-methyl-1-tosyl-3,4-dihydropyrimidin-2(1H)-one).

[0282] In some embodiments, the additional fungicide is fluazinam

[0283] In some embodiments, the additional fungicide is folpet

[0284] In some embodiments, the additional fungicide is captan.

[0285] In some embodiments, the additional fungicide is suspended in water or dissolved in a water-immiscible carrier.

[0286] In some embodiments, the additional fungicide is suspended in water and / or dissolved in a water-immiscible carrier.

[0287] In some embodiments, when the composition comprises two or more additional fungicides, at least one additional fungicide is dissolved in the water-immiscible carrier and at least one additional fungicide is suspended in water.

[0288] In some embodiments, when the composition comprises two or more additional fungicides, at least two of the additional fungicides are dissolved in the water-immiscible carrier.

[0289] In another embodiment, the composition comprises: (1) prothioconazole, (2) thiourea, and (3), wherein prothioconazole is dissolved in a water-immiscible carrier.

[0290] In another embodiment, the composition comprises: (1) prothioconazole, (2) thiourea, and (3), wherein prothioconazole is suspended in water.

[0291] In some embodiments, the water-immiscible carrier may include, but is not limited to, aromatic hydrocarbons (e.g., toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, isopropylbenzene, tert-butylbenzene, naphthalene, monoalkyl or polyalkyl substituted naphthalene), paraffins (e.g., octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane, heneicosane, docosane, tricosane, tetracosane, pentacosane, and branched chain isomers thereof), petroleum, Ketones (e.g., acetophenone, cyclohexanone), vegetable oils (e.g., olive oil, kapok oil, castor oil, papaya oil, camellia oil, palm oil, sesame oil, corn oil, rice bran oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil, linseed oil, tung oil, sunflower oil, safflower oil, tall oil), alkyl esters of vegetable oils (e.g., rapeseed oil methyl ester or rapeseed oil ethyl ester, rapeseed oil propyl ester, rapeseed oil butyl ester, tall oil fatty acid ester, etc.), diesel, mineral oil, fatty acid amides (e.g., C1-C3 amines, alkylamines or amines having C6-C 18 carboxylic acid), dimethyl amides of fatty acids, N,N-dimethylalkyl amides (NN-dimethyldecylamide, N,N-dimethyloctylamide, N,N-dimethyldodecylamide, N,N-dialkylalkanamides), N-alkylalkanamides, fatty acids, tall oil fatty acids, alkyl esters of fatty acids (e.g., C8 to C 22 C1-C4 monohydric alcohol esters of fatty acids, such as methyl oleate, ethyl oleate), modified vegetable oils and combinations thereof.

[0292] In preferred embodiments, the water-immiscible carrier may include, but is not limited to, aromatic hydrocarbons, fatty acid amides, alkyl esters of vegetable oils, and vegetable oils.

[0293] In some embodiments, the water-immiscible carrier is acetophenone.

[0294] In some embodiments, the water-immiscible carrier is a fatty acid amide.

[0295] In some embodiments, the water-immiscible carrier is N,N-dimethyldecanamide.

[0296] In an embodiment, the amount of the water-immiscible carrier can be about 0.1wt.%-20wt.%, about 1wt.%-15wt.%, or about 0.1wt.%-10wt.%, or about 1%-5% based on the total weight of the composition. In a specific embodiment, the non-aqueous liquid carrier can be present in a concentration of about 3% by weight based on the total weight of the composition.

[0297] In some embodiments, the composition further comprises an adjuvant.

[0298] In some embodiments, the adjuvant in the liquid carrier may include, but is not limited to, vegetable oils, alkyl esters of vegetable oils such as soybean methyl ester, soybean ethyl ester, rapeseed oil methyl ester or rapeseed oil ethyl ester, alkoxylated sorbitan esters such as sorbitan monolaurate alkoxylates, such as polyoxyethylene (16) sorbitan monolaurate (Tween TM 24), Polyoxyethylene (20) sorbitan monolaurate (Tween TM 20; PSML-20), polyoxyethylene (4) sorbitan monolaurate (Tween TM 21) Polyoxyethylene (8) sorbitan monolaurate (Tween TM 22), Polyoxyethylene (12) sorbitan monolaurate (Tween TM 23) Sorbitan monolaurate ( S / 20, LK, LC, 20), polyoxyethylene (20) sorbitan monostearate alkoxylate such as polyoxyethylene (20) sorbitan monostearate (Tween TM 60), polyoxyethylene (4) sorbitan monostearate (Tween TM 61) Sorbitan monostearate ( S / 90, S. 60), sorbitan monooleate alkoxylates such as polyoxyethylene (20) sorbitan monooleate (Tween TM 80. SMO 20, 80. SMO 20U), polyoxyethylene (5) sorbitan monooleate (Tween TM 81) Sorbitan monooleate ( S / 80, 80), and combinations thereof.

[0299] In some embodiments, the adjuvant is Synergen SOC.

[0300] In some embodiments, the agriculturally acceptable additive is a surfactant.

[0301] In some embodiments, the surfactant is a wetting agent, a dispersing agent, or a combination thereof.

[0302] In some embodiments, the composition comprises at least two surfactants.

[0303] In some embodiments, the dispersant is a polyelectrolyte block copolymer (as described in WO 2017 / 098325, the entire contents of which are hereby incorporated by reference into this application).

[0304] In some embodiments, the dispersant comprises a block polymer comprising 77% sodium 2-acrylamido-2-methylpropane-1-sulfonate (AMPS) monomer and 23% ethyl acrylate (EA) monomer.

[0305] In some embodiments, the dispersant is a 30% by weight aqueous solution of a block polymer comprising 77% sodium 2-acrylamido-2-methylpropane-1-sulfonate (AMPS) monomer and 23% ethyl acrylate (EA) monomer, which can be prepared as described in Example 1 of WO 2017 / 098325.

[0306] In some embodiments, the agriculturally acceptable additive is a dispersant. In some embodiments, the composition comprises at least one dispersant.

[0307] In some embodiments, the composition comprises at least one anionic dispersant and at least one nonionic surfactant.

[0308] The composition of the present invention may also contain two or more different dispersants. The dispersants are preferably present in an amount of between 0 and up to 10% (w / v), more preferably between 0.01 and up to 5% (w / v), more preferably between 0.02 and up to 2% (w / v),

[0309] In some embodiments, the dispersant is a modified acrylic polymer, unmodified acrylic acid, or any combination thereof.

[0310] In some embodiments, the modified acrylic polymer is a modified styrene acrylic, polymethyl methacrylate-polyethylene glycol graft copolymer or any combination thereof. In some embodiments, the modified acrylic polymer is a modified styrene acrylic polymer. In some embodiments, the modified styrene acrylic polymer is Atlox Metasperse 500L, Atlox Metsaperse 550S (sold by Croda). In some embodiments, the modified acrylic polymer is a polymethyl methacrylate-polyethylene glycol graft copolymer.

[0311] In some embodiments, the concentration of the dispersant in the composition is 0.01%-15% by weight based on the total weight of the composition.

[0312] In some embodiments, the concentration of the dispersant in the composition is 0.01%-12% by weight based on the total weight of the composition. In some embodiments, the concentration of the dispersant in the composition is 1%-12% by weight based on the total weight of the composition. In some embodiments, the concentration of the dispersant in the composition is 0.01%-10% by weight based on the total weight of the composition. In some embodiments, the concentration of the dispersant in the composition is 1%-5% by weight based on the total weight of the composition. In some embodiments, the concentration of the dispersant in the composition is 5%-10% by weight based on the total weight of the composition. In some embodiments, the concentration of the dispersant is about 2% by weight based on the total weight of the composition. In some embodiments, the concentration of the dispersant is about 5% by weight based on the total weight of the composition. In some embodiments, the concentration of the dispersant is about 6% by weight based on the total weight of the composition. In some embodiments, the concentration of the dispersant is about 7% by weight based on the total weight of the composition. In some embodiments, the concentration of the dispersant is about 8% by weight based on the total weight of the composition. In some embodiments, the concentration of the dispersant is about 9% by weight based on the total weight of the composition. In some embodiments, the concentration of the dispersant is about 10% by weight based on the total weight of the composition.

[0313] The composition according to the invention may further comprise at least one pH adjusting agent or buffer, such as an organic or inorganic base and / or an organic or inorganic acid.

[0314] In some embodiments, the composition comprises one or more additives, such as biocides (preservatives), defoamers, thickeners, and drift retardants.

[0315] The wetting agent may be selected from dioctyl sulfosuccinate, polyoxyethylene / polyoxypropylene, ethoxylated tristyrylphenol, ethoxylated tristyrylphenol sulfate, ethoxylated tristyrylphenol phosphate, ethoxylated propoxylated tristyrylphenol, and. The composition of the present invention may also comprise two or more different wetting agents. The wetting agent is preferably present in an amount of between 0 and up to 10% (w / v), more preferably between 0.01 and up to 5% (w / v), more preferably between 0.02 and up to 1% (w / v), more preferably about 0.05% (w / v).

[0316] In some embodiments, the concentration of the wetting agent in the composition is 1%-10% by weight based on the total weight of the composition. In some embodiments, the concentration of the wetting agent in the composition is 0%-5% by weight based on the total weight of the composition. In some embodiments, the concentration of the wetting agent in the composition is 1%-5% by weight based on the total weight of the composition. In some embodiments, the concentration of the wetting agent in the composition is 1%-3% by weight based on the total weight of the composition. In some embodiments, the concentration of the wetting agent in the composition is about 2% by weight based on the total weight of the composition.

[0317] In some embodiments, the composition comprises at least one rheology modifier.In some embodiments, the agriculturally acceptable additive is a rheology modifier.

[0318] In some embodiments, the rheology modifier is a thickener. In some embodiments, the composition comprises at least one thickener.

[0319] Thickeners (when present) are preferably selected from agar, alginic acid, alginates, carrageenan, gellan gum, xanthan gum, succinoglycan gum, guar gum, acetylated distarch adipate, acetylated oxidized starch, arabinogalactan, ethylcellulose, methylcellulose, locust bean gum, sodium starch octenylsuccinate and triethyl citrate. The composition of the present invention may also comprise two or more different thickeners. The thickener is preferably present in an amount of 0 to up to 10% (w / v), more preferably 0.01 to up to 5% (w / v), more preferably 0.02 to up to 1% (w / v), more preferably about 0.05% (w / v).

[0320] In some embodiments, the thickening agent is xanthan gum.

[0321] In some embodiments, the rheology modifier is Agrhopol 23, 23 (sold by Solvay). In some embodiments, the rheology modifier is xanthan gum.

[0322] In some embodiments, the antifoaming agent is SAG 1572.

[0323] In some embodiments, the concentration of the rheology modifier in the composition is 0.01%-10% by weight based on the total weight of the composition. In some embodiments, the concentration of the rheology modifier in the composition is 5%-10% by weight based on the total weight of the composition. In some embodiments, the concentration of the rheology modifier in the composition is about 6% by weight based on the total weight of the composition. In some embodiments, the concentration of the rheology modifier in the composition is about 8% by weight based on the total weight of the composition.

[0324] In some embodiments, the composition comprises at least one thickener and at least one biocide. In some embodiments, the amount of thickener and biocide in the composition is up to 1% by weight based on the total weight of the composition.

[0325] In some embodiments, the agriculturally acceptable additive is a preservative. In some embodiments, the composition comprises at least one preservative.

[0326] In some embodiments, the preservative is a biocide. In some embodiments, the composition comprises at least one biocide. In some embodiments, the preservative is MBS.

[0327] In some embodiments, the concentration of the preservative in the composition is 0.01%-5% by weight based on the total weight of the composition. In some embodiments, the concentration of the preservative in the composition is 0.01%-1% by weight based on the total weight of the composition. In some embodiments, the concentration of the preservative in the composition is about 0.1% by weight based on the total weight of the composition. In some embodiments, the concentration of the preservative in the composition is 0.083% by weight based on the total weight of the composition.

[0328] The compositions according to the invention may comprise additional biologically active ingredients, also referred to as additional agrochemicals, such as growth regulators, biostimulants, fungicides, herbicides, insecticides, acaricides, molluscicides, miticides, rodenticides; and / or bactericides.

[0329] Various agrochemicals can be used as additional biologically active ingredients. Examples of such agrochemicals are, but are not limited to, crop protection agents such as pesticides, safeners, plant growth regulators, insect repellents, biostimulants and preservatives such as bacteriostats or bactericides.

[0330] In some embodiments, the composition comprises at least one additional biologically active ingredient, preferably an additional insecticide, fungicide and / or herbicide.

[0331] Additional agricultural chemicals that can be used with the combinations and compositions of the present invention are described below.

[0332] The composition of the present invention may also include two or more additional biologically active ingredients, such as two or more fungicides, two or more herbicides, two or more insecticides, two or more miticides, two or more bactericides, or combinations thereof, such as at least one antifungal compound and at least one insecticide, at least one antifungal compound and at least one herbicide, at least one antifungal compound and at least one miticide, at least one antifungal compound and at least one bactericide, at least one herbicide and at least one insecticide, at least one herbicide and at least one miticide, at least one herbicide and at least one bactericide, at least one insecticide and at least one miticide, at least one insecticide and at least one bactericide, and at least one miticide and at least one bactericide. As known to the skilled person, some biologically active ingredients have a wide range of target organisms and are therefore included in more than one subgroup of biologically active ingredients. The at least one additional biologically active ingredient is preferably present in a concentration between 0.1 and 90 w / v%, more preferably between 1 and 70 w / v%, more preferably between 10 and 50 w / v%.

[0333] The additional biologically active ingredient is preferably an insecticide, a fungicide and / or a herbicide.

[0334] The invention provides a dilution composition comprising any of the compositions described herein and water.

[0335] The present invention provides a dilute composition comprising an azole fungicide, an additive (I) and water.

[0336] In some embodiments, the dilution composition comprises an azole fungicide, thiourea, and water.

[0337] In some embodiments, the azole fungicide is prothioconazole.

[0338] In some embodiments, the weight ratio between the azole fungicide and the additive (I) is between about 1:60 and 60: 1. In some embodiments, the weight ratio between the azole fungicide and the additive (I) is 7.1:1.

[0339] In some embodiments, the weight ratio between the azole fungicide and the thiourea is between about 1:60 and 60: 1. In some embodiments, the weight ratio between the azole fungicide and the thiourea is 7.1:1.

[0340] In some embodiments, the weight ratio between prothioconazole and thiourea is between about 1:60 and 60: 1. In some embodiments, the weight ratio between prothioconazole and thiourea is 7.1:1.

[0341] In some embodiments, when the composition comprises picoxystrobin and prothioconazole, the composition is free of a copper-based fungicide.

[0342] In some embodiments, when the composition comprises picoxystrobin and prothioconazole, the composition is free of Bordeaux mixture.

[0343] In some embodiments, when the composition comprises picoxystrobin and prothioconazole, the composition is free of cupric oxychloride.

[0344] In some embodiments, the composition is other than a SE composition comprising:

[0345] (i) 34.53% w / w Bordeaux mixture,

[0346] (ii) 2.70% w / w picoxystrobin,

[0347] (iii) 10% w / w glycerol,

[0348] (iv) 2% w / w T-77,

[0349] (v) 1% w / w Atlox Metasperse TM 500L,

[0350] (vi) 1% w / w ATLAS G5002L,

[0351] (vii) 0.1% w / w SAG 1572,

[0352] (viii) 0.02% w / w Proxel GXL,

[0353] (ix) 3% w / w prothioconazole,

[0354] (x) 3.5% w / w Adma 10,

[0355] (xi) 1% w / w Soprophor BSU,

[0356] (xii) 0.2% w / w Rhodopol AgrhO 23,

[0357] (xiii) 0.4% w / w thiourea, and

[0358] (xiv) 40.95% w / w water.

[0359] In some embodiments, the composition is other than a SE composition comprising:

[0360] (i) 34.29% w / w Bordeaux mixture,

[0361] (ii) 2.78% w / w picoxystrobin,

[0362] (iii) 5.00% w / w propylene glycol,

[0363] (iv) 1.00% w / w Metasperse 550S,

[0364] (v) 2.80% w / w Borresperse CA,

[0365] (vi) 2.00% w / w Geropon T-77,

[0366] (vii) 2.00% w / w Atlox 4894,

[0367] (viii) 0.10% w / w SAG 1572,

[0368] (ix) 0.05% w / w Proxel GXL,

[0369] (x) 41.66% w / w DM water,

[0370] (xi) 0.35% w / w thiourea,

[0371] (xii) 3.06% w / w prothioconazole,

[0372] (xiii) 3.06% w / w Armid DM 10,

[0373] (xiv) 1.50% w / w Emulsogen TS200,

[0374] (xv) 0.25% w / w triethanolamine, and

[0375] (xvi) 0.095% w / w Rhodopol 23.

[0376] In some embodiments, the composition is other than a SE composition comprising:

[0377] (i) 35.49% w / w Bordeaux mixture,

[0378] (ii) 39.72% w / w DM water,

[0379] (iii) 2.80% w / w picoxystrobin,

[0380] (iv) 3.16% w / w prothioconazole,

[0381] (v) 3.50% w / w Rhodiasolv Adma 10,

[0382] (vi) 2% w / w of Geropon T-77,

[0383] (vii) 1% w / w Soprophor BSU,

[0384] (viii) Atlox Metasperse 500L 1% w / w,

[0385] (ix) 1.00% w / w Atlas G5002L,

[0386] (x) 0.1% w / w SAG 1572,

[0387] (xi) 10% w / w glycerol,

[0388] (xii) 0.02% w / w Proxel GXL,

[0389] (xiii) 0.2% w / w Rhodopol 23, and

[0390] (xiv) 0.4% w / w thiourea.

[0391] In some embodiments, the composition is other than a SE composition comprising:

[0392] (i) 35.49% w / w Bordeaux mixture,

[0393] (ii) 2.80% w / w Borresperse CA,

[0394] (iii) 37.62% w / w DM water,

[0395] (iv) 2.80% w / w picoxystrobin,

[0396] (v) 3.16% w / w prothioconazole,

[0397] (vi) 3.50% w / w Rhodiasolv Adma 10,

[0398] (vii) 1% w / w Geropon T-77,

[0399] (viii) 1% w / w Soprophor BSU,

[0400] (ix) Atlox Metasperse 500L 1% w / w,

[0401] (x) 1.00% w / w Atlas G5002L,

[0402] (xi) 0.1% w / w SAG 1572,

[0403] (xii) 10% w / w glycerol,

[0404] (xiii) 0.02% w / w Proxel GXL,

[0405] (xiv) 0.1% w / w Rhodopol 23, and

[0406] (xv) 0.4% w / w thiourea.

[0407] In some embodiments, the composition is other than a SE composition comprising:

[0408] (i) 34.53% w / w Bordeaux mixture,

[0409] (ii) 2.70% w / w picoxystrobin,

[0410] (iii) 5.00% w / w propylene glycol,

[0411] (iv) 2.00% w / w of Geropon T-77,

[0412] (v) 1.00% w / w Borresperse CA,

[0413] (vi) Atlox Metasperse 500L 1.00% w / w,

[0414] (vii) 3.00% w / w Atlox 4894,

[0415] (viii) 0.10% w / w SAG 1572,

[0416] (ix) 0.10% w / w Proxel GXL,

[0417] (x) (a) 2% ethylenediamine, or (b) 0.32% thiourea, or (c) a mixture of 1% + 0.5% sodium thiosulfate and thiourea,

[0418] (xi) 3.00% w / w prothioconazole,

[0419] (xii) 3.00% w / w Rhodiasolv ADMA 10,

[0420] (xiii) 1.50% w / w Emulsogen TS200,

[0421] (xiv) 0.20% w / w Agrhopol 23, and

[0422] (xv) Water, made up to 100% w / w.

[0423] In some embodiments, the composition is other than a SE composition comprising:

[0424] (i) 22.89% w / w copper oxychloride (for industrial use),

[0425] (ii) 3.67% w / w picoxystrobin (technical use),

[0426] (iii) 4.14% w / w prothioconazole,

[0427] (iv) 0.45% w / w acetic acid,

[0428] (v) 13.22% w / w acetophenone,

[0429] (vi) 0.2% w / w AG-RH 23,

[0430] (vii) 1% w / w Agnique BP 420,

[0431] (viii) 2.64% w / w Agsolex 8,

[0432] (ix) 1.87% w / w Borresperse CA,

[0433] (x) 0.2% w / w chitosan,

[0434] (xi) 5% w / w PolyAgro A,

[0435] (xii) 3% w / w propylene glycol,

[0436] (xiii) 0.02% w / w Proxel GXL,

[0437] (xiv) 0.2% w / w SAG 1572,

[0438] (xv) 2.54% w / w sodium acetate,

[0439] (xvi) 2.02% w / w Soprophor TS / 16,

[0440] (xvii) 0.66% w / w Synergen SOC,

[0441] (xviii) 0.35% w / w thiourea,

[0442] (xix) 0.3% w / w Van Gel B, and

[0443] (xx) Water, made up to 100% w / w.

[0444] In some embodiments, the composition is other than a composition comprising:

[0445] (i) 30.08% w / w Bordeaux mixture (for industrial use),

[0446] (ii) 2.71% w / w of picoxystrobin (technical use),

[0447] (iii) 3.1% w / w prothioconazole,

[0448] (iv) 0.2% w / w AG-RH 23,

[0449] (v) 1% w / w ATLAS G-5002L-LQ-(CQ),

[0450] (vi) Atlox Metasperse 500L-LQ-RB 1% w / w,

[0451] (vii) 2% w / w GEROPON T 77,

[0452] (viii) 10% w / w glycerol,

[0453] (ix) 0.02% w / w Proxel GXL,

[0454] (x) 3.5% w / w RHODIASOLV ADMA 10,

[0455] (xi) 0.1% w / w SAG 1572,

[0456] (xii) 1% w / w Soprophor BSU,

[0457] (xiii) 0.4% w / w thiourea,

[0458] (xiv) 2.8% w / w Borresperse CA, and

[0459] (xv) Soft water, made up to 100% w / w.

[0460] Methods and uses

[0461] The invention provides a method of treating a plant or a locus thereof against pathogens comprising contacting the plant, a part of a plant, or the locus with any of the combinations and / or compositions described herein.

[0462] In some embodiments, the pathogen is a plant pathogenic fungus.

[0463] In some embodiments, treatment comprises controlling diseases caused by pathogens. In some embodiments, the method controls diseases caused by phytopathogenic fungi in plants or on their propagation materials, and the method comprises contacting these plants or their propagation materials with a composition according to the invention, including an aqueous dilution composition.

[0464] In some embodiments, treating comprises controlling diseases caused by phytopathogenic fungi in the plant or on its propagation material.

[0465] In some embodiments, the treatment includes preventing, reducing and / or eliminating the presence of pathogens on a plant, a part of a plant, or a place. In some embodiments, the method prevents, reduces and / or eliminates the presence of pathogens on a plant, a part of a plant, or a place, and the method includes contacting the plant, a part of a plant, or a place with an aqueous composition according to the present invention. In some embodiments, the method prevents, reduces and / or eliminates the presence of pathogens on a plant, a part of a plant, or a place, and the method includes contacting the plant, a part of a plant, or a place with any of the combinations and / or compositions described herein.

[0466] In some embodiments, the treatment comprises protecting a plant, a part of a plant, or a place against pathogens. In some embodiments, the method protects a plant, a part of a plant, or a place against pathogens and comprises contacting the plant, a part of a plant, or a place with a diluted aqueous composition according to the invention. In some embodiments, the method protects a plant, a part of a plant, or a place against pathogens and comprises contacting the plant, a part of a plant, or a place with any of the combinations and / or compositions described herein.

[0467] The present invention also provides a method for increasing the application rate of an azole fungicide to a plant or a plant part and / or increasing the frequency of application of an azole fungicide to a plant or a plant part without causing increased phytotoxicity to the plant, wherein the method comprises applying to the plant or the plant part an azole fungicide in combination with an additive (I) selected from the group consisting of: a thiourea-based compound, sodium thiosulfate, an alkylamine, a thioamide-based compound, and any combination thereof.

[0468] In some embodiments, the method improves pest control without causing increased phytotoxicity to the plant.

[0469] The present invention also provides a method of improving pest control using an azole fungicide without increasing phytotoxicity, wherein the method comprises applying any of any combinations and / or compositions described herein comprising an azole fungicide to a locus where pest control is desired.

[0470] In some embodiments, the locus is a plant. In some embodiments, the locus is soil.

[0471] The present invention also provides a method for reducing and / or eliminating phytotoxicity to plants or plant parts caused by azole fungicides applied to plants or plant parts, wherein the method comprises applying an azole fungicide in combination with an additive (I) selected from the group consisting of thiourea-based compounds, sodium thiosulfate, alkylamines, thioamide-based compounds, and any combination thereof.

[0472] In some embodiments, the phytotoxicity is leaf necrosis.

[0473] The present invention also provides a method for improving plant tolerance to a certain amount of azole fungicides, which comprises applying the amount of azole fungicides in combination with an additive (I) selected from the group consisting of thiourea-based compounds, sodium thiosulfate, alkylamines, thioamide-based compounds, and any combination thereof.

[0474] The present invention also provides a method for treating plants or loci seriously infected with or susceptible to fungal diseases, which comprises applying to the plants, plant parts, or loci an amount of an azole fungicide in combination with an additive (I) selected from the group consisting of thiourea-based compounds, sodium thiosulfate, alkylamines, thioamide-based compounds, and any combination thereof.

[0475] In certain embodiments, the azole fungicide and the additive (I) are applied simultaneously. In certain embodiments, the azole fungicide and the additive (I) are applied simultaneously.

[0476] In some embodiments, the method comprises administering any of the combinations and compositions described herein.

[0477] The present invention provides a method for using a composition comprising an azole fungicide, which method comprises applying the azole fungicide in combination with an additive (I).

[0478] The present invention provides a method for using a composition comprising an azole fungicide, the method comprising applying the azole fungicide in combination with a thiourea.

[0479] The present invention provides a method for using a composition comprising an azole fungicide, the method comprising applying the azole fungicide in the presence of an additive (I).

[0480] The present invention provides a method for using a composition comprising an azole fungicide, the method comprising applying the azole fungicide in the presence of thiourea.

[0481] In some embodiments, additive (I) and the azole are formulated as a premix composition.

[0482] In some embodiments, the thiourea and the azole are formulated as a premix composition.

[0483] In some embodiments, the thiourea and azole fungicides are applied simultaneously as a tank mix.

[0484] In some embodiments, the thiourea and azole fungicides are applied as a concurrent application.

[0485] The present invention provides the use of thiourea to reduce or eliminate the phytotoxicity associated with the application of azole fungicides in susceptible crops.

[0486] The present invention provides the use of an additive (I) selected from the group consisting of thiourea, sodium thiosulfate, alkylamines and any combination thereof for providing improved application of azole fungicides.

[0487] The present invention provides the use of an additive (I) selected from the group consisting of thiourea, sodium thiosulfate, alkylamines and any combination thereof for reducing phytotoxicity associated with the application of azole fungicides.

[0488] Therefore, the present invention also provides the use of additive (I) for increasing the plant health of plants when treated with an azole fungicide, wherein the plant health of plants treated with the azole fungicide in the presence of additive (I) is increased compared to the plant health of plants treated with the same amount of the same azole fungicide in the absence of additive (I).

[0489] The present invention therefore also provides the use of additive (I) for reducing or eliminating the phytotoxicity associated with the application of azole fungicides, wherein the phytotoxic effects on plants treated with an azole fungicide in the presence of additive (I) are lower than the phytotoxic effects on plants treated with the same amount of the same azole fungicide in the absence of additive (I).

[0490] The present invention therefore also provides the use of an additive (I) for reducing or eliminating the phytotoxicity of an azole fungicide, wherein the application rate and / or the extent of phytotoxic effects when the azole fungicide is applied in the presence of the additive (I) is reduced compared to the application rate and / or the extent of phytotoxic effects when the azole fungicide is applied in the absence of the additive (I).

[0491] The present invention also provides a method for controlling plant diseases caused by pathogens,

[0492] It comprises applying an effective amount of any of the combinations and / or compositions and / or diluted compositions described herein to plants, their loci, their propagation materials, or areas infected by undesirable pathogens to thereby control plant diseases caused by the pathogens.

[0493] The present invention also provides a method for controlling fungal diseases caused by undesirable fungi, which comprises applying an effective amount of any one of the combinations and / or compositions and / or diluted compositions described herein to plants, their loci, their propagation materials, areas infested by undesirable fungi to thereby control fungal diseases caused by undesirable fungi.

[0494] Control refers to prevention of fungal diseases, curative treatments and permanent treatments.

[0495] In some embodiments, the location of the plant is in the vicinity of the plant.

[0496] In some embodiments, the method comprises applying the combination and / or composition and / or diluted composition to an area infected with an undesirable pathogen.

[0497] The present invention provides a method for controlling pathogen infection, which comprises applying a composition comprising (1) an amount of an azole fungicide, (2) thiourea, and (3) at least one agriculturally acceptable additive.

[0498] The present invention provides a method for controlling pathogen infection, which comprises applying a composition comprising (1) an amount of an azole fungicide, (2) optionally one or more additional fungicides, (3) thiourea, and (4) at least one agriculturally acceptable additive.

[0499] The invention also provides the use of a combination, and / or composition, and / or diluted composition as described herein for treating a plant, or a part of a plant, against a pathogen.

[0500] The invention also provides the use of a combination, and / or composition and / or dilution composition as described herein for increasing the application rate of an azole fungicide.

[0501] The invention also provides the use of a combination, and / or composition and / or dilution composition as described herein for increasing the number of applications of an azole fungicide.

[0502] In some embodiments, when an azole fungicide is applied in the presence of thiourea, the number of applications / growing seasons is increased and / or treatments are more frequent and / or the time intervals between applications are shortened compared to if the same azole fungicide is applied in the same crop under the same conditions in the absence of thiourea.

[0503] The compositions and / or combinations according to the invention are suitable for controlling harmful organisms encountered in horticulture, agriculture and forestry. These compositions are effective against commonly sensitive and resistant harmful organisms and during all or individual developmental stages. Prior to use, the composition comprising the azole fungicide according to the invention is preferably dissolved or dispersed in water, or diluted with water, to provide an aqueous composition comprising between 0.001 and 10 w / v % of the azole fungicide.

[0504] The composition according to the invention is preferably diluted 2-5000 times, preferably about 200 times, with an aqueous solvent, preferably water, before contacting the plant, plant part or soil with the composition.

[0505] To achieve this effect, the plant or plant part, or soil is contacted with the combination, composition (including dilute aqueous compositions).

[0506] The combinations, compositions (including diluted aqueous compositions) are used, for example, to control soybean rust, powdery mildew and downy mildew infections on food / feed crops (including tree fruits, vegetable crops, field crops, grapes, ornamental plants and turf farms). For example, further uses are to control scab, including common scab, apple scab and scab on potatoes, pear scab, and powdery scab, brown rot of peach, currant and gooseberry leaf spot, peanut leaf spot, and mildew on roses. Other uses include protecting greenhouse-grown flowers and ornamental plants, home gardens and residential lawns. In addition, the compositions (including diluted aqueous compositions) can be contacted with isolated fruits, nuts, vegetables and / or flowers.

[0507] For the purposes and the method, preferably the composition (including the aqueous composition of dilution) is sprayed on the plant or its part. The spray application using the known automatic system reduces labor costs and is cost-effective. Methods and equipment well known to those skilled in the art can be used for this purpose. When the risk of infection is high, the composition (including the aqueous composition of dilution) can be sprayed regularly. When the risk of infection is lower, the spray interval time can be longer.

[0508] Other methods suitable for contacting plants or parts thereof with the compositions of the invention are also part of the invention. These include, but are not limited to, dipping, watering, soaking, introducing into a dump tank, evaporating, pulverizing, atomizing, fumigating, painting, brushing, spraying, dusting, foaming, smearing, packaging and coating (e.g., with the aid of wax or static electricity). In addition, the compositions (including diluted aqueous compositions) may be injected into the soil.

[0509] For example, plants or parts thereof can be coated with a diluted aqueous composition comprising an azole fungicide according to the present invention and an additive (I) by immersing the plants or parts thereof in the diluted aqueous composition to protect the plants or parts thereof against pathogens and / or prevent, reduce and / or eliminate the presence of pathogens on the plants or parts thereof. Preferred plant parts coated with the composition according to the present invention or its dilution are seeds. Another preferred plant part coated with the composition according to the present invention or its dilution is a leaf. Another preferred plant part coated with the composition according to the present invention or its dilution is a fruit, preferably a post-harvest fruit, such as, for example, citrus fruits (such as oranges, tangerines and limes), pome fruits (such as apples and pears), stone fruits (such as almonds, apricots, cherries, plums, nectarines, tomatoes, watermelons), tropical fruits (such as bananas, mangoes, lychees and tangerines). Preferred fruits are citrus fruits such as oranges and / or tropical fruits such as bananas.

[0510] Preparation method

[0511] The present invention provides a method for producing a composition comprising (1) an azole fungicide and (2) an additive (I) selected from the group consisting of: thiourea-based compounds, sodium thiosulfate, alkylamines, thioamide-based compounds, and any combination thereof, the method comprising the steps of: (a) preparing an aqueous composition of the azole fungicide and (b) adding the additive (I) selected from the group consisting of: thiourea, sodium thiosulfate, alkylamines, and any combination thereof to obtain a composition of the azole fungicide and the additive (I).

[0512] In some embodiments, additive (I) is selected from the group consisting of thiourea, sodium thiosulfate, alkylamines, and any combination thereof.

[0513] In some embodiments, the composition prepared in the methods is free of copper-based fungicides.

[0514] Azole fungicides

[0515] In some embodiments, the term "azole fungicide" may include but is not limited to azaconazole, bifenthrin, bromoconazole, cyproconazole, difenoconazole, diniconazole, fluepiconazole, eticonazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imipenem, methiconazole, metconazole, myclobutanil, penconazole, propiconazole, silyfloxacin, tebuconazole, tetrafluconazole, triadimefon, triadimenol, triathione, prothioconazole and clofoconazole, and in some embodiments, the azole fungicide includes any combination of two or more thereof.

[0516] In some embodiments, the azole fungicide is epoxiconazole.

[0517] In some embodiments, the azole fungicide is metconazole.

[0518] In some embodiments, the azole fungicide is mefenacet.

[0519] In some embodiments, the azole fungicide is prothioconazole.

[0520] In some embodiments, the azole fungicide is cyproconazole.

[0521] In some embodiments, the azole fungicide is difenoconazole.

[0522] In some embodiments, the azole fungicide is tebuconazole.

[0523] Additional fungicides

[0524] In some embodiments, the additional fungicide is selected from the group consisting of copper-based fungicides, strobilurin fungicides, benzamide fungicides, morpholines, QiI fungicides, SDHI, and any combination thereof.

[0525] In some embodiments, the additional fungicide is flumetylsulforim (5-fluoro-4-imino-3-methyl-1-tosyl-3,4-dihydropyrimidin-2(1H)-one).

[0526] In some embodiments, strobilurin fungicides may include, but are not limited to, azoxystrobin, syringystrobin, enoxastrobin, flutoxifen, picoxystrobin, pyraclostrobin, mandestrobin, pyraclostrobin, pyraclostrobin, chlorpyrifos, kresoxim-methyl, trifloxystrobin, diastereoisomer, enoxastrobin, fenoxystrobin, oxadiazon, tetrazobactam, and fluoxastrobin.

[0527] In some embodiments, the strobilurin fungicide is selected from the group consisting of picoxystrobin, trifloxystrobin, azoxystrobin, pyraclostrobin, fenoxystrobin, tetrazobactam, mandestroystrobin, and combinations thereof.

[0528] In some embodiments, the strobilurin fungicide is picoxystrobin.

[0529] In some embodiments, the strobilurin fungicide is azoxystrobin.

[0530] In some embodiments, the SDHI may include, but is not limited to, penthiopyrad, boscalid, flutolanil, fluopyram, indopyram, fluopyram, fluindopyram, benzodiflupyr, bixafen, and fluopyram.

[0531] In some embodiments, the SDHI fungicide is selected from the group consisting of: bixafen; fluopyram, fluoxapyram; indopyram, benzodiflupyram and fluopyram.

[0532] In some embodiments, the SDHI fungicide is pentocyclam.

[0533] In some embodiments, QiI fungicides may include, but are not limited to, cyazofamid, indazolesulfamide, and fenpicoxamid.

[0534] In some embodiments, QiI is pyridobactamide.

[0535] In some embodiments, the morpholine may include, but is not limited to, 4-dodecyl-2,6-dimethylmorpholine (aldimorph), fenpropimorph, tridemorph, dodecamorph, spiroxafil, fenpropimorph, and fenpropimorph.

[0536] In some embodiments, the additional fungicide is fluazinam.

[0537] In some embodiments, the additional fungicide is folpet.

[0538] In some embodiments, the additional fungicide is captan.

[0539] Preferred additional fungicides are selected from mancozeb, sodium o-phenylphenol, 2-phenylphenol; 8-hydroxyquinoline sulfate; acibenzolar-5-methyl; actinovate; 4-dodecyl-2,5 (or 2,6)-dimethylmorpholine (aldimorph); sulfamethoxam; 1-aminopropylphosphonic acid (ampropylfos); 1-aminopropylphosphonic acid potassium; andoprim; dithiocarb; azoxystrobin bensulfuron; oxadiazine; benomyl (1-(butylcarbamoyl) benzimidazol-2-ylcarbamic acid methyl ester); isopropylbenzyl; benzylcyanamide; isobutylbenzylcyanamide; bialaphos; binachlor; biphenyl; blasticidin-S; boscalid; ethiprole bupirimate; butylthiocarb; butylamine; calcium polysulfide; capsimycin; captamidophthal; captan (N-(trichloromethylthio)cyclohex-4-ene-1,2-dicarboximide); carbendazim; carboxin; cyproconazole; carvone; chloranil; chloranil; chloroneb; chlorothalonil; chlozolinate; cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol; chloranil; conazole fungicides, such as, for example, (RS)-1-(β-allyloxy-2,4-dichlorophenethyl)imidazole (chloranil; Janssen Pharmaceuticals, Inc. Pharmaceutica NV, Belgium) and N-propyl-N-[2-(2,4,6-trichlorophenoxy)ethyl]imidazole-1-carboxamide (prochloraz); cyazofamid; flutolanil; cymoxanil; cyprodinil; cyprodinil; siroxanil; Dagger G; debacarb; dichloranil; dichloronaphthoquinone; diclofenac; diclocymet; diclomezine; dicloran; ethotripsy; fluopyram; mefenamic acid; fenpropimorph; fenpropimorph; dimetho ... 3-Chloro-N-(3-chloro-5-trifluoromethyl-2-pyridyl)-α,α,α-trifluoro-2,6-dinitro-p-toluidine); flufenacet; fluoxathiapiprolin; fluoxamidopyrazone; flumorph; flucloroxanil; fluoxastrobin; fluopyram; fluopyram; flutriamide; flutolanil; flutolanil; flutolanil; fosetyl-A1; fosetyl sodium; furanil; furoxamyl; furoxamidopyrazone; dimethylfuran; seed dressing amine; biguanide salt; hexachlorobenzene; oxamexazole; biguanide triacetate; biguanide tri(alkylbenzene sulfonate);Iodocarb; iprobenfos; isoproconazole; propineb; irumamycin; chlorfenapyr; chlorfenapyr; kasugamycin; kresoxim-methyl; meferimzone; mefenamic acid; metalaxyl; metalaxyl-M; sulfamethoxam; methfiroxam; methyl 1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H-imidazole-5-carboxylate; methyl 2-[[[cyclopropyl[(4-methoxyphenyl)imino]methyl]thio]-methyl]-α-(methoxymethylene)phenylacetate; methyl 2-[2-[3-(4-chlorophenyl)imino]methyl]thio]-methyl]-α-(methoxymethylene)phenylacetate [1-(2-(4-(2-((4-((2-( ... phthalide; flupyrazone; picoxystrobin; pyraclostrobin; polyoxin; polyoxin; procymidone; propamocarb; propanosine-sodium; propineb; iodoquinazole; prothioconazole; pyraclostrobin; pyraclofos; pyrimethanil; pyroquilone; clopidogrel; pyrrolnitrine, quinconazole; quinoxyfen; pentachloronitrobenzene; silthiopyrad; sodium tetrathiocarbonate; spiroxafil; sulfur; chloranthal; tetrachloronitrobenzene; tetracyclazole; thiazole fungicides, such as, for example, 2-(thiazol-4-yl)benzimidazole (thiabendazole), thiabendazole; thiofuranil; thiophanate-methyl; thiophanate-butyl; thiocyanate; tolclofos-methyl; tolylfluanid; Leaf rust; triazoxide; tricyclamide; tricyclazole; tridemorph; trifloxystrobin; jinggangmycin A; vinclozolin; benzyl oxadiazole; (2S)-N-[2-[4-[[3-(4-chlorophenyl)-2-propynyl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(methylsulfonyl)amino]butyramide; 1-(1-naphthyl)-1H-pyrrole-2,5-dione; 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine; 2,4-dihydro-5-methoxy-2-methyl-4-[[[[1-[3-(trifluoromethyl)phenyl]-ethylidene]amino]oxy]methyl]phenyl]-3H-1,2,3-triazol-3-one;2-amino-4-methyl-N-phenyl-5-thiazolecarboxamide; 2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3-pyridinecarboxamide; 3,4,5-trichloro-2,6-pyridinedicarbonitrile; 3-[(3-bromo-6-fluoro-2-methyl-1H-indol-1-yl)sulfonyl]-N,N-dimethyl-1H-1,-2,4-triazole-1-sulfonamide, and / or a mixture thereof. ;

[0540] In some embodiments, the copper-based fungicide is soluble in water.

[0541] In some embodiments, the copper-based fungicide is insoluble in water.

[0542] In some embodiments, the copper-based fungicide is selected from the group consisting of copper acetate, copper chloride, copper chlorate, copper formate, copper hexafluorosilicate, copper nitrate, copper chromate, copper sulfate pentahydrate, Bordeaux mixture, copper hydroxide, cuprous oxide, cupric oxychloride, copper oxychlorosulfate (COCS), tribasic copper sulfate such as copper sulfate, cupric hydroxide hemihydrate, and any combination thereof.

[0543] In some embodiments, the copper-based fungicide can be, but is not limited to, copper acetate, copper chloride, copper chlorate, copper formate, copper hexafluorosilicate, copper nitrate, copper chromate, copper sulfate pentahydrate, Bordeaux mixture, copper hydroxide, cuprous oxide, cupric oxychloride, copper oxychlorosulfate (COCS), tribasic copper sulfate such as copper sulfate, cupric hydroxide hemihydrate, or any combination thereof.

[0544] In some embodiments, the copper-based fungicide is selected from the group consisting of copper acetate, copper chloride, copper chlorate, copper formate, copper hexafluorosilicate, copper nitrate, copper chromate, copper sulfate pentahydrate, Bordeaux mixture, cuprous oxide, cupric oxychloride, and any combination thereof.

[0545] In some embodiments, the copper-based fungicide is a Bordeaux mixture.

[0546] In some embodiments, the copper-based fungicide is copper hydroxide.

[0547] In some embodiments, the copper-based fungicide is copper oxychloride.

[0548] In some embodiments, the copper-based fungicide is selected from the group consisting of copper sulfate pentahydrate, Bordeaux mixture, and any combination thereof.

[0549] As used herein, the term "copper-based fungicide" refers to copper salts (such as copper sulfate, copper hydroxychloride, and copper oxide) and / or metallic copper.

[0550] As used herein, the term "metallic copper" refers to Cu 2+cation.

[0551] Additives (I)

[0552] The additive (I) is selected from the group consisting of

[0553] (i) thiourea-based compounds,

[0554] (ii) sodium thiosulfate,

[0555] (iii) alkylamines,

[0556] (iv) thioamide-based compounds, and

[0557] (v) any combination of (i), (ii), (iii) and (iv),

[0558] In some embodiments, additive (I) is selected from the group consisting of: (i) thiourea, (ii) sodium thiosulfate, (iii) alkylamines, and (iv) any combination of (i), (ii), and (iii).

[0559] In some embodiments, the alkylamine is ethylenediamine.

[0560] In some embodiments, the alkylamine is hexamethylenetetramine.

[0561] In some embodiments, the alkylamine is triethylamine.

[0562] In some embodiments, additive (I) is a mixture of two compounds selected from the group consisting of thiourea, hexamethylenetetramine, sodium thiosulfate, and ethylenediamine.

[0563] In some embodiments, additive (I) is thiourea.

[0564] In some embodiments, the additive (I) is selected from the group consisting of thiourea-based compounds, hexamethylenetetramine, sodium thiosulfate, ethylenediamine, and any combination thereof.

[0565] In some embodiments, the additive (I) is a mixture of two compounds selected from the group consisting of a thiourea-based compound, sodium thiosulfate, an alkylamine, and a thioamide-based compound.

[0566] In some embodiments, additive (I) is a mixture of two compounds selected from the group consisting of: a thiourea-based compound, hexamethylenetetramine, sodium thiosulfate, and ethylenediamine.

[0567] In some embodiments, additive (I) is a thiourea-based compound.

[0568] In some embodiments, the thiourea-based compound is thiourea.

[0569] In some embodiments, thiourea refers to a compound having the formula SC(NH2)2 and the structure H2N-C(=S)-NH2 (also known as thiourea material, CAS No.: 62-56-6).

[0570] The thiourea-based compound refers to a compound having a structure represented by the following formula:

[0571] R 1 NH-C(=S)-NHR 2

[0572] in,

[0573] (i)R 1 , R 2 All are H;

[0574] (ii) R 1 is H, and R 2 is an alkyl or alkenyl or alkynyl or aryl or heterocyclic group;

[0575] (iii) R 1 , R 2 are each independently alkyl, alkenyl or alkynyl;

[0576] (iv) R 1 , R 2 are each independently aryl or heterocyclic;

[0577] (v)R 1 is alkyl or alkenyl or alkynyl, and R 2 is an aryl or heterocyclic group, or

[0578] (vii) R 1 and R 2 may be taken together with the nitrogen atom to which they are attached to form a ring containing 2 to 4 carbon atoms and optionally one additional nitrogen, sulfur or oxygen atom, which ring may be saturated or unsaturated and optionally substituted by 1 to 4 substituents selected from the group consisting of C1-C2 alkyl, halogen, CN, NO2 and C1-C2 alkoxy.

[0579] In some embodiments, alkyl (which may be optionally substituted) represents a straight or branched chain or cyclic hydrocarbon group containing n carbon atoms, or up to 20 carbon atoms.

[0580] In some embodiments, alkyl represents a straight chain or branched chain or cyclic hydrocarbon group containing 1-8 carbon atoms.

[0581] In some embodiments, alkenyl (which may be optionally substituted) represents a straight or branched chain or cyclic hydrocarbon group containing n carbon atoms and at least one double bond.

[0582] In some embodiments, alkynyl (which may be optionally substituted) represents a straight or branched hydrocarbon group containing n carbon atoms and at least one triple bond.

[0583] In some embodiments, alkenyl and alkynyl groups contain 2-8 carbon atoms.

[0584] In some embodiments, aryl (which may be optionally substituted) represents a carbocyclic aromatic group having 6 to 14 carbon atoms.

[0585] In some embodiments, heterocycle (which may be optionally substituted) represents a saturated, partially saturated, or fully unsaturated cyclic group containing 3 to 6 ring atoms, wherein 1 to 4 of the ring atoms are from the group consisting of oxygen, nitrogen, and sulfur.

[0586] In some embodiments, the thiourea-based compound is butylthiourea, methylpropylthiourea, phenylthiourea, ethylphenylthiourea, or diphenylthiourea.

[0587] In some embodiments, the thiourea-based compound is a cyclic thiourea.

[0588] In some embodiments, additive (I) is not a fungicidal active ingredient.

[0589] In some embodiments, additive (I) is selected from thiourea-based compounds having no pesticidal activity.

[0590] In some embodiments, the selected additive (I) is a thioamide-based compound.

[0591] In some embodiments, thioamide-based compounds may include, but are not limited to, thioacetamide, thiobenzamide, furanthioamide, pyridinethioamide, and polythioamide.

[0592] In some embodiments, the thioamide-based compound is selected from the group consisting of thioacetamide, thiobenzamide, furanthioamide, pyridinethioamide, and polythioamide.

[0593] In some embodiments, additive (I) is sodium thiosulfate.

[0594] In some embodiments, additive (I) is an alkylamine. In some embodiments, additive (I) comprises one or more alkylamines.

[0595] In some embodiments, the alkylamine includes one or more monoamines.

[0596] In some embodiments, the alkylamine is a monoamine.

[0597] In some embodiments, the alkylamine is a diamine.

[0598] In some embodiments, the alkylamine is a polyamine.

[0599] In some embodiments, the polyamine is hexamethylenetetramine.

[0600] In some embodiments, the diamine is ethylenediamine.

[0601] In some embodiments, the alkylamine is represented by structure A;

[0602]

[0603] in:

[0604] (i)R 1 is hydrogen, alkyl, aryl, alkenyl, alkynyl or heterocyclyl; R 2 is hydrogen, alkyl, aryl, alkenyl, alkynyl or heterocyclyl; and R 3 is hydrogen, alkyl, aryl, alkenyl, alkynyl, or heterocyclyl; and

[0605] (ii) R 1 , R 2 , and R 3 At least one of the groups is an alkyl group, an aryl group, an alkenyl group, an alkynyl group or a heterocyclic group.

[0606] In some embodiments, the alkyl group (which may be optionally substituted) represents a straight chain or branched chain or cyclic hydrocarbon group containing n carbon atoms.

[0607] In some embodiments, alkenyl (which may be optionally substituted) represents a straight or branched chain or cyclic hydrocarbon group containing n carbon atoms and at least one double bond.

[0608] In some embodiments, alkynyl (which may be optionally substituted) represents a straight or branched chain hydrocarbon group containing n carbon atoms and at least one triple bond.

[0609] In some embodiments, aryl (which may be optionally substituted) represents a carbocyclic aromatic group having 6 to 14 carbon atoms.

[0610] In some embodiments, heterocycle (which may be optionally substituted) represents a saturated, partially saturated, or fully unsaturated cyclic group containing 3 to 6 ring atoms, wherein 1 to 4 of the ring atoms are from the group consisting of oxygen, nitrogen, and sulfur.

[0611] In some embodiments, substitution refers to a group (R 1 , R 2 and / or R 3 ) may or may not be replaced by one or more groups (such as C nAlkyl, aryl, halogen, hydroxy, thio, amino, cyano, oxo, nitro, acyl, amide, C 1-6 Alkoxy, C 1-6 Alkenyloxy, aryloxy, acyloxy, C 1-6 Alkylamino, arylamino, C 1-6 Alkylthio, alkylsulfonyl, arylsulfonyl, alkylsulfinyl, arylsulfinyl, C 1-8 alkylamide and carboxyl).

[0612] In some embodiments, R 1 , R 2 , R 3 Two or more of are the same.

[0613] In some embodiments, R 1 , R 2 , R 3 Each is different.

[0614] In which R 1 , R 2 , R 3 In some embodiments where one or more of the alkyl groups is alkyl, one or more of the alkyl groups is linear.

[0615] In some embodiments, the alkyl group is cyclic.

[0616] In some embodiments, the alkyl group is an alkyl fatty chain.

[0617] In some embodiments, R 1 , R 2 and R 3 It's methyl.

[0618] In some embodiments, R 1 , R 2 and R 3 It is ethyl.

[0619] In some embodiments, R 1 and R 2 is H and R 3 It is C 12 alkyl.

[0620] In some embodiments, R 1 and R 2 is H and R 3 It is C 18 Alkenyl.

[0621] In some embodiments, the selected additive (I) is an alkylamine, which is oleylamine.

[0622] In some embodiments, the alkylamine is dodecylamine.

[0623] In some embodiments, the alkylamine is benzylamine.

[0624] In some embodiments, additive (I) is hexamethylenetetramine.

[0625] In some embodiments, additive (I) is sodium thiosulfate.

[0626] In some embodiments, additive (I) is ethylenediamine.

[0627] In some embodiments, the alkylamine is butylamine.

[0628] In some embodiments, the alkylamine is diethylamine.

[0629] In some embodiments, the alkylamine is triethylamine.

[0630] In some embodiments, additive (I) comprises thiourea.

[0631] In some embodiments, additive (I) comprises a thioamide-based compound.

[0632] In some embodiments, additive (I) comprises sodium thiosulfate.

[0633] In some embodiments, additive (I) comprises an alkylamine

[0634] In some embodiments, additive (I) comprises ethylenediamine.

[0635] In some embodiments, the alkylamine comprises butylamine.

[0636] In some embodiments, the alkylamine comprises diethylamine.

[0637] In some embodiments, the alkylamine comprises triethylamine

[0638] In some embodiments, the additive (I) is a mixture of two compounds (I), and the weight ratio between them is 10:1 to 1:10.

[0639] In some embodiments, additive (I) is a mixture of thiourea and sodium thiosulfate.

[0640] In some embodiments, the weight ratio between thiourea and sodium thiosulfate is 10:1 to 1:10.

[0641] In some embodiments, the weight ratio between thiourea and sodium thiosulfate is 10:1 to 1:10.

[0642] In some embodiments, additive (I) is a mixture of hexamethylenetetramine and thiourea.

[0643] In some embodiments, the weight ratio between thiourea and hexamethylenetetramine is 10:1 to 1:10.

[0644] In some embodiments, additive (I) is a mixture of hexamethylenetetramine and sodium thiosulfate.

[0645] In some embodiments, the weight ratio between hexamethylenetetramine and sodium thiosulfate is 10:1 to 1:10.

[0646] In some embodiments, additive (I) is a mixture of sodium thiosulfate and ethylenediamine.

[0647] In some embodiments, the weight ratio between sodium thiosulfate and ethylenediamine is 10:1 to 1:10.

[0648] In some embodiments, additive (I) is a mixture of thiourea and ethylenediamine.

[0649] In some embodiments, the weight ratio between thiourea and ethylenediamine is 10:1 to 1:10.

[0650] Copper-based fungicides, additional fungicides and polyelectrolytes

[0651] Combinations, macromolecular complexes and compositions comprising a copper-based fungicide, a polyelectrolyte and an additional fungicide. The present invention relates to combinations and compositions comprising a copper-based fungicide and a polyelectrolyte. The present invention further relates to a method for preventing, reducing and / or eliminating the presence of plant pathogens on a plant or on one or more plant parts, comprising applying a composition of the present invention to the plant or plant part. The present invention provides a suspoemulsion composition comprising a copper-based fungicide, (2) a polyelectrolyte, (3) at least one additional fungicide selected from the group consisting of a strobilurin fungicide, an azole fungicide, a benzamide fungicide, a morpholine, a QiI fungicide, a SDHI and any combination thereof, (4) water and (5) a water-immiscible carrier, wherein the copper-based fungicide is suspended in the water and at least one of the additional fungicides is dissolved in the water-immiscible carrier.

[0652] It is an object of the present invention to provide compositions and methods that allow for a reduction in the amount of copper-based fungicides required to control phytopathogenic pests. Another object of the present invention is to develop methods and compositions that provide effective plant growth control. Plant growth control refers to preventing damage to plants by controlling pathogens and reducing negative effects on plant health.

[0653] It has been unexpectedly discovered that the combination of a copper-based fungicide and a polyelectrolyte can significantly reduce the amount of copper-based fungicide required to achieve a given level of pest control and enhance biological efficacy and plant health. The enhanced biological efficacy includes enhanced absorption and bioavailability.

[0654] As used herein, the term "copper-based fungicide" refers to copper salts (such as copper sulfate, copper hydroxychloride, and copper oxide) and / or metallic copper.

[0655] As used herein, the term "metallic copper" refers to Cu 2+ cation.

[0656] The copper-based fungicide and the polyelectrolyte can be components of a macromolecular complex that significantly reduces the amount of copper-based fungicide required to achieve a certain level of biological efficacy, enhances the biological efficacy of a given amount of copper-based fungicide, increases the persistence of the copper-based fungicide, and reduces the phytotoxicity of the copper-based fungicide when compared to applying the copper-based fungicide in the absence of the polyelectrolyte.

[0657] Furthermore, the macromolecular complex according to the invention reduces the drift of copper-based fungicides. The macromolecular complex unexpectedly results in a reduction in the mobility or leakage of copper-based fungicides in soil. The complex further results in a reduction in toxicity to plants when compared to copper-based fungicides not applied as part of the macromolecular complex as described in the present invention, thus resulting in less phytotoxicity.

[0658] The copper-based fungicide composition according to the present invention also has improved physical properties, such as viscosity, different morphology and particle size, when compared to free copper-based fungicide compositions without polyelectrolytes.

[0659] Combinations and compositions

[0660] The present invention provides a combination of a copper-based fungicide and a polyelectrolyte.

[0661] The present invention provides a composition comprising the combination described herein and at least one agriculturally acceptable additive.

[0662] The present invention provides a suspoemulsion composition comprising a copper-based fungicide, a polyelectrolyte and at least one additional fungicide.

[0663] The present invention provides a suspoemulsion composition comprising (1) a copper-based fungicide, (2) a polyelectrolyte, (3) at least one additional fungicide selected from the group consisting of strobilurin fungicides, azole fungicides, benzamide fungicides, morpholines, QiI fungicides, SDHI and any combination thereof, (4) water and (5) a water-immiscible carrier, wherein the copper-based fungicide is suspended in the water and the at least one additional fungicide is dissolved in the water-immiscible carrier.

[0664] In some embodiments, the suspoemulsion composition comprises a macromolecular complex comprising a copper-based fungicide and a polyelectrolyte.

[0665] In some embodiments, the copper-based fungicide can be, but is not limited to, copper acetate, copper chloride, copper chlorate, copper formate, copper hexafluorosilicate, copper nitrate, copper chromate, copper sulfate pentahydrate, Bordeaux mixture, copper hydroxide, copper oxychlorosulfate (COCS), tribasic copper sulfate such as copper sulfate, cupric hydroxide hemihydrate, or any combination thereof.

[0666] In some embodiments, the copper-based fungicide is selected from the group consisting of copper acetate, copper chloride, copper chlorate, copper formate, copper hexafluorosilicate, copper nitrate, copper chromate, copper sulfate pentahydrate, Bordeaux mixture, and any combination thereof.

[0667] In some embodiments, the copper-based fungicide is selected from the group consisting of copper sulfate pentahydrate, Bordeaux mixture, and any combination thereof.

[0668] In some embodiments, the composition comprises two additional fungicides. In some embodiments, the composition comprises two or more additional fungicides.

[0669] In some embodiments, when the composition comprises two or more additional fungicides, at least one additional fungicide is dissolved in the water-immiscible carrier and at least one additional fungicide is suspended in water and / or dissolved in the water-immiscible carrier.

[0670] In some embodiments, the copper-based fungicide is Bordeaux mixture and the additional fungicide is prothioconazole.

[0671] In some embodiments, the copper-based fungicide is Bordeaux mixture and the additional fungicide is tebuconazole.

[0672] In some embodiments, the copper-based fungicide is Bordeaux mixture and the additional fungicides are prothioconazole and picoxystrobin.

[0673] In some embodiments, the copper-based fungicide is Bordeaux mixture and the additional fungicides are prothioconazole and azoxystrobin.

[0674] In some embodiments, the copper-based fungicide is Bordeaux mixture and the additional fungicides are tebuconazole and picoxystrobin.

[0675] In some embodiments, the copper-based fungicide is Bordeaux mixture and the additional fungicides are tebuconazole and azoxystrobin.

[0676] In some embodiments, the copper-based fungicide is Bordeaux mixture and the additional fungicides are prothioconazole and fluopyraclostrobin.

[0677] In some embodiments, the copper-based fungicide is Bordeaux mixture and the additional fungicides are tebuconazole and azoxystrobin.

[0678] In some embodiments, the copper-based fungicide is copper oxychloride and the additional fungicide is prothioconazole.

[0679] In some embodiments, the copper-based fungicide is copper oxychloride and the additional fungicide is tebuconazole.

[0680] In some embodiments, the copper-based fungicide is copper oxychloride and the additional fungicides are prothioconazole and picoxystrobin.

[0681] In some embodiments, the copper-based fungicide is copper oxychloride and the additional fungicides are prothioconazole and azoxystrobin.

[0682] In some embodiments, the copper-based fungicide is a copper oxychloride mixture and the additional fungicides are tebuconazole and picoxystrobin.

[0683] In some embodiments, the copper-based fungicide is copper oxychloride and the additional fungicides are tebuconazole and azoxystrobin.

[0684] In some embodiments, the copper-based fungicide is copper oxychloride and the additional fungicides are prothioconazole and fluopyraclostrobin.

[0685] In some embodiments, the copper-based fungicide is copper oxychloride and the additional fungicides are tebuconazole and azoxystrobin.

[0686] In some embodiments, the amount of the copper-based fungicide in the composition is 1%-50% by weight based on the total weight of the composition. In some embodiments, the amount of the copper-based fungicide in the composition is 5%-40% by weight based on the total weight of the composition. In some embodiments, the amount of the copper-based fungicide in the composition is 5%-18% by weight based on the total weight of the composition.

[0687] In some embodiments, the amount of the one or more additional fungicides in the composition is 1%-50% by weight based on the total weight of the composition. In some embodiments, the amount of the one or more additional fungicides in the composition is 1%-30% by weight based on the total weight of the composition. In some embodiments, the amount of the one or more additional fungicides in the composition is 1%-20% by weight based on the total weight of the composition. In some embodiments, the amount of the one or more additional fungicides in the composition is 1%-15% by weight based on the total weight of the composition.

[0688] In some embodiments, the amount of strobilurin fungicide in the composition is 1%-15% by weight based on the total weight of the composition. In some embodiments, the amount of strobilurin fungicide in the composition is 1%-5% by weight based on the total weight of the composition. In some embodiments, the amount of strobilurin fungicide in the composition is 5%-10% by weight based on the total weight of the composition. In some embodiments, the amount of strobilurin fungicide in the composition is 10%-15% by weight based on the total weight of the composition.

[0689] In some embodiments, the amount of the azole fungicide in the composition is 1%-20% by weight based on the total weight of the composition. In some embodiments, the amount of the azole fungicide in the composition is 1%-5% by weight based on the total weight of the composition. In some embodiments, the amount of the azole fungicide in the composition is 5%-10% by weight based on the total weight of the composition. In some embodiments, the amount of the azole fungicide in the composition is 10%-15% by weight based on the total weight of the composition. In some embodiments, the amount of the azole fungicide in the composition is 15%-20% by weight based on the total weight of the composition.

[0690] In some embodiments, the amount of succinate dehydrogenase inhibitor fungicide (SDHI) in the composition is 1%-15% by weight based on the total weight of the composition. In some embodiments, the amount of succinate dehydrogenase inhibitor fungicide (SDHI) in the composition is 1%-5% by weight based on the total weight of the composition. In some embodiments, the amount of succinate dehydrogenase inhibitor fungicide (SDHI) in the composition is 5%-10% by weight based on the total weight of the composition. In some embodiments, the amount of succinate dehydrogenase inhibitor fungicide (SDHI) in the composition is 10%-15% by weight based on the total weight of the composition.

[0691] In some embodiments, the amount of benzamide fungicide in the composition is 1%-50% by weight based on the total weight of the composition.

[0692] In some embodiments, the amount of the one or more morpholines in the composition is 1%-50% by weight based on the total weight of the composition.

[0693] In some embodiments, the amount of the QiI fungicide in the composition is 1%-50% by weight based on the total weight of the composition.

[0694] In some embodiments, the copper-based fungicide is a Bordeaux mixture.

[0695] In some embodiments, the composition comprises 5%-18% by weight of Bordeaux mixture, 1%-15% by weight of a strobilurin fungicide, and 1%-20% by weight of an azole fungicide.

[0696] In some embodiments, the composition comprises 5%-18% by weight of Bordeaux mixture and 1%-20% by weight of the azole fungicide.

[0697] In some embodiments, the composition comprises 5%-18% by weight of Bordeaux mixture, 1%-20% by weight of azole fungicide, and 1%-15% by weight of SDHI.

[0698] In some embodiments, the composition comprises 5%-18% by weight of Bordeaux mixture and 1%-15% by weight of a strobilurin fungicide.

[0699] In some embodiments, the composition comprises 5%-18% by weight Bordeaux mixture and 1%-15% by weight SDHI.

[0700] In some embodiments, the copper-based fungicide is copper oxychloride.

[0701] In some embodiments, the composition comprises 5%-40% by weight cupric oxychloride, 1%-15% by weight strobilurin fungicide, and 1%-20% by weight azole fungicide.

[0702] In some embodiments, the composition comprises 5%-40% by weight cupric oxychloride, and 1%-20% by weight azole fungicide.

[0703] In some embodiments, the composition comprises 5%-40% by weight cupric oxychloride, 1%-20% by weight azole fungicide, and 1%-15% by weight SDHI.

[0704] In some embodiments, the composition comprises 5%-40% by weight cupric oxychloride and 1%-15% by weight strobilurin fungicide.

[0705] In some embodiments, the composition comprises 5%-40% by weight cupric oxychloride and 1%-15% by weight SDHI.

[0706] The innovative combination of the present invention increases the solubility and / or dispersibility of copper-based fungicides and improves their biological efficacy by controlling the formation and release of the active ingredient which is the copper ion. The net effect is that less copper-based fungicide is needed to achieve control of agricultural pests when compared to the same copper-based fungicide not formulated with a polyelectrolyte.

[0707] The present invention provides a combination of a copper-based fungicide and a polyelectrolyte. The present invention provides a combination of a copper-based fungicide and a polyanion. The present invention provides a combination of a certain amount of a copper-based fungicide and a certain amount of a polyelectrolyte.

[0708] In some embodiments, the combination is a macromolecular complex comprising a copper-based fungicide and a polyelectrolyte. In some embodiments, the combination is (1) a macromolecular complex comprising a copper-based fungicide and a polyelectrolyte and (2) at least one additional fungicide. In some embodiments, the combination is (1) a macromolecular complex comprising a copper-based fungicide and a polyelectrolyte and (2) at least two additional fungicides.

[0709] In some embodiments, the additional fungicide is selected from the group consisting of a strobilurin fungicide, an azole fungicide, a benzamide fungicide, a morpholine, a QiI fungicide, a SDHI, and any combination thereof.

[0710] The present invention provides a composition comprising the combination described herein and at least one agriculturally acceptable additive. In some embodiments, the composition comprises at least one additional fungicide.

[0711] In some embodiments, the macromolecular complex is characterized by intermolecular non-covalent interactions, preferably electrostatic interactions such as ionic interactions, hydrogen bonds, and van der Waals forces such as dipole-dipole interactions, between the polyelectrolyte and the copper-based fungicide. In some embodiments, the copper-based fungicide molecules chemically interact with the polyelectrolyte through one or more intermolecular forces.

[0712] The present invention provides a macromolecular complex of a copper-based fungicide and a polyelectrolyte, wherein the macromolecular complex is characterized by intermolecular non-covalent interactions, preferably electrostatic interactions such as ionic interactions, hydrogen bonds and van der Waals forces such as dipole-dipole interactions, between the polyelectrolyte and the copper-based fungicide.

[0713] The present invention provides a composition comprising (1) a copper-based fungicide, (2) a polyelectrolyte, and (3) at least one agriculturally acceptable additive. The present invention provides a composition comprising (1) an amount of a copper-based fungicide, (2) an amount of a polyelectrolyte, and (3) at least one agriculturally acceptable additive.

[0714] In some embodiments, the present invention provides a composition comprising (1) a copper-based fungicide, (2) a polyelectrolyte, (3) at least one additional fungicide, and (4) at least one agriculturally acceptable additive.

[0715] The present invention provides a composition comprising (1) an amount of a copper-based fungicide, (2) an amount of a polyelectrolyte, (3) at least one additional fungicide, and (4) at least one agriculturally acceptable additive.

[0716] In some embodiments, the composition comprises a macromolecular complex of a copper-based fungicide and a polyelectrolyte.

[0717] The present invention provides a composition comprising a macromolecular complex comprising a copper-based fungicide and a polyelectrolyte. The present invention provides a composition comprising (i) a macromolecular complex comprising a copper-based fungicide and a polyelectrolyte and (ii) at least one agriculturally acceptable additive. The present invention provides a composition comprising (i) a macromolecular complex comprising a copper-based fungicide and a polyelectrolyte and (ii) at least one additional fungicide.

[0718] The present invention provides a composition comprising (i) a macromolecular complex comprising a copper-based fungicide and a polyelectrolyte, (ii) at least one additional fungicide and (iii) at least one agriculturally acceptable additive.

[0719] The present invention provides a composition comprising a copper-based fungicide and a polyelectrolyte.

[0720] The present invention provides a composition comprising (i) a copper-based fungicide, (ii) a polyelectrolyte, (iii) at least one additional fungicide and (iv) at least one agriculturally acceptable additive.

[0721] In some embodiments, the polyelectrolyte comprises at least one polyanion. In some embodiments, the polyelectrolyte is a polyanion. In some embodiments, the polyelectrolyte comprises a polycation and a polyanion. In some embodiments, the polyelectrolyte is a complex of a polycation and a polyanion. The present invention provides a composition comprising any of the combinations or macromolecular complexes described herein and at least one acceptable additive.

[0722] In some embodiments, the agriculturally acceptable additive is an agriculturally acceptable carrier.

[0723] In some embodiments, the agriculturally acceptable carrier is water.

[0724] In some embodiments, the agriculturally acceptable carrier is a water-immiscible carrier.

[0725] In some embodiments, the copper-based fungicide is suspended in water.

[0726] In some embodiments, one or more additional fungicides are suspended in water.

[0727] In some embodiments, the compositions comprise at least two additional fungicides suspended in an aqueous carrier.

[0728] In some embodiments, the composition further comprises an organic phase.

[0729] In some embodiments, the composition comprises an organic phase comprising a water-immiscible carrier.

[0730] In some embodiments, the organic phase is oil-organic solvent droplets in water.

[0731] In some embodiments, the compositions comprise at least one additional fungicide dissolved in a water-immiscible carrier.

[0732] In some embodiments, the compositions comprise at least one additional fungicide suspended in an aqueous carrier.

[0733] In some embodiments, the composition comprises at least two additional fungicides dissolved in a water-immiscible carrier.

[0734] In some embodiments, the compositions include at least two additional fungicides, one of which is dissolved in the water-immiscible carrier and the other of which is suspended in the aqueous carrier.

[0735] In some embodiments, the composition has a viscosity in the range of 1500-1800 cPs (measured with a Brookfield spindle 63 at 12 rpm).

[0736] In some embodiments, the composition comprises particles having a particle size distribution (d90) of 10 microns or less. In some embodiments, the composition comprises particles having a particle size distribution (d90) of 7 microns or less. In some embodiments, the composition comprises particles having a particle size distribution (d90) of 4 microns or less.

[0737] In some embodiments, the composition has a pH in the range of 5.0-7.5.

[0738] In some embodiments, the composition has a density (g / ml) at 25°C of 1.26 ± 0.05.

[0739] The composition according to the invention is preferably in the form of a suspension concentrate (SC), water dispersible granules (WG), wettable powder (WP), dispersion concentrate (DC), dry seed treatment (DS), water slurry powder (WS), or flowable seed treatment (FS), or suspoemulsion (SE). Preferably, the composition of the invention is in the form of a suspension concentrate, or in the form of water dispersible granules. The most preferred composition is a suspension concentrate or a SE. In an embodiment, the SE is a dispersion of solid particles and oil-organic solvent droplets in water intended for dilution with water before use.

[0740] In some embodiments, the copper-based fungicide is suspended in water. In some embodiments, one or more additional fungicides may be suspended and / or dissolved in a water-immiscible carrier.

[0741] In some embodiments, the polyelectrolyte comprises at least one polyanion. In some embodiments, the polyelectrolyte is a polyanion. In some embodiments, the polyelectrolyte comprises a polycation and a polyanion. In some embodiments, the polyelectrolyte is a complex of a polycation and a polyanion.

[0742] In some embodiments, the weight ratio between the polyelectrolyte and metallic copper in the copper-based fungicide in the combination and / or composition is between 1:10 and 1:1. In some embodiments, the weight ratio between the polyelectrolyte and metallic copper in the copper-based fungicide in the combination and / or composition is between 1:1 and 1:7. In some embodiments, the weight ratio between the polyelectrolyte and metallic copper in the copper-based fungicide in the combination and / or composition is between 1:1 and 1:5. In some embodiments, the weight ratio between the polyelectrolyte and metallic copper in the copper-based fungicide in the combination and / or composition is between 1:3 and 1:5. In some embodiments, the weight ratio between the polyelectrolyte and metallic copper in the copper-based fungicide in the combination and / or composition is 1:3.5. In some embodiments, the weight ratio between the polyelectrolyte and metallic copper in the copper-based fungicide in the combination and / or composition is 1:4.4. In some embodiments, the weight ratio of polyelectrolyte to metallic copper in the copper-based fungicide in the combination and / or composition is between 1:10 and 1:1, more preferably at a ratio between 1:10 and 1:5 and more preferably at a ratio of 1:3.5.

[0743] In some embodiments, the polyelectrolyte comprises a polycation and a polyanion, and the weight ratio between the polyelectrolyte and metallic copper in the copper-based fungicide in the combinations and / or compositions described herein is in the range of 1:1 to 1:10.

[0744] In some embodiments, the polyelectrolyte comprises a polycation and a polyanion, and the weight ratio between the polyelectrolyte and metallic copper in the copper-based fungicide in the combinations and / or compositions described herein is 1:3.5.

[0745] In some embodiments, the polyelectrolyte comprises a polyanion, and the weight ratio between the polyelectrolyte and metallic copper in the copper-based fungicide in the combinations and / or compositions described herein is 1:4.4.

[0746] In some embodiments, the polyelectrolyte comprises a polycation and a polyanion, and the weight ratio between the polycation and the polyanion is 1:5.

[0747] In some embodiments, the polyelectrolyte comprises a polycation and a polyanion, and the weight ratio between the polycation and the polyanion is 1:9.

[0748] In some embodiments, the polyelectrolyte and copper have a neutral zeta potential. In some embodiments, a neutral zeta potential refers to ±5 Mv. In some embodiments, the zeta potential is measured in the absence of additional acceptable agricultural additives.

[0749] In some embodiments, the copper-based fungicide interacts with the polyelectrolyte through intermolecular non-covalent interactions, preferably electrostatic interactions such as ionic interactions, hydrogen bonds, and van der Waals forces such as dipole-dipole interactions, between the polycation and the copper-based fungicide.

[0750] In some embodiments, the macromolecular complex is characterized by non-covalent intermolecular interactions, preferably ionic interactions, and hydrogen bonding between the donor and acceptor groups of the polycation and the copper-based fungicide.

[0751] In some embodiments, the copper-based fungicide and the polyelectrolyte interact through non-covalent intermolecular interactions, preferably ionic interactions, and hydrogen bonding between the donor and acceptor groups of the polycation and the copper-based fungicide.

[0752] In some embodiments, the combination, macromolecular complex, and / or composition comprises greater than 1 part polyanion per 3 to 5 parts of metallic copper-based fungicides by weight. In some embodiments, the combination, macromolecular complex, and / or composition comprises greater than 1 part polyanion per 3 parts of metallic copper-based fungicides by weight. In some embodiments, the combination, macromolecular complex, and / or composition comprises greater than 1 part polyanion per 4 parts of metallic copper-based fungicides by weight. In some embodiments, the combination, macromolecular complex, and / or composition comprises greater than 1 part polyanion per 5 parts of metallic copper-based fungicides by weight.

[0753] In some embodiments, the batch of copper-based fungicides is a mixture of copper-based fungicides and at least one additive. In some embodiments, the batch of copper-based fungicides is a mixture of copper-based fungicides and stabilizers. In some embodiments, the stabilizer is a polyanion. In some embodiments, the additive is a polyanion.

[0754] The concentration of polyelectrolyte in the combination or composition according to the invention is preferably between 0.1 and 50 g / kg. In some embodiments, the concentration of polyelectrolyte in the combination or composition is between 0.1 and 50 g / kg.

[0755] The concentration of polyelectrolytes in the combination or composition according to the present invention is preferably 0.01%-5% by weight, more preferably 0.1%-4% by weight, such as 2%-3% by weight, based on the total weight of the combination or composition. In some embodiments, the concentration of polyelectrolytes in the combination or composition is 0.01%-10% by weight based on the total weight of the combination or composition. In some embodiments, the concentration of polyelectrolytes in the combination or composition is 0.1%-5% by weight based on the total weight of the combination or composition. In some embodiments, the concentration of polyelectrolytes in the combination or composition is 0.1%-4% by weight based on the total weight of the combination or composition. In some embodiments, the concentration of polyelectrolytes in the combination or composition is 0.1%-3% by weight based on the total weight of the combination or composition. In some embodiments, the concentration of polyelectrolytes in the combination or composition is about 2%-3% by weight based on the total weight of the combination or composition. In some embodiments, the concentration of polyelectrolytes in the combination or composition is about 3% by weight based on the total weight of the combination or composition. In some embodiments, the concentration of polyelectrolytes in the combination or composition is 2.3% by weight based on the total weight of the combination or composition. In some embodiments, the concentration of the polyelectrolyte in the combination or composition is 2.8% by weight based on the total weight of the combination or composition.

[0756] In some embodiments, the polycation is chitosan. In some embodiments, the polyanion is lignin sulfonate. In some embodiments, the lignin sulfonate is calcium lignin sulfonate.

[0757] In some embodiments, the concentration of calcium lignin sulfonate in the composition is between 2% and 3% by weight based on the total weight of the composition. In some embodiments, the concentration of calcium lignin sulfonate in the composition is about 2.3% by weight based on the total weight of the composition.

[0758] In some embodiments, the concentration of chitosan in the composition is between 0.1% and 1% by weight based on the total weight of the composition. In some embodiments, the concentration of chitosan in the composition is about 0.5% by weight based on the total weight of the composition.

[0759] In some embodiments, the composition is substantially free of or free of polycations. In some embodiments, the macromolecular complex is substantially free of or free of polycations. In some embodiments, the composition is substantially free of or free of chitosan. In some embodiments, the macromolecular complex is substantially free of or free of chitosan.

[0760] As used herein, "substantially free" refers to a concentration of less than 0.1% w / w, preferably less than 0.05% w / w, more preferably less than 0.01% w / w.

[0761] In some embodiments, the composition comprises a polyanion and a polycation. In some embodiments, the macromolecular complex comprises a polyanion and a polycation. In some embodiments, the polyelectrolyte comprises a polyanion and a polycation. In some embodiments, the composition comprises lignin sulfonate and chitosan. In some embodiments, the macromolecular complex comprises lignin sulfonate and chitosan. In some embodiments, the polyelectrolyte is a complex of lignin sulfonate and chitosan.

[0762] In some embodiments, the combined weight of lignin sulfonate and chitosan in the composition is between 1% and 10% by weight based on the total weight of the composition. In some embodiments, the combined weight of lignin sulfonate and chitosan in the composition is between 1% and 5% by weight based on the total weight of the composition. In some embodiments, the combined weight of lignin sulfonate and chitosan in the composition is between 2% and 3% by weight based on the total weight of the composition. In some embodiments, the combined weight of lignin sulfonate and chitosan in the composition is 2.8% by weight based on the total weight of the composition.

[0763] In some embodiments, the copper-based fungicide is added to the composition in the form of a formulation.

[0764] In some embodiments, the concentration of the copper-based fungicide is up to 25% by weight based on the total weight of the composition. In some embodiments, the concentration of the copper-based fungicide is up to 10% by weight based on the total weight of the composition. In some embodiments, the concentration of the copper-based fungicide in the composition is between 100 and 250 g / L. In some embodiments, the concentration of the copper-based fungicide in the composition is 110 g / L.

[0765] In some embodiments, the concentration of the copper-based fungicide is greater than 25% by weight based on the total weight of the composition. In some embodiments, the concentration of the copper-based fungicide is greater than 25% by weight based on the total weight of the composition. In some embodiments, the concentration of the copper-based fungicide in the composition is greater than 30% by weight based on the total weight of the composition.

[0766] In some embodiments, the concentration of metallic copper in the formulation comprising a copper-based fungicide is between 10 g / L and 250 g / L. In some embodiments, the concentration of metallic copper in the formulation comprising a copper-based fungicide is between 50 g / L and 150 g / L. In some embodiments, the concentration of metallic copper in the formulation comprising a copper-based fungicide is 100 g / L.

[0767] In some embodiments, the concentration of metallic copper in the formulation comprising a copper-based fungicide is 1%-25% by weight based on the total weight of the formulation. In some embodiments, the concentration of metallic copper in the formulation comprising a copper-based fungicide is 5%-25% by weight based on the total weight of the formulation. In some embodiments, the concentration of metallic copper in the formulation comprising a copper-based fungicide is 5%-15% by weight based on the total weight of the formulation. In some embodiments, the concentration of metallic copper in the formulation comprising a copper-based fungicide is about 10% by weight based on the total weight of the formulation. In some embodiments, the concentration of metallic copper in the formulation comprising a copper-based fungicide is 10.1% by weight based on the total weight of the formulation.

[0768] In some embodiments, the concentration of metallic copper in the formulation comprising a copper-based fungicide is up to 25% by weight based on the total weight of the formulation. In some embodiments, the concentration of metallic copper in the formulation comprising a copper-based fungicide is 10% by weight based on the total weight of the formulation.

[0769] In some embodiments, the concentration of metallic copper in the formulation comprising the copper-based fungicide is between 100 and 250 g / L, preferably 110 g / L.

[0770] In some embodiments, the concentration of the copper-based fungicide in the formulation is between 15% and 45% by weight based on the total weight of the formulation. In some embodiments, the concentration of the copper-based fungicide in the formulation is between 20% and 35% by weight based on the total weight of the formulation. In some embodiments, the concentration of the copper-based fungicide in the formulation is between 25% and 30% by weight based on the total weight of the formulation. In some embodiments, the concentration of the copper-based fungicide in the formulation is 28.8% by weight based on the total weight of the formulation.

[0771] In some embodiments, the concentration of the formulation comprising the copper-based fungicide in the composition is between 150 and 500 g / L. In some embodiments, the concentration of the formulation comprising the copper-based fungicide in the composition is between 300 g / L and 400 g / L. In some embodiments, the concentration of the formulation comprising the copper-based fungicide in the composition is 345 g / L.

[0772] In some embodiments, the concentration of metallic copper in the composition is 0.1% to 10% by weight based on the total weight of the composition. In some embodiments, the concentration of metallic copper in the composition is 0.5% to 5% by weight based on the total weight of the composition. In some embodiments, the concentration of metallic copper in the composition is 2% to 3% by weight based on the total weight of the composition. In some embodiments, the concentration of metallic copper in the composition is 2.9% by weight based on the total weight of the composition.

[0773] In some embodiments, the copper-based fungicide is copper sulfate. In some embodiments, the copper-based fungicide is copper oxychloride. In some embodiments, the copper-based fungicide is copper hydroxide.

[0774] The addition of additives affects the chemical and physical stability of the composition. The additives can, for example, improve the stability of the composition.

[0775] In some embodiments, agriculturally acceptable additives are selected from agriculturally acceptable carriers, buffers, acidulants, antifoams, antifreezes, solvents, cosolvents, stabilizers, light stabilizers, UV absorbers, free radical scavengers and antioxidants, adhesives, neutralizers, thickeners, binders, chelating agents, biocides, drift retardants, surfactants, dispersants, pigments, wetting agents, safeners and preservatives. The additives include, but are not limited to, surfactants, pigments, wetting agents and safeners, or such preservatives as bacteriostats or bactericides.

[0776] In some embodiments, the agriculturally acceptable additive is an agriculturally acceptable carrier. In some embodiments, the composition comprises at least one agriculturally acceptable carrier.

[0777] Adding a small amount of one or more agriculturally acceptable additives may affect parameters such as stability, efficacy and / or fastness to rain washout of the composition according to the invention. Adding a small amount of one or more agriculturally acceptable carriers preferably increases the stability, efficacy and / or fastness to rain washout of the composition according to the invention.

[0778] In some embodiments, the agriculturally acceptable carrier is water.

[0779] In some embodiments, the composition comprises 40%-80% water by weight. In some embodiments, the composition comprises 50%-70% water by weight. In some embodiments, the composition comprises 50%-55% water by weight. In some embodiments, the composition comprises about 52% water by weight. In some embodiments, the composition comprises about 53% water by weight. In some embodiments, the composition comprises about 54% water by weight. In some embodiments, the composition comprises about 55% water by weight.

[0780] In some embodiments, the composition is an aqueous composition.

[0781] The present invention also provides an aqueous composition comprising any one or any combination of the combinations and / or macromolecular complexes described herein, water, and an agriculturally acceptable additive.

[0782] In some embodiments, the concentration of metallic copper in the copper-based fungicide in the aqueous composition is 10.1% by weight based on the total weight of the composition, and the composition further comprises a stabilizer.

[0783] In some embodiments, the additive is a surfactant.

[0784] In some embodiments, the surfactant is a wetting agent, a dispersing agent, or a combination thereof.

[0785] In some embodiments, the dispersant is an anionic polymeric surfactant, such as Metasperse 500L.

[0786] In some embodiments, the dispersant is an anionic surfactant such as Tensiofix LB350.

[0787] In some embodiments, the dispersant is a nonionic surfactant, such as Tensiofix L051. In some embodiments, the dispersant is an anionic surfactant, such as ECOSURF TM In some embodiments, the dispersant is an anionic tristyrylphenol phosphate surfactant, such as Soprophor FL or 3D 33. In some embodiments, the dispersant is a nonionic surfactant such as TERGITOL TM XD. In some embodiments, the dispersant is a nonionic surfactant such as Atlox TM 4913.

[0788] In some embodiments, the dispersant is a mixture of anionic and nonionic surfactants, such as Tensiofix CGA213.

[0789] In some embodiments, the dispersant is a polyelectrolyte block copolymer (as described in WO 2017 / 098325).

[0790] In some embodiments, the dispersant comprises a block polymer comprising 77% sodium 2-acrylamido-2-methylpropane-1-sulfonate (AMPS) monomer and 23% ethyl acrylate (EA) monomer.

[0791] In some embodiments, the dispersant is a 30% by weight aqueous solution of a block polymer comprising 77% sodium 2-acrylamido-2-methylpropane-1-sulfonate (AMPS) monomer and 23% ethyl acrylate (EA) monomer, which can be prepared as described in Example 1 of WO 2017 / 098325.

[0792] In one embodiment, the dispersant is T-77.

[0793] In certain embodiments, when the composition is a suspoemulsion, the dispersant is Geropon T-77.

[0794] In some embodiments, the wetting agent is a high HLB polymer wetting agent, such as Atlas G65002L.

[0795] In some embodiments, the high HLB is greater than 10. In some embodiments, the high HLB is greater than 12. In some embodiments, the high HLB is greater than 13. In some embodiments, the high HLB is greater than 14.

[0796] In some embodiments, the nonionic polyalkylene oxide block polymer surfactant has a High HLB greater than 10. In some embodiments, the nonionic polyalkylene oxide block polymer surfactant has a High HLB greater than 12. In some embodiments, the nonionic polyalkylene oxide block polymer surfactant has a High HLB greater than 13. In some embodiments, the nonionic polyalkylene oxide block polymer surfactant has a High HLB greater than 14.

[0797] In some embodiments, the wetting agent is Adsee 900, decyl alcohol ethoxylate.

[0798] In some embodiments, the composition further comprises a stabilizer.

[0799] In some embodiments, the concentration of metallic copper in the copper-based fungicide in the aqueous composition is greater than 10% by weight based on the total weight of the composition, and the dispersant is an anionic polymeric surfactant Metasperse 500L, an anionic surfactant Tensiofix LB350, an anionic surfactant ECOSURF TM EH-6, anionic tristyrylphenol phosphate surfactant Soprophor FL or 3D 33. Nonionic surfactants such as TERGITOL TM XD, nonionic surfactant Atlox TM 4913, or nonionic surfactant Tensiofix L051. The wetting agent is a high HLB polymer wetting agent Atlas G65002L, and the composition further comprises a stabilizer.

[0800] In some embodiments, the concentration of metallic copper in the copper-based fungicide in the aqueous composition is greater than 10% by weight based on the total weight of the composition, and the surfactant is an anionic and nonionic surfactant such as Tensiofix CGA213 or TERGITOL TM XD combination.

[0801] The present invention also provides an aqueous composition comprising (1) a macromolecular complex comprising (i) a copper-based fungicide and (ii) a polyelectrolyte, (2) water and (3) at least one agriculturally acceptable additive, wherein (i) the viscosity is in the range of 1500-1800 cPs (measured with a Brookfield spindle 63 at 12 rpm), (ii) the particle size distribution (d90) is less than 4 microns, (iii) the pH is in the range of 5.0-7.5, and / or (iv) the density (g / ml) is 1.26±0.05 at 25°C.

[0802] In some embodiments, viscosity is measured using a Brookfield spindle 63 at 12 rpm.

[0803] In some embodiments, the viscosity in the composition is in the range of 1500-1800 cPs (measured with a Brookfield spindle 63 at 12 rpm).

[0804] In some embodiments, the particle size distribution (d90) in the composition is less than 10 microns and the particle size distribution (d50) is less than 5 microns.

[0805] In some embodiments, the pH in the composition is in the range of 5.0-7.5.

[0806] In some embodiments, the density of the composition at 25°C (g / ml) is 1.26 ± 0.05.

[0807] In some embodiments, the agriculturally acceptable additive is a dispersant. In some embodiments, the composition comprises at least one dispersant.

[0808] In some embodiments, the composition comprises at least one anionic dispersant and at least one nonionic surfactant.

[0809] The composition of the present invention may also contain two or more different dispersants. The dispersants are preferably present in an amount of between 0 and up to 10% (w / v), more preferably between 0.01 and up to 5% (w / v), more preferably between 0.02 and up to 2% (w / v),

[0810] In some embodiments, the dispersant is a modified acrylic polymer, unmodified acrylic acid, or any combination thereof.

[0811] In some embodiments, the modified acrylic polymer is a modified styrene acrylic, a polymethyl methacrylate-polyethylene glycol graft copolymer, or any combination thereof. In some embodiments, the modified acrylic polymer is a modified styrene acrylic polymer. In some embodiments, the modified styrene acrylic polymer is Atlox Metasperse TM 500L (sold by Croda). In some embodiments, the modified acrylic polymer is a polymethyl methacrylate-polyethylene glycol graft copolymer.

[0812] In some embodiments, the concentration of the dispersant in the composition is 0.01%-15% by weight based on the total weight of the composition.

[0813] In some embodiments, the concentration of the dispersant in the composition is 0.01%-12% by weight based on the total weight of the composition. In some embodiments, the concentration of the dispersant in the composition is 1%-12% by weight based on the total weight of the composition. In some embodiments, the concentration of the dispersant in the composition is 0.01%-10% by weight based on the total weight of the composition. In some embodiments, the concentration of the dispersant in the composition is 1%-5% by weight based on the total weight of the composition. In some embodiments, the concentration of the dispersant in the composition is 5%-10% by weight based on the total weight of the composition. In some embodiments, the concentration of the dispersant is about 2% by weight based on the total weight of the composition. In some embodiments, the concentration of the dispersant is about 5% by weight based on the total weight of the composition. In some embodiments, the concentration of the dispersant is about 6% by weight based on the total weight of the composition. In some embodiments, the concentration of the dispersant is about 7% by weight based on the total weight of the composition. In some embodiments, the concentration of the dispersant is about 8% by weight based on the total weight of the composition. In some embodiments, the concentration of the dispersant is about 9% by weight based on the total weight of the composition. In some embodiments, the concentration of the dispersant is about 10% by weight based on the total weight of the composition.

[0814] The composition according to the invention may further comprise at least one pH adjusting agent or buffer, such as an organic or inorganic base and / or an organic or inorganic acid.

[0815] In some embodiments, the compositions comprise one or more physical stabilizers, such as buffers, acidifiers, antifoaming agents, thickeners, and drift retarders.

[0816] In some embodiments, the composition comprises at least one stabilizer.In some embodiments, the agriculturally acceptable additive is a stabilizer.

[0817] When the polyelectrolyte is a complex of a polyanion and a polycation, a stabilizer may be used. When present, the stabilizer is preferably selected from carboxylic acids such as citric acid, acetic acid, and / or dodecylbenzenesulfonic acid, orthophosphoric acid dodecylbenzenesulfonic acid and suitable salts thereof. The composition of the present invention may also comprise two or more different stabilizers. The stabilizer is preferably present in an amount of 0 to up to 10% (w / v), more preferably 0.01 to up to 5% (w / v), more preferably 0.02 to up to 1% (w / v), more preferably about 0.05% (w / v).

[0818] In some embodiments, the stabilizer is an acid. In some embodiments, the acid is acetic acid. Acids are used to obtain dissolution of some polyelectrolytes. For example, chitosan is an amino polysaccharide composed of β-(1right4)-linked D-aminoglucose residues. In an acidic environment, the overall protonation of the 2-amino group produces cationic chitosan.

[0819] In some embodiments, the concentration of the acid in the composition is 0%-5% by weight based on the total weight of the composition. In some embodiments, the concentration of the acid in the composition is 0.01%-5% by weight based on the total weight of the composition. In some embodiments, the concentration of the acid in the composition is 0.1%-0.5% by weight based on the total weight of the composition. In some embodiments, the concentration of the acid in the composition is about 0.3% by weight based on the total weight of the composition. In some embodiments, the concentration of the acid in the composition is 1%-3% by weight based on the total weight of the composition. In some embodiments, the concentration of the acid in the composition is 1.5%-2% by weight based on the total weight of the composition. In some embodiments, the composition comprises at least one antifoaming agent. In some embodiments, the agriculturally acceptable additive is an antifoaming agent.

[0820] In certain embodiments, composition comprises at least one antifoaming agent.In certain embodiments, agriculturally acceptable additive is an antifoaming agent.When present, antifoaming agent is preferably selected from polymethylsiloxane, polydimethylsiloxane, dimethicone octanol and silicone oil.Composition of the present invention can also comprise two or more different antifoaming agents.Antifoaming agent preferably exists in an amount of 0 to up to 10% (w / v), more preferably 0.05 to up to 5% (w / v), more preferably 0.1 to up to 1% (w / v), more preferably about 0.05% (w / v).

[0821] In some embodiments, the antifoam agent is silicone based.

[0822] In some embodiments, the concentration of the anti-foam forming agent is 0.01%-5% by weight based on the total weight of the composition. In some embodiments, the concentration of the anti-foam forming agent is 0.1%-1% by weight based on the total weight of the composition. In some embodiments, the concentration of the anti-foam forming agent is about 0.4% by weight based on the total weight of the composition. In some embodiments, the concentration of the anti-foam forming agent is about 0.5% by weight based on the total weight of the composition.

[0823] In some embodiments, the composition comprises at least one antifreeze agent. In some embodiments, the agriculturally acceptable additive is an antifreeze agent.

[0824] When present, an antifreezing agent (or "antifreeze") is preferably selected from glycerol, ethylene glycol, hexylene glycol and propylene glycol. The composition of the present invention may also comprise two or more different antifreezes. The antifreeze is preferably present in an amount between 0 and up to 10% (w / v), more preferably between 0.01 and up to 5% (w / v), more preferably between 0.02 and up to 1% (w / v), more preferably about 0.05% (w / v).

[0825] In some embodiments, the antifreeze agent is propylene glycol.

[0826] In some embodiments, the concentration of the antifreeze in the composition is 1%-10% by weight based on the total weight of the composition. In some embodiments, the concentration of the antifreeze in the composition is 1%-5% by weight based on the total weight of the composition. In some embodiments, the concentration of the antifreeze in the composition is about 4% by weight based on the total weight of the composition. In some embodiments, the concentration of the antifreeze in the composition is about 5% by weight based on the total weight of the composition. In some embodiments, the concentration of the antifreeze in the composition is 4.2% by weight based on the total weight of the composition.

[0827] In some embodiments, the composition comprises at least one surfactant.In some embodiments, the agriculturally acceptable additive is a surfactant.

[0828] Surfactants may include, but are not limited to, ionic or nonionic surfactants. Examples of surfactants are alkyl-terminated ethoxylated glycols, alkyl-terminated alkyl block alkoxylated glycols, dialkyl sulfosuccinates, phosphated esters, alkyl sulfonates, alkyl aryl sulfonates, tristyrylphenol alkoxylates, natural or synthetic fatty acid alkoxylates, natural or synthetic fatty alcohol alkoxylates, alkoxylated alcohols (such as n-butyl alcohol polyglycol ethers), block copolymers (such as ethylene oxide-propylene oxide block copolymers and ethylene oxide-butylene oxide block copolymers) or combinations thereof.

[0829] Examples of surfactants include, but are not limited to, emulsifiers and wetting agents.

[0830] In some embodiments, the surfactant is a nonionic surfactant. In some embodiments, the nonionic surfactant is Tensiofix L051. In some embodiments, the concentration of the nonionic surfactant in the composition is between 0.1% and 0.5% by weight based on the total weight of the composition. In some embodiments, the concentration of the nonionic surfactant in the composition is about 0.2% by weight based on the total weight of the composition.

[0831] In some embodiments, the surfactant is an anionic surfactant. In some embodiments, the anionic surfactant is Tensiofix LB350. In some embodiments, the anionic surfactant is a tristyrylphenol phosphate surfactant. In some embodiments, the tristyrylphenol phosphate surfactant is Soprophor FL or 3D 33. In some embodiments, the concentration of the anionic surfactant in the composition is between 1% and 3% by weight based on the total weight of the composition. In some embodiments, the concentration of the anionic surfactant in the composition is about 2% by weight based on the total weight of the composition.

[0832] In some embodiments, the surfactant is a combination of anionic and nonionic surfactants. In some embodiments, the surfactant is Tensiofix CGA213. In some embodiments, the concentration of the surfactant containing the combination of anionic and nonionic surfactants in the composition is between 0.1% and 2% by weight based on the total weight of the composition. In some embodiments, the concentration of the surfactant containing the combination of anionic and nonionic surfactants in the composition is about 1% by weight based on the total weight of the composition.

[0833] In some embodiments, the concentration of the surfactant in the composition is 0%-0.5% by weight based on the total weight of the composition. In some embodiments, the concentration of the surfactant in the composition is 0.001%-0.5% by weight based on the total weight of the composition. In some embodiments, the concentration of the surfactant in the composition is 0.01%-1% by weight based on the total weight of the composition. In some embodiments, the concentration of the surfactant in the composition is about 0.1% by weight based on the total weight of the composition.

[0834] In some embodiments, the surfactant is a nonionic hydrocarbon-based surfactant.

[0835] In some embodiments, the concentration of the nonionic hydrocarbon-based surfactant in the composition is 0.001%-0.5% by weight based on the total weight of the composition. In some embodiments, the concentration of the nonionic hydrocarbon-based surfactant in the composition is about 0.1% by weight based on the total weight of the composition. In some embodiments, the concentration of the nonionic hydrocarbon-based surfactant in the composition is 0.001%-0.1% by weight based on the total weight of the composition.

[0836] In some embodiments, the total concentration of one or more surfactants in the composition is 2-5% w / w by weight based on the total weight of the total composition. In some embodiments, the total concentration of one or more surfactants in the composition is 3-4% w / w by weight based on the total weight of the total composition. In some embodiments, the total concentration of one or more surfactants in the composition is about 3.2% w / w by weight based on the total weight of the total composition.

[0837] In some embodiments, when the polyelectrolyte is a complex with chitosan, the composition further comprises a cosolvent. In some embodiments, the cosolvent is an antifreeze agent. In some embodiments, the cosolvent is propylene glycol. In some embodiments, the antifreeze agent is propylene glycol.

[0838] In some embodiments, wherein the composition comprises at least one wetting agent. In some embodiments, the agriculturally acceptable additive is a wetting agent.

[0839] The wetting agent may be selected from dioctyl succinate, polyoxyethylene / polypropylene, decyl alcohol ethoxylate and tristearyl sulfonate / tristearyl phosphate. The composition of the present invention may also comprise two or more different wetting agents. The wetting agent is preferably present in an amount of between 0 and up to 10% (w / v), more preferably between 0.01 and up to 5% (w / v), more preferably between 0.02 and up to 1% (w / v), more preferably about 0.05% (w / v).

[0840] In some embodiments, the wetting agent is a polyoxyalkylene block copolymer. In some embodiments, the wetting agent is a butyl block copolymer. In some embodiments, the butyl block copolymer is Atlas TM G5002L (sold by Croda Corporation). In some embodiments, the wetting agent is Adsee 900, decyl alcohol ethoxylate.

[0841] In some embodiments, the concentration of the wetting agent in the composition is 1%-10% by weight based on the total weight of the composition. In some embodiments, the concentration of the wetting agent in the composition is 0%-5% by weight based on the total weight of the composition. In some embodiments, the concentration of the wetting agent in the composition is 1%-5% by weight based on the total weight of the composition. In some embodiments, the concentration of the wetting agent in the composition is 1%-3% by weight based on the total weight of the composition. In some embodiments, the concentration of the wetting agent in the composition is about 2% by weight based on the total weight of the composition.

[0842] In some embodiments, the composition comprises at least one rheology modifier.In some embodiments, the agriculturally acceptable additive is a rheology modifier.

[0843] In some embodiments, the rheology modifier is a thickener. In some embodiments, the composition comprises at least one thickener.

[0844] Thickeners (when present) are preferably selected from agar, alginic acid, alginates, carrageenan, gellan gum, xanthan gum, succinoglycan gum, guar gum, acetylated distarch adipate, acetylated oxidized starch, arabinogalactan, ethylcellulose, methylcellulose, locust bean gum, sodium starch octenylsuccinate and triethyl citrate. The composition of the present invention may also comprise two or more different thickeners. The thickener is preferably present in an amount of 0 to up to 10% (w / v), more preferably 0.01 to up to 5% (w / v), more preferably 0.02 to up to 1% (w / v), more preferably about 0.05% (w / v).

[0845] In some embodiments, the thickening agent is xanthan gum.

[0846] In some embodiments, the rheology modifier is 23 (sold by Solvay). In some embodiments, the rheology modifier is xanthan gum.

[0847] In some embodiments, the concentration of the rheology modifier in the composition is 0.01%-10% by weight based on the total weight of the composition. In some embodiments, the concentration of the rheology modifier in the composition is 5%-10% by weight based on the total weight of the composition. In some embodiments, the concentration of the rheology modifier in the composition is about 6% by weight based on the total weight of the composition. In some embodiments, the concentration of the rheology modifier in the composition is about 8% by weight based on the total weight of the composition.

[0848] In some embodiments, the composition comprises at least one thickener and at least one biocide. In some embodiments, the amount of thickener and biocide in the composition is up to 1% by weight based on the total weight of the composition.

[0849] In some embodiments, the agriculturally acceptable additive is a preservative. In some embodiments, the composition comprises at least one preservative.

[0850] In some embodiments, the preservative is a biocide. In some embodiments, the composition comprises at least one biocide. In some embodiments, the preservative is MBS.

[0851] In some embodiments, the concentration of the preservative in the composition is 0.01%-5% by weight based on the total weight of the composition. In some embodiments, the concentration of the preservative in the composition is 0.01%-1% by weight based on the total weight of the composition. In some embodiments, the concentration of the preservative in the composition is about 0.1% by weight based on the total weight of the composition. In some embodiments, the concentration of the preservative in the composition is 0.083% by weight based on the total weight of the composition.

[0852] The compositions according to the invention may comprise additional biologically active ingredients, also referred to as additional agrochemicals, such as growth regulators, biostimulants, fungicides, herbicides, insecticides, acaricides, molluscicides, miticides, rodenticides; and / or bactericides.

[0853] Various agrochemicals can be used as additional biologically active ingredients. Examples of such agrochemicals are, but are not limited to, crop protection agents such as pesticides, safeners, plant growth regulators, insect repellents, biostimulants and preservatives such as bacteriostats or bactericides.

[0854] In some embodiments, the composition comprises at least one additional biologically active ingredient, preferably an additional insecticide, fungicide and / or herbicide.

[0855] Additional agrochemicals that can be used with the combinations, compositions and macromolecular complexes of the present invention are described below.

[0856] The composition of the present invention may also include two or more additional biologically active ingredients, such as two or more fungicides, two or more herbicides, two or more insecticides, two or more miticides, two or more bactericides, or combinations thereof, such as at least one antifungal compound and at least one insecticide, at least one antifungal compound and at least one herbicide, at least one antifungal compound and at least one miticide, at least one antifungal compound and at least one bactericide, at least one herbicide and at least one insecticide, at least one herbicide and at least one miticide, at least one herbicide and at least one bactericide, at least one insecticide and at least one miticide, at least one insecticide and at least one bactericide, and at least one miticide and at least one bactericide. As known to the skilled person, some biologically active ingredients have a wide range of target organisms and are therefore included in more than one subgroup of biologically active ingredients. The at least one additional biologically active ingredient is preferably present in a concentration between 0.1 and 90 w / v%, more preferably between 1 and 70 w / v%, more preferably between 10 and 50 w / v%.

[0857] The additional biologically active ingredient is preferably an insecticide, a fungicide and / or a herbicide.

[0858] Preferred additional insecticides are carbamates such as carbofuran, propoxur, methomyl, benfenchlor, oxamyl and aldicarb, organochlorines such as methoxychlor, kelthane, lindane, toxaphene, and cyclodiene insecticides such as aldrin, dieldrin, endrin, mirex, chlordane, heptachlor and endosulfan, organophosphates such as parathion, malathion, methyl parathion, chlorpyrifos, diazinon, dichlorvos, phosmet, fenitrothion, chlorpyrifos, methylpyraclostrobin, azinphos-terbufos and terbufos, formamidines such as amitraz, chlordimeform, chlorfenapyr, carbendazim and monoformamidine, organosulfurs such as thiamethoxam, avermectins such as ivermectin, doramectin, selamectin, milbemycin oxime and moxidectin, nicotine Pesticides of the type A such as acetamiprid, clothianidine, imidacloprid, nitenpyram, nithiazine, thiacloprid and thiamethoxam and / or pyrethroid insecticides such as allethrin, bifenthrin, cyfluthrin, cypermethrin, phenothrin, deltamethrin, esfenvalerate, etofenprox, cypermethrin, fenvalerate, flucythrin, flucythrin, fmiprothrin, lambda-cyhalothrin, metofluthrin, permethrin, resmethrin, silafluthrin, etofenprox, tau-fluvalinate, tefluthrin, tetramethrin, tralomethrin and transfluthrin.

[0859] Preferred additional fungicides are selected from mancozeb, sodium o-phenylphenol, 2-phenylphenol; 8-hydroxyquinoline sulfate; acibenzolar-5-methyl; actinovate; 4-dodecyl-2,5 (or 2,6)-dimethylmorpholine (aldimorph); sulfamethoxam; 1-aminopropylphosphonic acid (ampropylfos); 1-aminopropylphosphonic acid potassium; andoprim; dithiocarb; azoxystrobin bensulfuron; oxadiazine; benomyl (1-(butylcarbamoyl) benzimidazol-2-ylcarbamic acid methyl ester); isopropylbenzyl; benzylcyanamide; isobutylbenzylcyanamide; bialaphos; binachlor; biphenyl; blasticidin-S; boscalid; ethiprole bupirimate; butylthiocarb; butylamine; calcium polysulfide; capsimycin; captamidophthal; captan (N-(trichloromethylthio)cyclohex-4-ene-1,2-dicarboximide); carbendazim; carboxin; cyproconazole; carvone; chloranil; chloranil; chloroneb; chlorothalonil; chlozolinate; cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol; chloranil; conazole fungicides, such as, for example, (RS)-1-(β-allyloxy-2,4-dichlorophenethyl)imidazole (chloranil; Janssen Pharmaceuticals, Inc. Pharmaceutica NV, Belgium) and N-propyl-N-[2-(2,4,6-trichlorophenoxy)ethyl]imidazole-1-carboxamide (prochloraz); cyazofamid; flutolanil; cymoxanil; cyprodinil; cyprodinil; siroxanil; Dagger G; debacarb; dichloranil; dichloronaphthoquinone; diclofenac; diclocymet; diclomezine; dicloran; ethotripsy; fluopyram; mefenamic acid; fenpropimorph; fenpropimorph; dimetho ... 3-Chloro-N-(3-chloro-5-trifluoromethyl-2-pyridyl)-α,α,α-trifluoro-2,6-dinitro-p-toluidine); flufenacet; fluoxathiapiprolin; fluoxamidopyrazone; flumorph; flucloroxanil; fluoxastrobin; fluopyram; fluopyram; flutriamide; flutolanil; flutolanil; flutolanil; fosetyl-A1; fosetyl sodium; furanil; furoxamyl; furoxamidopyrazone; dimethylfuran; seed dressing amine; biguanide salt; hexachlorobenzene; oxamexazole; biguanide triacetate; biguanide tri(alkylbenzene sulfonate);Iodocarb; iprobenfos; isoproconazole; propineb; irumamycin; chlorfenapyr; chlorfenapyr; kasugamycin; kresoxim-methyl; meferimzone; mefenamic acid; metalaxyl; metalaxyl-M; sulfamethoxam; methfiroxam; methyl 1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H-imidazole-5-carboxylate; methyl 2-[[[cyclopropyl[(4-methoxyphenyl)imino]methyl]thio]-methyl]-α-(methoxymethylene)phenylacetate; methyl 2-[2-[3-(4-chlorophenyl)imino]methyl]thio]-methyl]-α-(methoxymethylene)phenylacetate [1-(2-(4-(2-((4-((2-( ... phthalide; flupyrazone; picoxystrobin; pyraclostrobin; polyoxin; polyoxin; procymidone; propamocarb; propanosine-sodium; propineb; iodoquinazole; prothioconazole; pyraclostrobin; pyraclofos; pyrimethanil; pyroquilone; clopidogrel; pyrrolnitrine, quinconazole; quinoxyfen; pentachloronitrobenzene; silthiopyrad; sodium tetrathiocarbonate; spiroxafil; sulfur; chloranthal; tetrachloronitrobenzene; tetracyclazole; thiazole fungicides, such as, for example, 2-(thiazol-4-yl)benzimidazole (thiabendazole), thiabendazole; thiofuranil; thiophanate-methyl; thiophanate-butyl; thiocyanate; tolclofos-methyl; tolylfluanid; Leaf rust; triazoxide; tricyclamide; tricyclazole; tridemorph; trifloxystrobin; jinggangmycin A; vinclozolin; benzyl oxadiazole; (2S)-N-[2-[4-[[3-(4-chlorophenyl)-2-propynyl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(methylsulfonyl)amino]butyramide; 1-(1-naphthyl)-1H-pyrrole-2,5-dione; 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine; 2,4-dihydro-5-methoxy-2-methyl-4-[[[[1-[3-(trifluoromethyl)phenyl]-ethylidene]amino]oxy]methyl]phenyl]-3H-1,2,3-triazol-3-one;2-amino-4-methyl-N-phenyl-5-thiazolecarboxamide; 2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3-pyridinecarboxamide; 3,4,5-trichloro-2,6-pyridinedicarbonitrile; 3-[(3-bromo-6-fluoro-2-methyl-1H-indol-1-yl)sulfonyl]-N,N-dimethyl-1H-1,-2,4-triazole-1-sulfonamide, and / or a mixture thereof. ;

[0860] In some embodiments, the additional fungicide is natamycin. The composition of the present invention may also include two or more additional fungicides, such as, for example, natamycin and strobilurin type fungicides such as azoxystrobin, picoxystrobin, natamycin and triazole type fungicides such as cyproconazole, prothioconazole, natamycin and succinate dehydrogenase inhibitor type fungicides such as boscalid, natamycin and phthalimide / phthalonitrile type fungicides such as thiophanate-methyl, natamycin and captan, natamycin and benzimidazole type fungicides such as thiabendazole, natamycin and carbendazim. Acid ester fungicides such as propamocarb, natamycin and carboxamide type fungicides such as pyraclostrobin, natamycin and dicarboxamide type fungicides such as isopyram, natamycin and morpholine type fungicides such as dimethamorph, natamycin and organophosphate type fungicides such as fosetyl, natamycin and azole fungicides such as prothioconazole, benzamide type fungicides (such as fluopyram), natamycin and phenylamide type fungicides such as metalaxyl, natamycin and fungicides not belonging to a specific group of fungicides such as fludioxynil and / or folpet.

[0861] Preferred additional herbicides are selected from inhibitors of amino acid synthesis such as inhibitors of 5-enolpyruvyl-shikimate-3-phosphate synthase, acetolactate synthase and glutamine synthase, such as glyphosate, sulfonylureas, imidazolinones, glufosinate and / or 1,2,4-triazole [1,5A] pyrimidine; photosynthetic inhibitors that bind to D-1: quinone binding proteins, including anilines, benzimidazoles, biscarbamates, pyridazinones, triazinediones, triazines, triazinones, uracils, substituted ureas, quinones, Hydroxybenzonitriles and several unclassified heterocycles; inhibitors of acetyl-CoA carboxylase, such as aryloxyphenoxyalkanoic acids and cyclohexanedione; inhibitors of cell division, such as phosphoramides and dinitroanilines; inhibitors of the terpenoid synthesis pathway, such as substituted pyridazinones, m-phenoxybenzamides, fluazifop, difunone, 4-hydroxypyridine, aminotriazole cypermethrin, 6-methylpyrimidine, isoxazolidinone; inhibitors of dihydropteroate synthase, such as sulfamethoxazole, and / or mixtures thereof.

[0862] Such preferred additional herbicides are preferably selected from the group consisting of bicyclon, mesotrione, sulcotrione, furansulfuron, tampron, 2,4-dichlorophenoxyacetic acid, 3,6-dichloro-2-methoxybenzoic acid (dicamba), 4-hydroxy-3-[[2-(2-methoxyethoxy)methyl]-6-(trifluoromethyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.1]-oct-3-ene-2-one (flupyridone), ketospiradox or its free acid, pyraclostrobin, pyrazoline, pyrazol, benzylpyrazol, [2-chloro- [3-(2-methoxyethoxy)-4-(methylsulfonyl)phenyl](l-ethyl-5-hydroxy-1H-pyrazol-4-yl)-methanone, (2,3-dihydro-3,3,4-trimethyl-1,1-dioxobenzo[b]thiophen-5-yl)(5-hydroxy-1-methyl-1H-pyrazol-4-yl)-methanone, isoxaflutole, isoxaflutole, a-(cyclopropylcarbonyl)-2-(methylsulfonyl)-oxo-4-chloro-benzenepropionitrile and a-(cyclopropylcarbonyl)-2-(methylsulfonyl)-oxo-4-(trifluoromethyl)-benzenepropionitrile.

[0863] Preferred additional fungicides are strobilurin fungicides and azole fungicides.

[0864] The strobilurin fungicide may be, but is not limited to, picoxystrobin, azoxystrobin, or a combination thereof.

[0865] The azole fungicide may be, but is not limited to, tebuconazole, prothioconazole, or a combination thereof.

[0866] In some embodiments, the benzamide fungicide is fluopyram,

[0867] In some embodiments, when one or more additional fungicides are added to the composition, the dispersant is a mixture of an anionic tristyrylphenol phosphate surfactant (such as Soprophor FL or Soprophor 3D33) and a high HLB nonionic polyalkylene oxide block polymer surfactant (such as Atlas G5002L) or a nonionic alcohol ethoxylate (such as ECOSURFEH6).

[0868] In some embodiments, the combinations, compositions and macromolecular complexes of the present invention are combined with two additional fungicides. In some embodiments, the combinations, compositions and macromolecular complexes of the present invention are combined with picoxystrobin and tebuconazole. In some embodiments, the combinations, compositions and macromolecular complexes are combined with picoxystrobin and tebuconazole. In some embodiments, the combinations, compositions and macromolecular complexes are combined with prothioconazole. In some embodiments, the combinations, compositions and macromolecular complexes are combined with picoxystrobin and prothioconazole. In some embodiments, the combinations, compositions and macromolecular complexes are combined with fluopyram.

[0869] In some embodiments, the combinations, compositions, and macromolecular complexes are combined with azoles and carboxamides. In some embodiments, the carboxamide is fluopyrabdo.

[0870] In some embodiments, the combinations, compositions, and macromolecular complexes are combined with a morpholine. In some embodiments, the morpholine is fenpropidin.

[0871] In some embodiments, the composition comprising a copper-based fungicide and a polyelectrolyte further comprises picoxystrobin and tebuconazole. In some embodiments, the composition comprising a copper-based fungicide and a polyelectrolyte further comprises prothioconazole. In some embodiments, the composition comprising a copper-based fungicide and a polyelectrolyte further comprises picoxystrobin and prothioconazole. In some embodiments, the composition comprising a copper-based fungicide and a polyelectrolyte further comprises fluopyram.

[0872] In some embodiments, the polyelectrolyte comprises at least one polyanion. In some embodiments, the polyelectrolyte is a polyanion. In some embodiments, the polyelectrolyte comprises a polycation and a polyanion. In some embodiments, the polyelectrolyte is a complex of a polycation and a polyanion.

[0873] The composition of the present invention may also include two or more additional biologically active ingredients, such as two or more fungicides, two or more herbicides, two or more insecticides, two or more miticides, two or more bactericides, or combinations thereof, such as at least one antifungal compound and at least one insecticide, at least one antifungal compound and at least one herbicide, at least one antifungal compound and at least one miticide, at least one antifungal compound and at least one bactericide, at least one herbicide and at least one insecticide, at least one herbicide and at least one miticide, at least one herbicide and at least one bactericide, at least one insecticide and at least one miticide, at least one insecticide and at least one bactericide, and at least one miticide and at least one bactericide. As known to the skilled person, some biologically active ingredients have a wide range of target organisms and are therefore included in more than one subgroup of biologically active ingredients. The at least one additional biologically active ingredient is preferably present in a concentration between 0.1 and 90 w / v%, more preferably between 1 and 70 w / v%, more preferably between 10 and 50 w / v%.

[0874] The additional biologically active ingredient is preferably an insecticide, a fungicide and / or a herbicide.

[0875] In some embodiments, the additional biologically active ingredient is an azole fungicide.

[0876] In some embodiments, the additional biologically active ingredients are an azole fungicide and a strobilurin fungicide. In some embodiments, the strobilurin fungicide is picoxystrobin. In some embodiments, the azole fungicide is prothioconazole.

[0877] In some embodiments, the additional biologically active ingredients are azole fungicides and carboxamide fungicides. In some embodiments, the carboxamide fungicide is fluopyraclostrobin.

[0878] In some embodiments, the additional biologically active ingredient is a benzamide fungicide. In some embodiments, the benzamide fungicide is fluopyram.

[0879] In some embodiments, the additional biologically active ingredients are azole fungicides and morpholine fungicides. In some embodiments, the morpholine fungicide is fenpropidin.

[0880] In some embodiments, the copper-based fungicide used in combination with the azole fungicide, strobilurin fungicide, carboxamide fungicide, and / or morpholine fungicide is copper oxychloride, copper hydroxide, copper sulfate, copper acetate, copper chloride, copper chlorate, copper formate, copper hexafluorosilicate, copper nitrate, copper chromate, copper sulfate pentahydrate, Bordeaux mixture, and / or any combination thereof.

[0881] In some embodiments, the composition is substantially free of agriculturally acceptable organic solvents. In some embodiments, the composition is aqueous.

[0882] In some embodiments, the composition is a suspension concentrate.

[0883] In some embodiments, the suspension concentrate composition comprises:

[0884] The present invention provides a concentrate composition comprising (1) a copper-based fungicide, (2) a polyelectrolyte, and (3) an aqueous carrier.

[0885] The present invention provides a suspension concentrate comprising (1) a copper-based fungicide, (2) a polyelectrolyte, and (3) an aqueous carrier.

[0886] The present invention provides a concentrate composition comprising (1) a macromolecular complex comprising (i) a copper-based fungicide and (ii) a polyelectrolyte and (2) an aqueous carrier.

[0887] The present invention also provides a suspension concentrate comprising (1) a macromolecular complex comprising (i) a copper-based fungicide and (ii) a polyelectrolyte and (2) an aqueous carrier.

[0888] The present invention provides a composition comprising (i) a macromolecular complex comprising a copper-based fungicide and a polyelectrolyte, (ii) at least one additional fungicide and (iii) at least one agriculturally acceptable additive.

[0889] The present invention provides a composition comprising a copper-based fungicide and a polyelectrolyte.

[0890] The present invention provides a composition comprising (i) a copper-based fungicide, (ii) a polyelectrolyte, (iii) at least one additional fungicide and (iv) at least one agriculturally acceptable additive.

[0891] In some embodiments, the composition comprises 40%-80% water by weight. In some embodiments, the composition comprises 50%-70% water by weight. In some embodiments, the composition comprises 50%-55% water by weight. In some embodiments, the composition comprises 40%-80% water by weight. In some embodiments, the composition comprises about 51% water by weight. In some embodiments, the composition comprises about 62% water by weight. In some embodiments, the composition comprises 30%-50% water by weight. In some embodiments, the composition comprises 30%-60% water by weight. In some embodiments, the composition comprises 30%-80% water by weight.

[0892] In some embodiments, the additional fungicide is selected from the group consisting of azole fungicides, strobilurin fungicides, benzamide fungicides, morpholines, QiI fungicides, SDHI, and any combination thereof.

[0893] In some embodiments, the azole fungicide is a triazole fungicide.

[0894] In some embodiments, azole fungicides may include, but are not limited to, azaconazole, bifenthrin, bromoconazole, cyproconazole, difenoconazole, diniconazole, fluconazole, ethoconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imipenem, methiconazole, metconazole, myclobutanil, penconazole, propiconazole, silyconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triathione, and prothioconazole, and clofoconazole.

[0895] In some embodiments, strobilurin fungicides may include, but are not limited to, azoxystrobin, syringystrobin, enoxastrobin, flutoxifen, picoxystrobin, pyraclostrobin, mandestrobin, pyraclostrobin, pyraclostrobin, chlorpyrifos, kresoxim-methyl, trifloxystrobin, diastereoisomer, enoxastrobin, fenoxystrobin, oxadiazon, tetrazobactam, and fluoxastrobin.

[0896] In some embodiments, the strobilurin fungicide is selected from the group consisting of picoxystrobin, trifloxystrobin, azoxystrobin, pyraclostrobin, fenoxystrobin, tetracycline, mandestroystrobin, and combinations thereof.

[0897] In some embodiments, the SDHI may include, but is not limited to, penthiopyrad, boscalid, flutolanil, fluopyram, indopyram, fluopyram, fluindopyram, benzodiflupyr, bixafen, and fluopyram.

[0898] In some embodiments, the SDHI fungicide is selected from the group consisting of: bixafen; fluopyram, fluoxapyram; indopyram, benzodiflupyram and fluopyram.

[0899] In some embodiments, QiI fungicides may include, but are not limited to, cyazofamid, indazolesulfamide, and fenpicoxamid.

[0900] In some embodiments, the morpholine may include, but is not limited to, 4-dodecyl-2,6-dimethylmorpholine, fenpropimorph, tridemorph, dodecamorph, spiroxafil, fenpropimorph, and fenpropimorph.

[0901] In a preferred embodiment, the subject matter relates to a composition comprising: a) a copper-based fungicide, prothioconazole, and picoxystrobin suspended in water.

[0902] In another preferred embodiment, the subject matter relates to a composition comprising: a) a copper-based fungicide and picoxystrobin suspended in water; and b) prothioconazole dissolved in a water-immiscible carrier.

[0903] In a preferred embodiment, the suspoemulsion composition comprises: (i) a copper-based fungicide, (ii) a strobilurin, (iii) an azole fungicide, (iv) water, (v) a water-immiscible carrier, and (vi) a polyelectrolyte, wherein (1) the copper-based fungicide is copper oxychloride, (2) the strobilurin is picoxystrobin, (3) the azole fungicide is prothioconazole, (4) the copper-based fungicide and the strobilurin are suspended in water and (5) the azole is dissolved in the water-immiscible carrier.

[0904] In another preferred embodiment, the suspoemulsion composition comprises: (i) a copper-based fungicide, (ii) a strobilurin, (iii) an azole fungicide, (iv) water, (v) a water-immiscible carrier and (vi) a polyelectrolyte, wherein (1) the copper-based fungicide is Bordeaux mixture, (2) the strobilurin is picoxystrobin, (3) the azole fungicide is prothioconazole, (4) the copper-based fungicide and the strobilurin are suspended in water and (5) the azole fungicide is dissolved in the water-immiscible carrier.

[0905] In another preferred embodiment, the suspoemulsion composition comprises: (i) a copper-based fungicide, (ii) a strobilurin, (iii) an azole fungicide, (iv) water, (v) a water-immiscible carrier, and (vi) a polyelectrolyte, wherein (1) the copper-based fungicide is copper oxychloride, (2) the strobilurin is picoxystrobin, (3) the azole fungicide is tebuconazole, (4) the copper-based fungicide and the strobilurin are suspended in water and (5) the azole fungicide is dissolved in the water-immiscible carrier.

[0906] In another preferred embodiment, the suspoemulsion composition comprises: (i) a copper-based fungicide, (ii) a strobilurin, (iii) an azole fungicide, (iv) water, (v) a water-immiscible carrier, and (vi) a polyelectrolyte, wherein (1) the copper-based fungicide is Bordeaux mixture, (2) the strobilurin is picoxystrobin, (3) the azole fungicide is tebuconazole, (4) the copper-based fungicide and the strobilurin are suspended in water and (5) the azole fungicide is dissolved in the water-immiscible carrier.

[0907] In another preferred embodiment, the suspoemulsion composition comprises: (i) a copper-based fungicide, (ii) a strobilurin, (iii) an azole fungicide, (iv) water, (v) a water-immiscible carrier and (vi) a polyelectrolyte, wherein (1) the copper-based fungicide is copper oxychloride, (2) the strobilurin is azoxystrobin, (3) the azole fungicide is prothioconazole, (4) the copper-based fungicide and the strobilurin are suspended in water and (5) the azole fungicide is dissolved in the water-immiscible carrier.

[0908] In another preferred embodiment, the suspoemulsion composition comprises: (i) a copper-based fungicide, (ii) a strobilurin, (iii) an azole fungicide, (iv) water, (v) a water-immiscible carrier and (vi) a polyelectrolyte, wherein (1) the copper-based fungicide is Bordeaux mixture, (2) the strobilurin is azoxystrobin, (3) the azole fungicide is prothioconazole, (4) the copper-based fungicide and the strobilurin are suspended in water and (5) the azole fungicide is dissolved in the water-immiscible carrier.

[0909] In another preferred embodiment, the suspoemulsion composition comprises: (i) a copper-based fungicide, (ii) a strobilurin, (iii) an azole fungicide, (iv) water, (v) a water-immiscible carrier, and (vi) a polyelectrolyte, wherein (1) the copper-based fungicide is copper oxychloride, (2) the strobilurin is azoxystrobin, (3) the azole fungicide is tebuconazole, (4) the copper-based fungicide and the strobilurin are suspended in water and (5) the azole fungicide is dissolved in the water-immiscible carrier.

[0910] In another preferred embodiment, the suspoemulsion composition comprises: (i) a copper-based fungicide, (ii) a strobilurin, (iii) an azole fungicide, (iv) water, (v) a water-immiscible carrier and (vi) a polyelectrolyte, wherein (1) the copper-based fungicide is Bordeaux mixture, (2) the strobilurin is azoxystrobin, (3) the azole fungicide is tebuconazole, (4) the copper-based fungicide and the strobilurin are suspended in water and (5) the azole fungicide is dissolved in the water-immiscible carrier.

[0911] In another preferred embodiment, the suspoemulsion composition comprises: (i) a copper-based fungicide, (ii) a strobilurin, (iii) an azole fungicide, (iv) water, (v) a water-immiscible carrier, and (vi) a polyelectrolyte, wherein (1) the copper-based fungicide is copper oxychloride, (2) the strobilurin is picoxystrobin, (3) the azole fungicide is prothioconazole, (4) the copper-based fungicide is suspended in water, and (5) the azole fungicide and the strobilurin are dissolved in the water-immiscible carrier.

[0912] Dissolve in a water-immiscible carrier.

[0913] In another preferred embodiment, the suspoemulsion composition comprises: (i) a copper-based fungicide, (ii) a strobilurin, (iii) an azole fungicide, (iv) water, (v) a water-immiscible carrier and (vi) a polyelectrolyte, wherein (1) the copper-based fungicide is Bordeaux mixture, (2) the strobilurin is picoxystrobin, (3) the azole fungicide is prothioconazole, (4) the copper-based fungicide is suspended in water and (5) the azole fungicide and the strobilurin are dissolved in the water-immiscible carrier.

[0914] In another preferred embodiment, the suspoemulsion composition comprises: (i) a copper-based fungicide, (ii) a strobilurin, (iii) an azole fungicide, (iv) water, (v) a water-immiscible carrier, and (vi) a polyelectrolyte, wherein (1) the copper-based fungicide is copper oxychloride, (2) the strobilurin is picoxystrobin, (3) the azole fungicide is tebuconazole, (4) the copper-based fungicide is suspended in water, and (5) the azole fungicide and the strobilurin are dissolved in the water-immiscible carrier.

[0915] In another preferred embodiment, the suspoemulsion composition comprises: (i) a copper-based fungicide, (ii) a strobilurin, (iii) an azole fungicide, (iv) water, (v) a water-immiscible carrier and (vi) a polyelectrolyte, wherein (1) the copper-based fungicide is Bordeaux mixture, (2) the strobilurin is picoxystrobin, (3) the azole fungicide is tebuconazole, (4) the copper-based fungicide is suspended in water and (5) the azole fungicide and the strobilurin are dissolved in the water-immiscible carrier.

[0916] In another preferred embodiment, the suspoemulsion composition comprises: (i) a copper-based fungicide, (ii) a strobilurin, (iii) an azole fungicide, (iv) water, (v) a water-immiscible carrier and (vi) a polyelectrolyte, wherein (1) the copper-based fungicide is copper oxychloride, (2) the strobilurin is azoxystrobin, (3) the azole fungicide is prothioconazole, (4) the copper-based fungicide is suspended in water and (5) the azole fungicide and the strobilurin are dissolved in the water-immiscible carrier.

[0917] In another preferred embodiment, the suspoemulsion composition comprises: (i) a copper-based fungicide, (ii) a strobilurin, (iii) an azole fungicide, (iv) water, (v) a water-immiscible carrier and (vi) a polyelectrolyte, wherein (1) the copper-based fungicide is Bordeaux mixture, (2) the strobilurin is azoxystrobin, (3) the azole fungicide is prothioconazole, (4) the copper-based fungicide is suspended in water and (5) the azole fungicide and the strobilurin are dissolved in the water-immiscible carrier.

[0918] In another preferred embodiment, the suspoemulsion composition comprises: (i) a copper-based fungicide, (ii) a strobilurin, (iii) an azole fungicide, (iv) water, (v) a water-immiscible carrier, and (vi) a polyelectrolyte, wherein (1) the copper-based fungicide is copper oxychloride, (2) the strobilurin is azoxystrobin, (3) the azole fungicide is tebuconazole, (4) the copper-based fungicide is suspended in water, and (5) the azole fungicide and the strobilurin are dissolved in the water-immiscible carrier.

[0919] In another preferred embodiment, the suspoemulsion composition comprises: (i) a copper-based fungicide, (ii) a strobilurin, (iii) an azole fungicide, (iv) water, (v) a water-immiscible carrier and (vi) a polyelectrolyte, wherein (1) the copper-based fungicide is Bordeaux mixture, (2) the strobilurin is azoxystrobin, (3) the azole fungicide is tebuconazole, (4) the copper-based fungicide is suspended in water and (5) the azole fungicide and the strobilurin are dissolved in the water-immiscible carrier.

[0920] In another preferred embodiment, the composition comprises: (i) a copper-based fungicide, (ii) a strobilurin, (iii) an azole fungicide, (iv) water and (v) a polyelectrolyte, wherein (1) the copper-based fungicide is copper oxychloride, (2) the strobilurin is picoxystrobin, (3) the azole fungicide is prothioconazole and (4) the copper-based fungicide, the azole fungicide and the strobilurin are suspended in water.

[0921] In another preferred embodiment, the subject matter is directed to a composition comprising: (i) a copper-based fungicide, (ii) a strobilurin, (iii) an azole fungicide and (iv) water, wherein (1) the copper-based fungicide is Bordeaux mixture, (2) the strobilurin is picoxystrobin, (3) the azole fungicide is prothioconazole and (4) the copper-based fungicide, the azole fungicide and the strobilurin are suspended in water.

[0922] In another preferred embodiment, the subject matter relates to a composition comprising: (i) a copper-based fungicide, (ii) a strobilurin, (iii) an azole fungicide, and (iv) water, wherein (1) the copper-based fungicide is copper oxychloride, (2) the strobilurin is picoxystrobin dissolved in a water-immiscible carrier; and (3) the azole fungicide is tebuconazole, and (4) the copper-based fungicide, azole fungicide, and strobilurin are suspended in water.

[0923] In another preferred embodiment, the subject matter is directed to a composition comprising: (i) a copper-based fungicide, (ii) a strobilurin, (iii) an azole fungicide and (iv) water, wherein (1) the copper-based fungicide is Bordeaux mixture, (2) the strobilurin is picoxystrobin, (3) the azole fungicide is tebuconazole and (4) the copper-based fungicide, the azole fungicide and the strobilurin are suspended in water.

[0924] In another preferred embodiment, the subject matter relates to a composition comprising: (i) a copper-based fungicide, (ii) a strobilurin, (iii) an azole fungicide and (iv) water, wherein (1) the copper-based fungicide is copper oxychloride, (2) the strobilurin is azoxystrobin, (3) the azole fungicide is prothioconazole and (4) the copper-based fungicide, the azole fungicide and the strobilurin are suspended in the water.

[0925] In another preferred embodiment, the subject matter relates to a composition comprising: (i) a copper-based fungicide, (ii) a strobilurin, (iii) an azole fungicide and (iv) water, wherein (1) the copper-based fungicide is Bordeaux mixture, (2) the strobilurin is azoxystrobin, (3) the azole fungicide is prothioconazole and (4) the copper-based fungicide, the azole fungicide and the strobilurin are suspended in water.

[0926] In another preferred embodiment, the subject matter relates to a composition comprising: (i) a copper-based fungicide, (ii) a strobilurin, (iii) an azole fungicide, and (iv), wherein (1) the copper-based fungicide is copper oxychloride, (2) the strobilurin is azoxystrobin, (3) the azole fungicide is tebuconazole and (4) the copper-based fungicide, the azole fungicide and the strobilurin are suspended in water.

[0927] In another preferred embodiment, the subject matter relates to a composition comprising: (i) a copper-based fungicide, (ii) a strobilurin, (iii) an azole fungicide and (iv) water, wherein (1) the copper-based fungicide is Bordeaux mixture, (2) the strobilurin is azoxystrobin, (3) the azole fungicide is tebuconazole and (4) the copper-based fungicide, the azole fungicide and the strobilurin are suspended in water.

[0928] In another preferred embodiment, the suspoemulsion composition comprises: (i) a copper-based fungicide, (ii) a SDHI, (iii) an azole fungicide, (iv) a water-immiscible carrier, (v) water, and (vi) a polyelectrolyte, wherein (1) the copper-based fungicide is copper oxychloride, (2) the SDHI is fluopyraclostrobin, (3) the azole fungicide is prothioconazole, (4) the copper-based fungicide is suspended in water, and (5) the azole fungicide and the SDHI are suspended in the water-immiscible carrier.

[0929] In another preferred embodiment, the suspoemulsion composition comprises: (i) a copper-based fungicide, (ii) a SDHI, (iii) an azole fungicide, (iv) a water-immiscible carrier, (v) water and (vi) a polyelectrolyte, wherein (1) the copper-based fungicide is a Bordeaux mixture, (2) the SDHI is fluopyraclostrobin, (3) the azole fungicide is prothioconazole, (4) the copper-based fungicide is suspended in water and (5) the SDHI and the azole fungicide are dissolved in the water-immiscible carrier.

[0930] In another preferred embodiment, the suspension composition comprises: (i) a copper-based fungicide, (ii) a SDHI, (iii) an azole fungicide, (iv) a water-immiscible carrier, (v) water, and (vi) a polyelectrolyte, wherein (1) the copper-based fungicide is copper oxychloride, (2) the SDHI is fluopyraclostrobin, (3) the azole fungicide is tebuconazole, (4) the copper-based fungicide is suspended in water, and (5) the azole fungicide and the SDHI are dissolved in the water-immiscible carrier.

[0931] In another preferred embodiment, the suspoemulsion composition comprises: (i) a copper-based fungicide, (ii) a SDHI, (iii) an azole fungicide, (iv) a water-immiscible carrier, (v) water, and (vi) a polyelectrolyte, wherein (1) the copper-based fungicide is a Bordeaux mixture, (2) the SDHI is fluopyraclostrobin, (3) the azole fungicide is tebuconazole, (4) the copper-based fungicide is suspended in water, and (5) the SDHI and the azole fungicide are dissolved in the water-immiscible carrier.

[0932] In another preferred embodiment, the suspoemulsion composition comprises: (i) a copper-based fungicide, (ii) a SDHI, (iii) an azole fungicide, (iv) a water-immiscible carrier, (v) water, and (vi) a polyelectrolyte, wherein (1) the copper-based fungicide is copper oxychloride, (2) the SDHI is fluopyraclostrobin, (3) the azole fungicide is prothioconazole, (4) the copper-based fungicide is suspended in water, and (5) the azole fungicide and the SDHI are suspended in the water-immiscible carrier.

[0933] In another preferred embodiment, the suspoemulsion composition comprises: (i) a copper-based fungicide, (ii) a SDHI, (iii) an azole fungicide, (iv) a water-immiscible carrier, (v) water and (vi) a polyelectrolyte, wherein (1) the copper-based fungicide is a Bordeaux mixture, (2) the SDHI is fluopyraclostrobin, (3) the azole fungicide is prothioconazole, (4) the copper-based fungicide is suspended in water and (5) the SDHI and the azole fungicide are dissolved in the water-immiscible carrier.

[0934] In another preferred embodiment, the suspension composition comprises: (i) a copper-based fungicide, (ii) a SDHI, (iii) an azole fungicide, (iv) a water-immiscible carrier, (v) water, and (vi) a polyelectrolyte, wherein (1) the copper-based fungicide is copper oxychloride, (2) the SDHI is fluopyraclostrobin, (3) the azole fungicide is tebuconazole, (4) the copper-based fungicide is suspended in water, and (5) the azole fungicide and the SDHI are dissolved in the water-immiscible carrier.

[0935] In another preferred embodiment, the suspoemulsion composition comprises: (i) a copper-based fungicide, (ii) a SDHI, (iii) an azole fungicide, (iv) a water-immiscible carrier, (v) water, and (vi) a polyelectrolyte, wherein (1) the copper-based fungicide is a Bordeaux mixture, (2) the SDHI is fluopyraclostrobin, (3) the azole fungicide is tebuconazole, (4) the copper-based fungicide is suspended in water, and (5) the SDHI and the azole fungicide are dissolved in the water-immiscible carrier.

[0936] In some embodiments, the polyelectrolyte comprises at least one polyanion. In some embodiments, the polyelectrolyte is a polyanion. In some embodiments, the polyelectrolyte comprises a polycation and a polyanion. In some embodiments, the polyelectrolyte is a complex of a polycation and a polyanion.

[0937] In some embodiments, the composition comprises a macromolecular complex comprising a copper-based fungicide and a polyelectrolyte.

[0938] In some embodiments, the polyanion is lignin sulfonate.

[0939] In another preferred embodiment, the subject matter relates to a composition comprising: a) a copper-based fungicide and fluopyram suspended in water.

[0940] In an embodiment, an amount of one or more additional fungicides may be present in a concentration of about 0.1 wt.%-30 wt.% based on the total weight of the composition. In a further embodiment, an amount of one or more additional fungicides may be present in a concentration of about 1%-15% by weight based on the total weight of the composition. In another embodiment, an amount of one or more additional fungicides may be present in a concentration of about 1%-10% by weight based on the total weight of the composition. In yet another embodiment, an amount of one or more additional fungicides may be present in a concentration of about 3%-8% by weight based on the total weight of the composition. In a specific embodiment, an amount of one or more additional fungicides may be present in a concentration of about 5.6% by weight based on the total weight of the composition.

[0941] In some embodiments, the water-immiscible carrier may include, but is not limited to, aromatic hydrocarbons (e.g., toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, isopropylbenzene, tert-butylbenzene, naphthalene, mono- or poly-alkyl-substituted naphthalenes), chain alkanes (e.g., octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane, heneicosane, docosane, tricosane, tetracosane, pentacosane, and branched chain isomers thereof), petroleum, Ketones (e.g., acetophenone, cyclohexanone), vegetable oils (e.g., olive oil, kapok oil, castor oil, papaya oil, camellia oil, palm oil, sesame oil, corn oil, rice bran oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil, linseed oil, tung oil, sunflower oil, safflower oil, tall oil), alkyl esters of vegetable oils (e.g., rapeseed oil methyl ester or rapeseed oil ethyl ester, rapeseed oil propyl ester, rapeseed oil butyl ester, tall oil fatty acid ester, etc.), diesel, mineral oil, fatty acid amides (e.g., C1-C3 amines, alkylamines or amines having C6-C 18 carboxylic acid), alkanolamines, fatty acids, tall oil fatty acids, alkyl esters of fatty acids (e.g., C8 to C 22 C1-C4 monohydric alcohol esters of fatty acids, such as methyl oleate, ethyl oleate), modified vegetable oils and combinations thereof.

[0942] In preferred embodiments, the water-immiscible carrier may include, but is not limited to, aromatic hydrocarbons, fatty acid amides, alkyl esters of vegetable oils, and vegetable oils.

[0943] In an embodiment, the amount of the water-immiscible carrier can be about 0.1wt.%-20wt.%, about 1wt.%-15wt.%, or about 0.1wt.%-10wt.%, or about 1%-5% based on the total weight of the composition. In a specific embodiment, the non-aqueous liquid carrier can be present in a concentration of about 3% by weight based on the total weight of the composition.

[0944] In some embodiments, the adjuvant in the liquid carrier may include, but is not limited to, vegetable oils, alkyl esters of vegetable oils such as soybean methyl ester, soybean ethyl ester, rapeseed oil methyl ester or rapeseed oil ethyl ester, alkoxylated sorbitan esters such as sorbitan monolaurate alkoxylates, such as polyoxyethylene (16) sorbitan monolaurate (Tween TM 24), Polyoxyethylene (20) sorbitan monolaurate (Tween TM 20; PSML-20), polyoxyethylene (4) sorbitan monolaurate (Tween TM 21) Polyoxyethylene (8) sorbitan monolaurate (Tween TM 22), Polyoxyethylene (12) sorbitan monolaurate (Tween TM23) Sorbitan monolaurate ( S / 20, LK, LC, 20), polyoxyethylene (20) sorbitan monostearate alkoxylate such as polyoxyethylene (20) sorbitan monostearate (Tween TM 60), polyoxyethylene (4) sorbitan monostearate (Tween TM 61) Sorbitan monostearate ( S / 90, S. 60), sorbitan monooleate alkoxylates such as polyoxyethylene (20) sorbitan monooleate (Tween TM 80. SMO 20, 80. SMO 20U), polyoxyethylene (5) sorbitan monooleate (Tween TM 81) Sorbitan monooleate ( S / 80, 80), and combinations thereof.

[0945] The compositions according to the present invention provide stable aqueous suspensions comprising high concentrations of up to about 30% (w / w) of copper-based fungicides having enhanced fungicidal activity and / or effective control of plant health compared to commercially available formulations of said copper-based fungicides.

[0946] The compositions according to the present invention provide stable aqueous suspensions comprising high concentrations of copper-based fungicides up to about 50% (w / v) with enhanced fungicidal activity and / or effective control of plant health in the presence of relatively low amounts of adjuvants as agriculturally acceptable carriers compared to commercially available formulations of the copper-based fungicides.

[0947] In some embodiments, the macromolecular complex is prepared by premixing the polyelectrolyte and the copper-based fungicide prior to adding another additive.

[0948] In some embodiments, the amount of copper-based fungicide is more effective than if the same type and amount of copper-based fungicide were formulated in the absence of the polyelectrolyte.

[0949] In some embodiments, the amount of copper-based fungicide is more effective in promoting growth of crop plants in the presence of fungi than if the same type and amount of copper-based fungicide were formulated in the absence of the polyelectrolyte.

[0950] In some embodiments, more effective refers to, but is not limited to, biocontrol, rainwater resistance, adherence to foliage, controlled release, preventive efficacy, and / or increased plant health.

[0951] The present invention also provides a composition comprising (1) a copper-based fungicide, (2) a polyelectrolyte, and (3) at least one agriculturally acceptable additive, wherein the composition has any one or any combination of the following characteristics:

[0952] a. the composition is more fungicidally effective than a copper-based fungicide composition prepared without the presence of a polyelectrolyte,

[0953] b. the composition is more fungicidally effective than a copper-based fungicide composition formulated in the absence of a polyelectrolyte,

[0954] c. the composition has improved leaf adhesion compared to a copper-based fungicide composition formulated in the absence of a polyelectrolyte,

[0955] d. the composition has improved resistance to rainwater washoff compared to a copper-based fungicide composition formulated in the absence of a polyelectrolyte,

[0956] e. the composition has reduced drift compared to a copper-based fungicide composition formulated in the absence of a polyelectrolyte, and

[0957] f. The composition has controlled bioavailability compared to a copper-based fungicide composition formulated in the absence of a polyelectrolyte.

[0958] In some embodiments, controlled bioavailability means that Cu 2+ controlled release rate.

[0959] The present invention provides a composition comprising:

[0960] (i) 28.8% by weight of Bordeaux mixture,

[0961] (ii) 53.8% by weight of water,

[0962] (iii) 0.5% by weight of chitosan,

[0963] (iv) 2.3% by weight of calcium lignin sulfonate,

[0964] (v) 2% by weight of Metasperse 500L,

[0965] (vi) 2% by weight of Atlas G5002L,

[0966] (vii) 0.4% by weight of Silicolapse 426R,

[0967] (viii) 4.2% by weight of propane-1,2-diol,

[0968] (ix) 0.083% by weight MBS, and

[0969] (x) 6% by weight of Rhodopol 23.

[0970] The present invention provides a composition comprising:

[0971] (i) 28.8% by weight of Bordeaux mixture,

[0972] (ii) 55% by weight of water,

[0973] (iii) 0.5% by weight of chitosan,

[0974] (iv) 2.3% by weight of calcium lignin sulfonate,

[0975] (v) 1% by weight of Tensiofix CGA213,

[0976] (vi) 2% by weight of Tensiofix LB350,

[0977] (vii) 0.2% by weight of Tensiofix L051,

[0978] (viii) 4.2% by weight of propane-1,2-diol,

[0979] (ix) 0.083% by weight MBS, and

[0980] (x) 6% by weight of Rhodopol 23.

[0981] The present invention provides a composition comprising:

[0982] (i) 28.8% by weight of Bordeaux mixture,

[0983] (ii) 52.3% by weight of water,

[0984] (iii) 2.3% by weight of calcium lignin sulfonate,

[0985] (iv) 2% by weight of Metasphere 500L,

[0986] (v) 2% by weight of Atlas G5002L,

[0987] (vi) 0.4% by weight of Silicolapse 426R,

[0988] (vii) 4.2% by weight of propane-1,2-diol,

[0989] (viii) 0.083% by weight MBS, and

[0990] (ix) 8% by weight of Rhodopol 23.

[0991] The present invention provides a composition comprising:

[0992] (i) 28.8% by weight of Bordeaux mixture,

[0993] (ii) 53.4% ​​by weight of water,

[0994] (iii) 2.3% by weight of calcium lignin sulfonate,

[0995] (iv) 1% by weight of Tensiofix CGA213,

[0996] (v) 2% by weight of Tensiofix LB350,

[0997] (vi) 0.2% by weight of Tensiofix L051,

[0998] (vii) 4.2% by weight of propane-1,2-diol,

[0999] (viii) 0.083% by weight MBS, and

[1000] (ix) 8% by weight of Rhodopol 23.

[1001] The present invention provides a composition comprising:

[1002] (i) 30.5% by weight of cupric oxychloride,

[1003] (ii) 5% by weight of picoxystrobin (99)

[1004] (iii) 5.8% by weight of prothioconazole (99,3)

[1005] (iv) 35.8% by weight of water,

[1006] (v) 2.6% by weight of sodium citrate

[1007] (vi) 2.8% by weight of calcium lignin sulfonate,

[1008] (vii) 0.3% by weight of chitosan

[1009] (viii) 5% by weight of Tergitol XD,

[1010] (ix) 0.9% by weight of Ecosurf EH6,

[1011] (x) 3.6% by weight of propane-1,2-diol,

[1012] (xi) 0.4% by weight of Silcolapse 426R, and

[1013] (xii) 7.5% by weight of Rhodopol 23.

[1014] The present invention provides a composition comprising:

[1015] (i) 31.7% by weight of Bordeaux blend

[1016] (ii) 2.6% by weight of picoxystrobin (99)

[1017] (iii) 3.0% by weight of prothioconazole (99,3)

[1018] (iv) 41.2% by weight of water,

[1019] (v) 1.5% by weight of sodium citrate

[1020] (vi) 1.0% by weight of calcium lignin sulfonate,

[1021] (vii) 0.2% by weight of chitosan

[1022] (viii) 7.4% by weight of soprophor FL,

[1023] (ix) 1.5% by weight of atlas G5002L,

[1024] (x) 3.7% by weight of propane-1,2-diol,

[1025] (xi) 0.7% by weight of Silcolapse 426R,

[1026] (xii) 0.1% by weight of acticide MBS, and

[1027] (xiii) 6.3% by weight of Rhodopol 23.

[1028] The present invention provides a composition comprising:

[1029] (i) 31.7% by weight of Bordeaux blend,

[1030] (ii) 2.6% by weight of picoxystrobin (99),

[1031] (iii) 3.0% by weight of prothioconazole (99,3),

[1032] (iv) 38.8% by weight of water,

[1033] (v) 1.5% by weight of dipotassium hydrogen phosphate,

[1034] (vi) 2.1% by weight of calcium lignin sulfonate,

[1035] (vii) 0.4% by weight of chitosan,

[1036] (viii) 0.2% by weight of acetic acid,

[1037] (ix) 7.4% by weight of soprophor FL,

[1038] (x) 1.5% by weight of atlas G5002L,

[1039] (xi) 3.7% by weight of propane-1,2-diol,

[1040] (xii) 0.7% by weight of Silcolapse 426R,

[1041] (xiii) 0.1% by weight of acticide MBS, and

[1042] (xiv) 6.3% by weight of Rhodopol 23.

[1043] The present invention provides a composition comprising:

[1044] (i) 31.7% by weight of Bordeaux blend,

[1045] (ii) 2.6% by weight of picoxystrobin (99),

[1046] (iii) 3.0% by weight of prothioconazole (99,3),

[1047] (iv) 41.9% by weight of water,

[1048] (v) 1.5% by weight of sodium citrate,

[1049] (vi) 2% by weight of calcium lignin sulfonate,

[1050] (vii) 0.5% by weight of chitosan,

[1051] (viii) 7.4% by weight of soprophor FL,

[1052] (ix) 1.5% by weight of atlas G5002L,

[1053] (x) 3.7% by weight of propane-1,2-diol,

[1054] (xi) 0.7% by weight of Silcolapse 426R,

[1055] (xii) 0.1% by weight of acticide MBS, and

[1056] (xiii) 3.4% by weight of Rhodopol 23.

[1057] The present invention provides a composition comprising:

[1058] (i) 35.5% by weight of cupric oxychloride,

[1059] (ii) 5.6% by weight of fluopyram,

[1060] (iii) 36.9% by weight of water,

[1061] (iv) 3.6% by weight of calcium lignin sulfonate,

[1062] (v) 0.4% by weight of chitosan,

[1063] (vi) 2.5% by weight of soprophor 3D33,

[1064] (vii) 1.0% by weight of ecosurf EH6,

[1065] (viii) 4.2% by weight of propane-1,2-diol,

[1066] (ix) 0.4% by weight of Silcolapse 426R, and

[1067] (x) 10% by weight of Rhodopol 23.

[1068] The present invention provides a composition comprising:

[1069] (i) 35.5% by weight of cupric oxychloride,

[1070] (ii) 5.6% by weight of fluopyram,

[1071] (iii) 41.5% by weight of water,

[1072] (iv) 3.6% by weight of calcium lignin sulfonate,

[1073] (v) 0.7% by weight PAA

[1074] (vi) 2.5% by weight of atlox 4913,

[1075] (vii) 1.0% by weight of ADSEE 900,

[1076] (viii) 4.2% by weight of propane-1,2-diol,

[1077] (ix) 0.4% by weight of Silcolapse 426R, and

[1078] (x) 5% by weight of Rhodopol 23.

[1079] The present invention provides a composition comprising:

[1080] (i) 35.5% by weight of cupric oxychloride,

[1081] (ii) 5.6% by weight of fluopyram,

[1082] (iii) 39.4% by weight of water,

[1083] (iv) 3.3% by weight of calcium lignin sulfonate,

[1084] (v) 0.7% by weight chitosan

[1085] (vi) 2.5% by weight of atlox 4913,

[1086] (vii) 1.0% by weight of ADSEE 900,

[1087] (viii) 4.2% by weight of propane-1,2-diol,

[1088] (ix) 0.4% by weight of Silcolapse 426R, and

[1089] (x) 7.5% by weight of Rhodopol 23.

[1090] The present invention provides a composition comprising:

[1091] (i) 34.29% by weight of Bordeaux blend,

[1092] (ii) 2.78% by weight of picoxystrobin,

[1093] (iii) 5.0% by weight of propane-1,2-diol,

[1094] (iv) 1.0% by weight of Metasperse 550S,

[1095] (v) 2.8% by weight of Borresperse CA

[1096] (vi) 2% by weight T-77,

[1097] (vii) 2.0% by weight of Atlox 4894

[1098] (viii) 0.1% by weight of SAG 1572,

[1099] (ix) 0.05% by weight of Proxel GXL,

[1100] (x) 36.86% by weight of DM water,

[1101] (xi) 3.06% by weight of prothioconazole, and

[1102] (xii) 3.06% by weight of Armid DM 10.

[1103] The present invention provides a composition comprising:

[1104] (i) 34.29% by weight of Bordeaux blend,

[1105] (ii) 2.78% by weight of picoxystrobin,

[1106] (iii) 5.0% by weight of propane-1,2-diol,

[1107] (iv) 1.0% by weight of Metasperse 550S,

[1108] (v) 2.8% by weight of Borresperse CA

[1109] (vi) 2% by weight T-77,

[1110] (vii) 2.0% by weight of Atlox 4894

[1111] (viii) 0.1% by weight of SAG 1572,

[1112] (ix) 0.05% by weight of Proxel GXL,

[1113] (x) 36.86% by weight of DM water,

[1114] (xi) 3.06% by weight of prothioconazole, and

[1115] (xii) 3.06% by weight of Armid DM 10.

[1116] The present invention provides a composition comprising:

[1117] (i) 30% by weight of Bordeaux mixture,

[1118] (ii) 2.5% by weight of picoxystrobin,

[1119] (iii) 5.0% by weight of propane-1,2-diol,

[1120] (iv) 1.0% by weight of Metasperse 550S,

[1121] (v) 2.8% by weight of Borresperse CA

[1122] (vi) 2% by weight T-77,

[1123] (vii) 2.0% by weight of Atlox 4894

[1124] (viii) 0.1% by weight of SAG 1572,

[1125] (ix) 0.05% by weight of Proxel GXL,

[1126] (x) 36.86% by weight of DM water,

[1127] (xi) 3.06% by weight of prothioconazole, and

[1128] (xii) 3.06% by weight of Armid DM 10.

[1129] The present invention provides a composition comprising:

[1130] (i) about 22.89% by weight of cupric oxychloride,

[1131] (ii) about 3.67% by weight of picoxystrobin,

[1132] (iii) about 4.1% by weight of prothioconazole,

[1133] (iv) about 35.63% by weight of water,

[1134] (v) about 1.87% by weight of calcium lignin sulfonate,

[1135] (vi) about 0.2% by weight of chitosan,

[1136] (vii) about 0.45% by weight of acetic acid,

[1137] (viii) about 13.22% by weight of acetophenone,

[1138] (ix) about 1% by weight of Agnique BP 420,

[1139] (x) about 2.64% by weight of Agsolex 8,

[1140] (xi) about 5% by weight of POLYAGRO A,

[1141] (xii) about 3% by weight of propylene glycol,

[1142] (xiii) about 0.02% by weight of Proxel GXL,

[1143] (xiv) about 0.2% by weight of SAG 1572,

[1144] (xv) about 2.54% by weight of sodium acetate,

[1145] (xvi) about 2.02% by weight of Soprophor TS / 16,

[1146] (xvii) about 0.66% by weight of Synergen SOC,

[1147] (xviii) about 0.35% by weight of thiourea,

[1148] (xix) about 0.3% by weight of Van Gel B, and

[1149] (xx) about 0.2% by weight of AG-RH 23

[1150] The present invention provides a composition comprising (1) a macromolecular complex comprising (i) a copper-based fungicide and (ii) a polyelectrolyte, (2) at least one agriculturally acceptable additive and optionally (3) at least one additional fungicide.

[1151] The present invention also provides a composition comprising (1) a copper-based fungicide, (2) a polyelectrolyte, (3) at least one agriculturally acceptable additive, and optionally (4) at least one additional fungicide.

[1152] The present invention also provides an aqueous composition comprising (1) a copper-based fungicide, (2) a polyelectrolyte, (3) water, and (4) at least one agriculturally acceptable additive.

[1153] The present invention provides a composition comprising (1) a macromolecular complex comprising (i) a copper-based fungicide and (ii) a polyanion, optionally (2) at least one additional fungicide and (3) at least one agriculturally acceptable additive.

[1154] The present invention provides a macromolecular complex comprising (i) a copper-based fungicide and (ii) a polyanion.

[1155] Delivery System

[1156] The present invention also provides a pesticide delivery system comprising any of the combinations, compositions or macromolecular complexes described herein.

[1157] How to use

[1158] The present invention provides a method for controlling pathogen infection comprising applying a composition comprising (1) an amount of a copper-based fungicide, (2) an amount of a polyelectrolyte, and (3) at least one agriculturally acceptable additive, wherein the application rate of the copper-based fungicide when formulated with the polyelectrolyte is less than when the same type of copper-based fungicide is formulated in the absence of the polyelectrolyte.

[1159] In some embodiments, the amount of copper-based fungicide is more effective than if the same type and amount of copper-based fungicide were formulated in the absence of the polyelectrolyte.

[1160] The present invention provides a method for improving the efficacy of a copper-based fungicide, comprising interacting the copper-based fungicide with a polyelectrolyte through intermolecular non-covalent interactions prior to applying the copper-based fungicide.

[1161] In some embodiments, enhanced efficacy includes, but is not limited to, biocontrol, rainwater resistance, adhesion to leaves, controlled release, preventive efficacy.

[1162] In some embodiments, the amount of copper-based fungicide is more effective in promoting growth of crop plants in the presence of fungi than if the same type and amount of copper-based fungicide were formulated in the absence of the polyelectrolyte.

[1163] The present invention also provides the use of the combinations, macromolecular complexes, compositions, and / or delivery systems described herein for treating a plant, or a part of a plant, against a pathogen.

[1164] The present invention also provides the use of the combinations, macromolecular complexes, compositions, and / or delivery systems described herein to reduce the application rate required for treating a plant, or a part of a plant, against a pathogen.

[1165] The method or use of the composition, combination, delivery system and / or macromolecular complex comprising a copper-based fungicide and a polyelectrolyte may result in a reduced application rate of the copper-based fungicide.

[1166] The terms "reduced application rate" and "increased biological activity" may refer to an application rate that is reduced by more than 20%, preferably more than 50%, when compared to the application rate of the same copper-based fungicide as a free copper-based fungicide.

[1167] The present invention provides a method for treating a plant, or a part of a plant, against pathogens, comprising contacting the plant, or a part of a plant, with any one or any combination of the macromolecular complexes described herein, and / or any one or any combination of the compositions described herein.

[1168] In some embodiments, treating includes preventing, reducing and / or eliminating the presence of a pathogen on a plant or a portion of a plant. In some embodiments, treating includes controlling a disease caused by a pathogen.

[1169] The present invention provides a method of increasing crop yield, comprising contacting a plant, or a part of a plant, with any of the combinations, compositions, macromolecular complexes and / or delivery systems described herein.

[1170] The present invention also provides a method for increasing plant vigor, comprising contacting the plant, or a part of the plant, with any of the combinations, compositions, macromolecular complexes and / or delivery systems described herein.

[1171] In some embodiments, a method of treating a plant, or a part of a plant, against a pathogen comprises protecting a plant, or a part of a plant, against a pathogen comprising contacting the plant, or a part of a plant, with any of the combinations, compositions, macromolecular complexes, and / or delivery systems described herein.

[1172] In some embodiments, methods of treating a plant, or a portion of a plant, against pathogens include preventing, reducing and / or eliminating the presence of the pathogen on a plant, or a portion of a plant, comprising contacting the plant, or a portion of a plant, with any of the combinations, compositions, macromolecular complexes, and / or delivery systems described herein.

[1173] In some embodiments, a method of treating a plant, or a portion of a plant, against pathogens comprises controlling diseases caused by phytopathogenic fungi in the plant or on its propagation material, the method comprising contacting the plant, or its propagation material, with any of the combinations, compositions, macromolecular complexes, and / or delivery systems described herein.

[1174] In some embodiments, a method of treating a plant, or a portion of a plant, against a pathogen comprises improving pest control comprising applying any of the combinations, compositions, macromolecular complexes, and / or delivery systems described herein to the plant and / or soil.

[1175] In some embodiments, a method of treating a plant, or a portion of a plant, against a pathogen comprises extending the control effect of a copper-based fungicide, comprising applying any of the combinations, compositions, macromolecular complexes, and / or delivery systems described herein to the plant and / or soil.

[1176] In some embodiments, the pathogen is a phytopathogenic fungus, and the method comprises controlling a disease caused by a phytopathogenic fungus in a plant or on its propagation material, comprising contacting the plant, or its propagation material, with any of the combinations, compositions, macromolecular complexes, and / or delivery systems described herein.

[1177] The present invention further provides a method for protecting plants or plant parts against pathogens, which comprises contacting said plants or said plant parts with a diluted aqueous composition according to the present invention.

[1178] The present invention further provides a method for preventing, reducing and / or eliminating the presence of pathogens on a plant or a part of a plant, comprising contacting the plant, or the part of the plant, with an aqueous composition according to the present invention.

[1179] In some embodiments, the method of treating a plant, or a part of a plant, against a pathogen comprises preventing, reducing and / or eliminating the presence of the pathogen on the plant, or a part of a plant, comprising contacting the plant, or a part of a plant, with any of the combinations, compositions, macromolecular complexes, and / or delivery systems described herein.

[1180] The present invention further provides a method of controlling diseases caused by phytopathogenic fungi in plants or on their propagation material, which method comprises contacting these plants or their propagation material with a composition (including aqueous dilution compositions) according to the invention.

[1181] The present invention also provides a method for controlling pests, which comprises contacting (i) pests or their sites, (ii) plants or their sites or propagation materials, (iii) soil, and / or (iv) areas to be protected from pest infection with the macromolecular complex of the present invention. The macromolecular complex of the present invention is preferably provided as a composition according to the present invention, and / or a delivery system according to the present invention.

[1182] The present invention also provides a method for improved pest control comprising applying any of the compositions, complexes or delivery systems described herein to plants and / or soil.

[1183] The present invention also provides a method for prolonging the controlling effect of a copper-based fungicide, comprising applying any of the compositions, complexes or delivery systems described herein to plants and / or soil.

[1184] The present invention provides a method for controlling the release rate of copper cations from a copper-based fungicide, which comprises interacting the copper-based fungicide with a polyelectrolyte through intermolecular non-covalent interactions prior to applying the copper-based fungicide.

[1185] In some embodiments, the combination of the polyelectrolyte and the copper-based fungicide is prior to the addition of the co-formulator.

[1186] The application rate may refer to an application rate of 22 g ai / ha (copper-based fungicide (ai) / ha) to 2.2 g ai. / ha, 0.22 g ai / ha, 0.022 g ai / ha, 0.0022 g ai / ha, 750 g ai / ha, 450 g ai / ha, 375, 150 g ai / ha, 15 g ai / ha, 2.9 gr ai / lit, 11.6 gr ai / lit, preferably 0.0022 g ai / ha to 0.75 kg ai / ha. The application rate may refer to an application rate of 22 g ai / ha to 2.2 g ai / ha of a copper-based fungicide. In some embodiments, a copper-based fungicide is applied at an application rate of 750 g ai / ha, 605 mg ai / ha, or 500 mg ai / ha.

[1187] In some embodiments, the combination, composition, and / or delivery system is applied in an amount of 0.01-5 g / ha of a copper-based fungicide. In some embodiments, the combination, composition, and / or delivery system is applied in an amount of 0.01-3 g / ha of a copper-based fungicide. In some embodiments, the combination, composition, and / or delivery system is applied in an amount of 0.01-2 g / ha of a copper-based fungicide. In some embodiments, the combination, composition, and / or delivery system is applied in an amount of 0.01-1 g / ha of a copper-based fungicide.

[1188] In some embodiments, the combination, composition, and / or delivery system is applied in an amount of 0.018 g / ha of a copper-based fungicide. In some embodiments, the combination, composition, and / or delivery system is applied in an amount of 0.97 g / ha of a copper-based fungicide. In some embodiments, the combination, composition, and / or delivery system is applied in an amount of 0.39 g / ha of a copper-based fungicide. In some embodiments, the combination, composition, and / or delivery system is applied in an amount of 1.56 g / ha of a copper-based fungicide.

[1189] In some embodiments, the combination, composition, and / or delivery system is applied in an amount of copper metal between 0.001 g / ha and 1000 g / ha. In some embodiments, the combination, composition, and / or delivery system is applied in an amount of copper metal between 100 g / ha and 1000 g / ha. In some embodiments, the combination, composition, and / or delivery system is applied in an amount of copper metal between 100 g / ha and 500 g / ha. In some embodiments, the combination, composition, and / or delivery system is applied in an amount of copper metal between 500 g / ha and 1000 g / ha. In some embodiments, the combination, composition, and / or delivery system is applied in an amount of copper metal between 0.001 g / ha and 100 g / ha. In some embodiments, the combination, composition, and / or delivery system is applied in an amount of copper metal between 0.001 g / ha and 50 g / ha. In some embodiments, the combination, composition, and / or delivery system is applied in an amount of between 0.001 g / ha to 25 g / ha of copper metal. In some embodiments, the combination, composition, and / or delivery system is applied in an amount of between 0.001 g / ha to 10 g / ha of copper metal.

[1190] In some embodiments, the combination, composition, and / or delivery system is applied in an amount of about 0.0022 g / ha, 0.022 g / ha, 0.22 g / ha, 2.2 g / ha, or 22 g / ha of copper metal.

[1191] In some embodiments, the combination, composition, and / or delivery system is applied in an amount of about 0.0075 g / ha, 0.075 g / ha, 0.75 g / ha, 7.5 g / ha, or 75 g / ha of copper metal.

[1192] In some embodiments, the combination, composition, and / or delivery system is applied in an amount of about 0.0052 g / ha of copper metal. In some embodiments, the combination, composition, and / or delivery system is applied in an amount of about 0.001 g / ha of copper metal. In some embodiments, the combination, composition, and / or delivery system is applied in an amount of about 0.059 g / ha of copper metal. In some embodiments, the combination, composition, and / or delivery system is applied in an amount of about 0.0095 g / ha of copper metal.

[1193] In some embodiments, the combination, composition, and / or delivery system is applied in an amount of about 15 g / ha of copper metal. In some embodiments, the combination, composition, and / or delivery system is applied in an amount of about 150 g / ha of copper metal. In some embodiments, the combination, composition, and / or delivery system is applied in an amount of about 375 g / ha of copper metal. In some embodiments, the combination, composition, and / or delivery system is applied in an amount of about 450 g / ha of copper metal. In some embodiments, the combination, composition, and / or delivery system is applied in an amount of about 750 g / ha of copper metal.

[1194] The compositions, combinations, macromolecular complexes and / or delivery systems according to the present invention are suitable for controlling harmful organisms encountered in horticulture, agriculture and forestry. These macromolecular complexes are active against common sensitive and resistant harmful organisms and during all or a single developmental stage. Before use, the composition comprising the macromolecular complex according to the present invention is preferably dissolved or dispersed in water, or diluted with water, to provide an aqueous composition containing between 0.001 and 10 w / v% of a copper-based fungicide. If necessary, an agriculturally acceptable carrier such as a sticker is added to the diluted aqueous composition.

[1195] The composition according to the invention is preferably diluted 2-5000 times, preferably about 200 times, with an aqueous solvent, preferably water, to contain between 0.0001 and 10% (w / v) of the copper-based fungicide before contacting the plant, plant part or soil with the composition.

[1196] For the control of agricultural pests, the present invention provides the use of a composition comprising a macromolecular complex according to the present invention for protecting a plant or a part of a plant against pathogens. To achieve this effect, the plant or plant part, or soil is contacted with the composition (including a diluted aqueous composition).

[1197] The compositions are used, for example, to control powdery mildew and downy mildew infections on food / feed crops, including tree fruits, vegetable crops, field crops, grapes, ornamental plants, and turf farms. For example, further uses are to control scab, including common scab, apple scab and scab on potatoes, pear scab, and powdery scab, brown rot of peach, currant and gooseberry leaf spot, peanut leaf spot, and mildew on roses. Other uses include protecting greenhouse-grown flowers and ornamental plants, home gardens, and residential lawns. In addition, the compositions (including diluted aqueous compositions) can be contacted with isolated fruits, nuts, vegetables, and / or flowers.

[1198] For the purposes and the method, preferably the composition (including the aqueous composition of dilution) is sprayed on the plant or its part. The spray application using the known automatic system reduces labor costs and is cost-effective. Methods and equipment well known to those skilled in the art can be used for this purpose. When the risk of infection is high, the composition (including the aqueous composition of dilution) can be sprayed regularly. When the risk of infection is lower, the spray interval time can be longer.

[1199] Other methods suitable for contacting plants or parts thereof with the compositions of the invention are also part of the invention. These include, but are not limited to, dipping, watering, soaking, introducing into a dump tank, evaporating, pulverizing, atomizing, fumigating, painting, brushing, spraying, dusting, foaming, smearing, packaging and coating (e.g., by wax or static electricity). In addition, the compositions (including diluted aqueous compositions) may be injected into the soil.

[1200] For example, plants or parts thereof can be coated with a diluted aqueous composition comprising a copper-based fungicide according to the invention by immersing the plants or parts thereof in the diluted aqueous composition to protect the plants or parts thereof against pathogens and / or to prevent, reduce and / or eliminate the presence of pathogens on the plants or parts thereof. Preferred plant parts coated with the composition according to the invention or a dilution thereof are seeds. Another preferred plant part coated with the composition according to the invention or a dilution thereof is a leaf. Another preferred plant part coated with the composition according to the invention or a dilution thereof is a fruit, preferably a post-harvest fruit, such as, for example, citrus fruits (such as oranges, mandarins and limes), pome fruits (such as apples and pears), stone fruits (such as almonds, apricots, cherries, plums, nectarines, tomatoes, watermelons), tropical fruits (such as bananas, mangoes, lychees and tangerines). Preferred fruits are citrus fruits such as oranges and / or tropical fruits such as bananas.

[1201] The present invention provides a method for (i) increasing the biological activity of a copper-based fungicide on a target, (ii) increasing the persistence of a copper-based fungicide in a target, (iii) increasing the retention of a copper-based fungicide by a target, (iv) increasing the absorption rate of a copper-based fungicide by a target, and / or (v) increasing or enhancing the bioavailability of a copper-based fungicide to a target, wherein the method comprises interacting the copper-based fungicide with a polyelectrolyte prior to applying the copper-based fungicide to a plant, plant part, and / or soil.

[1202] In some embodiments, the method comprises interacting the copper-based fungicide with the polyelectrolyte via complexing by non-covalent electrostatic interactions prior to applying the copper-based fungicide to the plant, plant part, and / or soil.

[1203] In some embodiments, the method comprises interacting the copper-based fungicide with a polyelectrolyte to form a macromolecular complex prior to applying the copper-based fungicide to the plant, plant part, and / or soil.

[1204] In some embodiments, the method comprises partially or completely complexing, trapping, or encapsulating the copper-based fungicide within a polyelectrolyte prior to applying the copper-based fungicide to the plant, plant part, and / or soil. In some embodiments, the method comprises partially or completely trapping the copper-based fungicide within a polyelectrolyte prior to applying the copper-based fungicide to the plant, plant part, and / or soil.

[1205] The present invention provides uses of the macromolecular complexes, compositions or delivery systems of the present invention for (i) increasing the biological activity of a copper-based fungicide on a target, (ii) increasing the absorption of a copper-based fungicide in a target, (iii) increasing the retention of a copper-based fungicide by a target, (iv) increasing the absorption rate of a copper-based fungicide by a target, and / or (v) increasing or enhancing the bioavailability of a copper-based fungicide to a target.

[1206] In some embodiments, the bioavailability of a copper-based fungicide is increased or enhanced by controlling the release rate of copper ions from the copper-based fungicide.

[1207] In some embodiments, the target is a plant. In some embodiments, the target is a plant part. In some embodiments, the target is a fungus.

[1208] The present invention provides a method for (i) reducing copper-based fungicide biodrift, (ii) increasing foliar adhesion of copper-based fungicides, (iii) increasing rainfastness of copper-based fungicides, (iv) increasing persistence of copper-based fungicides, and / or (v) reducing phytotoxicity of copper-based fungicides, wherein the method comprises interacting the copper-based fungicide with a polyelectrolyte prior to applying the copper-based fungicide.

[1209] In some embodiments, the method comprises interacting the copper-based fungicide with the polyelectrolyte via complexing via non-covalent electrostatic interactions.

[1210] In some embodiments, the method includes interacting a copper-based fungicide with a polyelectrolyte to form a macromolecular complex.

[1211] The present invention provides uses of the macromolecular complexes, compositions, or delivery systems of the present invention for (i) reducing drift of copper-based fungicides, (ii) increasing leaf adhesion of copper-based fungicides, (iii) increasing rainfastness of copper-based fungicides, and / or (iv) increasing persistence of copper-based fungicides.

[1212] The present invention also provides a method for reducing the phytotoxicity of a copper-based fungicide to a plant, comprising interacting the copper-based fungicide with a polyelectrolyte through complexing by intermolecular electrostatic interactions prior to applying the copper-based fungicide to the plant, a part of the plant and / or the soil.

[1213] Aspects of the present invention provide the use of a macromolecular complex, composition, and / or delivery system according to the present invention comprising a copper-based fungicide and a polyelectrolyte for increasing the biological activity of the copper-based fungicide.

[1214] Aspects of the present invention provide the use of polyelectrolytes for increasing the biological activity of copper-based fungicides.

[1215] Aspects of the present invention provide the use of a polyelectrolyte for reducing the application rate of a copper-based fungicide.

[1216] Aspects of the present invention provide the use of a polyelectrolyte for controlling the bioavailability of a copper-based fungicide by controlling the release characteristics of copper ions from the copper-based fungicide.

[1217] The present invention also provides a method for reducing the phytotoxicity of a copper-based fungicide, comprising interacting the fungicide with a polyelectrolyte through complexation of intermolecular electrostatic interactions prior to applying the fungicide to a plant, a part of a plant and / or soil.

[1218] The present invention also provides a method for reducing the phytotoxicity of a copper-based fungicide comprising formulating the copper-based fungicide with a polyelectrolyte.

[1219] The present invention also provides a method for increasing the biological activity of a copper-based fungicide against fungi, comprising interacting the copper-based fungicide with a polyelectrolyte through complexing by intermolecular electrostatic interactions prior to applying the copper-based fungicide to a plant, a part of a plant and / or soil.

[1220] The present invention also provides a method for increasing the fungicidal activity of a copper-based fungicide against fungi, comprising interacting the copper-based fungicide with a polyelectrolyte through complexing by intermolecular electrostatic interactions prior to applying the copper-based fungicide to a plant, a part of a plant and / or soil.

[1221] The present invention also provides a method for increasing the absorption of a copper-based fungicide by a target, comprising interacting the copper-based fungicide with a polyelectrolyte through complexing by intermolecular electrostatic interactions prior to applying the copper-based fungicide to a plant, a part of a plant and / or soil.

[1222] The present invention also provides a method for increasing the absorption of a copper-based fungicide by a target, comprising interacting the copper-based fungicide with a polyelectrolyte through complexing by intermolecular electrostatic interactions prior to applying the copper-based fungicide to a plant, a part of a plant and / or soil.

[1223] The present invention also provides a method for reducing drift of a copper-based fungicide, comprising interacting the copper-based fungicide with a polyelectrolyte to form a macromolecular complex, preferably by partially or completely complexing or entrapping the copper-based fungicide within the polyelectrolyte, prior to applying the copper-based fungicide to plants, plant parts, and / or soil.

[1224] The present invention also provides a method for increasing foliar adhesion of a copper-based fungicide, comprising interacting a copper-based fungicide with a polyelectrolyte to form a macromolecular complex, preferably by partially or completely complexing or entrapping the copper-based fungicide within the polyelectrolyte, prior to applying the copper-based fungicide to a plant, plant part, and / or soil.

[1225] The present invention also provides a method for increasing the rainfastness of a copper-based fungicide, comprising interacting the copper-based fungicide with a polyelectrolyte to form a macromolecular complex, preferably by partially or completely complexing or entrapping the copper-based fungicide within the polyelectrolyte, prior to applying the copper-based fungicide to plants, plant parts, and / or soil.

[1226] The present invention also provides a method for increasing the persistence of a copper-based fungicide, comprising interacting the copper-based fungicide with a polyelectrolyte to form a macromolecular complex, preferably by partially or completely complexing or entrapping the copper-based fungicide within the polyelectrolyte, prior to applying the copper-based fungicide to plants, plant parts, and / or soil.

[1227] In some embodiments, the target is a plant. In some embodiments, the target is a pest. In some embodiments, the pest is a fungus.

[1228] The present invention also provides a method for increasing the bioavailability of a copper-based fungicide, comprising interacting a copper-based fungicide with a polyelectrolyte by complexing the copper-based fungicide with the polyelectrolyte or encapsulating the copper-based fungicide within the polyelectrolyte prior to applying the copper-based fungicide to a plant, a part of a plant and / or soil.

[1229] The present invention also provides a method for increasing the biological activity of a copper-based fungicide against harmful organisms, which comprises interacting the copper-based fungicide with a polyelectrolyte through complexing of intermolecular electrostatic interactions before applying the copper-based fungicide to a plant, a part of a plant and / or soil.

[1230] The term "increasing biological activity" refers to curative, knockout, preventive and / or durable properties.

[1231] The present invention also provides a method for increasing the absorption of a copper-based fungicide by a target, comprising interacting the copper-based fungicide with a polyelectrolyte through complexing by intermolecular electrostatic interactions prior to applying the copper-based fungicide to a plant, a part of a plant and / or soil.

[1232] In some embodiments, the target is a plant. In some embodiments, the target is a pest. In some embodiments, the pest is a fungus.

[1233] The present invention also provides a method for increasing the absorption rate of a copper-based fungicide by plant tissue, which comprises interacting the copper-based fungicide with a polyelectrolyte through complexing by intermolecular electrostatic interactions before applying the copper-based fungicide to a plant, a part of a plant and / or soil.

[1234] The present invention also provides a method for increasing the biological activity of a copper-based fungicide against harmful organisms, which comprises interacting the copper-based fungicide with a polyelectrolyte through complexing of intermolecular electrostatic interactions before applying the copper-based fungicide to a plant, a part of a plant and / or soil.

[1235] The present invention also provides a method for increasing plant absorption of a copper-based fungicide, comprising interacting the copper-based fungicide with a polyelectrolyte through complexing by intermolecular electrostatic interactions prior to applying the copper-based fungicide to a plant, a part of a plant and / or soil.

[1236] The present invention also provides a method for increasing the bioavailability of a copper-based fungicide, comprising interacting the copper-based fungicide with a polyelectrolyte by complexing or trapping or encapsulating molecules of the copper-based fungicide with molecules of the polyelectrolyte prior to applying the copper-based fungicide to a plant, a part of a plant and / or soil.

[1237] The present invention also provides a method for increasing the biological activity of a copper-based fungicide on plants, comprising interacting the copper-based fungicide with a polyelectrolyte through non-covalent electrostatic interactions prior to applying the copper-based fungicide to the plant, a part of the plant and / or the soil.

[1238] The present invention also provides a method of increasing plant uptake of a copper-based fungicide, increasing plant retention of a copper-based fungicide, and / or increasing the bioavailability of a copper-based fungicide to a plant, comprising interacting the copper-based fungicide with a polyelectrolyte via complexing via non-covalent electrostatic interactions prior to applying the copper-based fungicide to a plant, a plant portion, and / or soil.

[1239] The present invention also provides a method for increasing the biological activity of a copper-based fungicide on plants, comprising interacting the copper-based fungicide with a polyelectrolyte through complexation via electrostatic intermolecular interactions prior to applying the copper-based fungicide to plants and / or soil.

[1240] The present invention also provides a method of increasing plant uptake of a copper-based fungicide, increasing plant retention of a copper-based fungicide, and / or increasing the bioavailability of a copper-based fungicide to a plant, comprising interacting the copper-based fungicide with a polyelectrolyte via complexing via electrostatic intermolecular interactions prior to applying the copper-based fungicide to a plant, a plant part, and / or soil.

[1241] The method preferably comprises allowing the copper-based fungicide to interact with the polyelectrolyte via non-covalent electrostatic interactions prior to application.

[1242] The invention provides the use of a complex according to the invention for reducing the application rate of copper-based fungicides.

[1243] The present invention provides the use of the macromolecular complex according to the invention for reducing the application rate of copper-based fungicides

[1244] The present invention provides the use of a complex according to the invention for increasing the biological activity of a copper-based fungicide.

[1245] The present invention provides the use of the macromolecular complex according to the invention for increasing the biological activity of a copper-based fungicide.

[1246] The present invention also provides a method for increasing the bioavailability of a copper-based fungicide, comprising interacting the copper-based fungicide with a polyelectrolyte by fully or partially complexing, entrapping or encapsulating molecules of the copper-based fungicide within molecules of the polyelectrolyte prior to applying the copper-based fungicide to a plant, a part of a plant and / or soil.

[1247] The present invention provides the use of a complex according to the invention for enhancing the biological activity of a copper-based fungicide.

[1248] The present invention provides the use of the macromolecular complex according to the invention for enhancing the biological activity of copper-based fungicides.

[1249] The present invention also provides a method for enhancing the bioavailability of a copper-based fungicide, comprising interacting the copper-based fungicide with a polyelectrolyte by fully or partially complexing, entrapping or encapsulating molecules of the copper-based fungicide within molecules of the polyelectrolyte prior to applying the copper-based fungicide to a plant, a part of a plant and / or soil.

[1250] The present invention provides the use of the macromolecular complex according to the invention for prolonging the fungicidal effect of a copper-based fungicide.

[1251] At least one polyelectrolyte is used for formulating an aqueous suspension concentrate comprising a copper-based fungicide.

[1252] At least one dispersant and a macromolecular complex are used for formulating an aqueous suspension concentrate containing a copper-based fungicide.

[1253] At least one dispersant and a macromolecular complex are used for formulating an aqueous suspension concentrate containing a copper-based fungicide.

[1254] In some embodiments, the molecules of the copper-based fungicide are fully complexed with the molecules of the polyelectrolyte by electrostatic interactions prior to application. In some embodiments, the molecules of the copper-based fungicide are fully complexed with the molecules of the polyanion by electrostatic interactions prior to application. In some embodiments, the molecules of the copper-based fungicide are partially complexed with the molecules of the polyelectrolyte prior to application. In some embodiments, the molecules of the copper-based fungicide are partially complexed with the molecules of the polyanion prior to application.

[1255] In some embodiments, prior to application, the molecules of the copper-based fungicide are completely trapped within the polyelectrolyte to form a macromolecular complex. In some embodiments, prior to application, the molecules of the copper-based fungicide are completely trapped within the polyanion to form a macromolecular complex. In some embodiments, prior to application, the molecules that are the biologically active ingredients of the copper-based fungicide are partially trapped within the polyanion to form a macromolecular complex. In some embodiments, prior to application, the molecules that are the biologically active ingredients of the copper-based fungicide are partially trapped within the polyelectrolyte to form a macromolecular complex.

[1256] In some embodiments, prior to application, the molecules of the copper-based fungicide are completely trapped within the polyelectrolyte to form a macromolecular complex. In some embodiments, prior to application, the molecules of the copper-based fungicide are completely trapped within the polyanion to form a macromolecular complex. In some embodiments, prior to application, the molecules that are the biologically active ingredients of the copper-based fungicide are partially trapped within the polyanion to form a macromolecular complex. In some embodiments, prior to application, the molecules that are the biologically active ingredients of the copper-based fungicide are partially trapped within the polyelectrolyte to form a macromolecular complex.

[1257] The present invention also provides a method for controlling pests that cause plant diseases

[1258] In some embodiments, prior to application, at least 20% of the molecules of the copper-based fungicide are complexed by electrostatic interactions with the polyelectrolyte molecules. In some embodiments, prior to application, at least 20% of the molecules of the copper-based fungicide are within the polyelectrolyte to form a complex.

[1259] The present invention also provides a method for controlling pests by preventive, curative or permanent treatment of plant diseases caused by phytopathogenic fungi, which comprises contacting a plant, its locus or its propagation material with an effective amount of any one of the combinations, compositions, complexes, or delivery systems disclosed herein.

[1260] The present invention also provides a method for controlling pests by preventive, curative and / or permanent treatment of plant diseases caused by phytopathogenic fungi, which comprises contacting a plant, its locus or its propagation material with an effective amount of any one of the macromolecular complexes comprising a copper-based fungicide disclosed herein.

[1261] The present invention provides the use of a complex according to the invention for increasing the uptake of a copper-based fungicide in a plant, increasing the retention of a copper-based fungicide by a plant and / or increasing the bioavailability of a copper-based fungicide to a plant.

[1262] The present invention provides the use of a macromolecular complex according to the invention for increasing the uptake of a copper-based fungicide in a plant, increasing the retention of a copper-based fungicide by a plant and / or increasing the bioavailability of a copper-based fungicide to a plant.

[1263] The present invention also provides the use of polyelectrolytes for reducing the phytotoxicity of copper-based fungicides.

[1264] The described (macromolecular) complexes, compositions and / or delivery systems can be applied to healthy or diseased plants. The described (macromolecular) complexes, compositions and / or delivery systems can be used on various plants, including but not limited to crops, seeds, bulbs, propagation materials, or ornamental species.

[1265] The present invention provides a method of controlling diseases caused by phytopathogenic fungi on plants or their propagation materials, which comprises contacting the plants, their loci or their propagation materials with at least one of the combinations, matrices, compositions, or delivery systems defined herein.

[1266] The present invention provides a method for increasing the bioavailability of a copper-based fungicide, comprising interacting the copper-based fungicide with a polyelectrolyte to form a macromolecular matrix prior to applying the copper-based fungicide to plants, plant parts, and / or soil.

[1267] In some embodiments, the polyelectrolyte interacts with the copper-based fungicide by partially or completely entrapping the copper-based fungicide within the polyelectrolyte.

[1268] In some embodiments, the polyelectrolyte interacts with the copper-based fungicide by partially or completely complexing or encapsulating the copper-based fungicide within the polyelectrolyte.

[1269] The invention provides the use of any of the combinations or compositions described herein for protecting a plant, or a part of a plant, against a pathogen.

[1270] In some embodiments, the composition is sprayed onto a plant or a portion of a plant.

[1271] In some embodiments, the plant part is leaves, seeds, and / or fruits.

[1272] In some embodiments, the combination, matrix, macromolecular complex, or composition is applied in an amount of 0.01-2 g / ha of copper-based fungicide.

[1273] The present invention also provides a method of protecting a plant, or a part of a plant, against a pathogen, comprising contacting the plant, or the part of the plant, with any one or any combination of the compositions described herein.

[1274] The present invention also provides a method of preventing, reducing and / or eliminating the presence of a pathogen on a plant, or a part of a plant, comprising contacting the plant, or the part of the plant, with any one of the compositions described herein.

[1275] In some embodiments, the plant part is leaves, seeds, and / or fruits.

[1276] The present invention also provides a method for controlling diseases caused by phytopathogenic fungi in plants or on their propagation materials, which comprises contacting the plants or their propagation materials with any of the combinations and compositions described herein.

[1277] The present invention also provides a method for reducing drift of a copper-based fungicide, comprising interacting the copper-based fungicide with a polyelectrolyte to form a macromolecular complex prior to applying the copper-based fungicide to plants, plant parts, and / or soil.

[1278] The present invention also provides a method for increasing the rainfastness of a copper-based fungicide, comprising interacting the copper-based fungicide with a polyelectrolyte to form a macromolecular complex before applying the copper-based fungicide to plants, plant parts, and / or soil. The present invention also provides a method for increasing the persistence of a copper-based fungicide, comprising interacting the copper-based fungicide with a polyelectrolyte to form a macromolecular complex before applying the copper-based fungicide to plants, plant parts, and / or soil.

[1279] In some embodiments, the fungus is one of: leaf spot of wheat (Mycosphaeria graminicola; anamorph: Septoria tritici, wheat leaf rust (Puccinia tritici), stripe rust (Puccinia striatum), apple scab (Puccinia inaelii)), maize blister smut (Ustilago maydis), grape powdery mildew (Uncinula vinifera), barley moire (Moire hordei), rice blast (Magnesia oryzae), soybean rust (Puccinia sojae), wheat glume blight (Mycosphaeria glumensis), wheat powdery mildew (Erysiphacia graminicola), barley powdery mildew (Erysiphacia graminicola), cucurbit powdery mildew (Erysiphacia graminicola), cucurbit anthracnose (Aspergillus cucurbitae), beet brown spot (Erysiphacia betae), tomato early blight (Alternaria solani), and barley web blotch (Pyricularia terrestris).

[1280] In some embodiments, the macromolecular complexes, compositions and / or delivery systems according to the present invention are applied as a foliar application.

[1281] In some embodiments, the macromolecular complexes, compositions and / or delivery systems according to the present invention are applied as a soil application.

[1282] In some embodiments, the pesticide is applied at an application rate effective for controlling pests. In some embodiments, the pesticide is applied at an application rate effective for preventing infection by pests. In some embodiments, the pesticide is applied at an application rate effective for curing infection by pests.

[1283] In some embodiments, the method of the present invention is effective for preventing infection by harmful organisms. In some embodiments, the method is effective for curing infection by harmful organisms. In some embodiments, the method is effective for increasing the pesticidal activity of copper-based fungicides. In some embodiments, the method is effective for extending the pesticidal effect of copper-based fungicides. In some embodiments, the method is effective for increasing the absorption of pesticides by plants, increasing the retention of copper-based fungicides by plants, and / or increasing the bioavailability of copper-based fungicides for plants.

[1284] In some embodiments, the methods of the present invention are effective for reducing the half maximal effective concentration (EC50) of a copper-based fungicide. In some embodiments, the methods are effective for reducing the EC50 by at least 10%. In some embodiments, the methods are effective for reducing the EC50 by at least 25%. In some embodiments, the methods are effective for reducing the EC50 by at least 35%. In some embodiments, the methods are effective for reducing the EC50 by at least 50%.

[1285] In some embodiments, the methods of the present invention are effective for reducing the LC50 of a copper-based fungicide. In some embodiments, the methods are effective for reducing the LC50 by at least 10%. In some embodiments, the methods are effective for reducing the LC50 by at least 25%. In some embodiments, the methods are effective for reducing the LC50 by at least 50%. In some embodiments, the methods are effective for reducing the LC50 by at least 75%. In some embodiments, the methods are effective for reducing the LC50 by at least 90%.

[1286] In some embodiments, the methods of the present invention are effective for reducing the LC90 of a copper-based fungicide. In some embodiments, the methods are effective for reducing the LC90 by at least 10%. In some embodiments, the methods are effective for reducing the LC90 by at least 25%. In some embodiments, the methods are effective for reducing the LC90 by at least 50%. In some embodiments, the methods are effective for reducing the LC90 by at least 75%. In some embodiments, the methods are effective for reducing the LC90 by at least 90%.

[1287] In some embodiments, the methods of the invention further comprise applying at least one additional agricultural chemical to the pest, plant part, plant, locus, or propagation material thereof.

[1288] In some embodiments, the macromolecular complex, composition, or delivery system is tank mixed with an additional agricultural chemical. In some embodiments, the macromolecular complex, composition, or delivery system is applied sequentially with the additional agricultural chemical. In some embodiments, the macromolecular complex, composition, or delivery system is applied simultaneously with the additional agricultural chemical.

[1289] In some embodiments, the macromolecular complex, composition, or delivery system is tank mixed with additional adjuvants. In some embodiments, the macromolecular complex, composition, or delivery system and additional adjuvants are administered sequentially.

[1290] In some embodiments, the adjuvant is selected from the group consisting of plant oil derivatives. In some embodiments, the plant oil derivative is a vegetable oil derivative. In some embodiments, the plant oil derivative is soybean oil methyl ester.

[1291] In some embodiments, the combination, macromolecular complex, composition, or delivery system is tank mixed with an additional agricultural chemical. In some embodiments, the macromolecular complex, composition, or delivery system is applied sequentially with the additional agricultural chemical. In some embodiments, the macromolecular complex, composition, or delivery system is applied simultaneously with the additional agricultural chemical.

[1292] Method for preparation

[1293] The present invention provides a method for preparing a composition comprising a macromolecular complex containing a copper-based fungicide and a polyelectrolyte, the method comprising preparing a solution of an antifreeze agent in water, adding a polyanion and a polycation to form a polyelectrolyte complex, adding a dispersant and a wetting agent, adding the copper-based fungicide, adding 80% of an antifoaming agent, milling the formulation to a desired particle size range, adding the remaining 20% ​​of the antifoaming agent, adding a solution of a rheology modifier in water and stirring until a homogeneous mixture is obtained.

[1294] The present invention provides a method for preparing a composition comprising a macromolecular complex containing a copper-based fungicide and a polyelectrolyte, the method comprising preparing a solution of an antifreeze agent in water, adding a polyanion, adding a dispersant and a wetting agent, and adding a copper-based fungicide.

[1295] The present invention provides a method for preparing a composition comprising a macromolecular complex containing a copper-based fungicide and a polyelectrolyte, the method comprising preparing a solution of an antifreeze agent in water, adding a polyanion, adding a dispersant and a wetting agent, adding a copper-based fungicide, adding 80% of an antifoaming agent, milling the formulation to a desired particle size range, adding the remaining 20% ​​of the antifoaming agent, adding a solution of a rheology modifier in water and stirring until a homogeneous mixture is obtained.

[1296] In some embodiments, the method comprises preparing a solution of an antifreeze agent in water, adding only the polyanion to the copper-based fungicide to form a macromolecular complex, adding a dispersant and a wetting agent, adding 80% of an antifoaming agent, milling the formulation to a desired particle size range, adding the remaining 20% ​​of the antifoaming agent, adding a solution of a rheology modifier in water, and stirring until a homogeneous mixture is obtained.

[1297] In some embodiments, the macromolecular complex is prepared by premixing the polyelectrolyte and the copper-based fungicide before adding other additives, dispersants, wetting agents, antifoaming agents, and rheology modifiers.

[1298] In some embodiments, the macromolecular complex is prepared by premixing the polyelectrolyte with the dispersant prior to adding the copper-based fungicide.

[1299] The present invention provides a method for producing the macromolecular complex of the present invention, comprising the following steps:

[1300] (a) providing an aqueous polyelectrolyte composition,

[1301] (b) mixing a copper-based fungicide into an aqueous composition, and

[1302] (c) thereby producing a macromolecular complex of the polyelectrolyte and the copper-based fungicide in the aqueous composition.

[1303] In some embodiments, the method further comprises the step of milling or grinding the resulting macromolecular complex to reduce its particle size to any particle size described herein.

[1304] In some embodiments, the method further comprises milling or grinding the resulting macromolecular complex to reduce its particle size such that the particles have a d90 of 10 microns or less and a d50 of 5 microns or less.

[1305] The present invention provides a method for producing a combination or composition as described herein by mixing a macromolecular complex as described herein with at least one agriculturally acceptable additive.

[1306] In some embodiments, the macromolecular complex is prepared by premixing the polyelectrolyte and the copper-based fungicide prior to adding another additive.

[1307] In some embodiments, the surfactant is added prior to the addition of the active ingredient.

[1308] In some embodiments, the compositions comprise at least one additional fungicide.

[1309] The present invention provides a method for preparing a composition comprising (1) a macromolecular complex comprising a copper-based fungicide and a polyelectrolyte and (2) one or more additional fungicides, the method comprising preparing a solution of an antifreeze agent in water, adding a polyanion and a polycation to form a polyelectrolyte complex, adding a dispersant and a wetting agent, adding a copper-based fungicide, wherein the additional fungicide is added at any time after the addition of the copper-based fungicide.

[1310] The present invention provides a method for preparing a composition comprising (1) a macromolecular complex comprising a copper-based fungicide and a polyelectrolyte and (2) one or more additional fungicides, the method comprising preparing a solution of an antifreeze agent in water, adding a polyanion and a polycation to form a polyelectrolyte complex, adding a dispersant and a wetting agent, adding the copper-based fungicide, adding 80% of an antifoaming agent, milling the formulation to a desired particle size range, adding the remaining 20% ​​of the antifoaming agent, adding a solution of a rheology modifier in water and stirring until a homogeneous mixture is obtained, wherein the additional fungicide is added at any time after the addition of the copper-based fungicide. In some embodiments, the method comprises preparing a solution of an antifreeze agent in water, adding only the polyanion to the copper-based fungicide to form a macromolecular complex, adding a dispersant and a wetting agent, adding 80% of the antifoaming agent, milling the formulation to a desired particle size range, adding the remaining 20% ​​of the antifoaming agent, adding a solution of a rheology modifier in water and stirring until a homogenous mixture is obtained, wherein additional fungicide is added at any time after the addition of the copper-based fungicide.

[1311] The present invention provides a method for preparing a composition comprising a macromolecular complex containing a copper-based fungicide and a polyelectrolyte, the method comprising preparing a solution of an antifreeze agent in water, adding a polyanion, adding a dispersant and a wetting agent, adding a copper-based fungicide, wherein additional fungicide is added at any time after the addition of the copper-based fungicide.

[1312] The present invention provides a method for preparing a composition comprising a macromolecular complex containing a copper-based fungicide and a polyelectrolyte, the method comprising preparing a solution of an antifreeze agent in water, adding a polyanion, adding a dispersant and a wetting agent, adding the copper-based fungicide, adding 80% of an antifoaming agent, milling the formulation to a desired particle size range, adding the remaining 20% ​​of the antifoaming agent, adding a solution of a rheology modifier in water and stirring until a homogeneous mixture is obtained, wherein additional fungicide is added at any time after the addition of the copper-based fungicide.

[1313] The present invention provides a method for preparing a composition comprising (1) a macromolecular complex comprising a copper-based fungicide and a polyelectrolyte and optionally (2) at least one additional fungicide, the method comprising preparing a solution of an antifreeze agent in water, adding a polyanion and a polycation to form a polyelectrolyte complex, adding a dispersant and a wetting agent and adding a copper-based fungicide.

[1314] The present invention provides a method for preparing a composition comprising (1) a macromolecular complex comprising a copper-based fungicide and a polyelectrolyte and optionally (2) at least one additional fungicide, the method comprising preparing a solution of an antifreeze agent in water, adding a polyanion, adding a dispersant and a wetting agent and adding a copper-based fungicide.

[1315] In some embodiments, when the composition further comprises a water-immiscible carrier (SE), the process further comprises mixing with an emulsifiable concentrate (EC) comprising an additional fungicide.

[1316] In some embodiments, the emulsifiable concentrate (EC) comprises a solution of an azole, a strobilurin, and / or any other fungicide other than a copper-based fungicide in a water-immiscible carrier.

[1317] In some embodiments, the organic phase includes at least one water-immiscible carrier.

[1318] In some embodiments, the water-immiscible carrier is a fatty acid amide.

[1319] In some embodiments, the organic phase includes at least one water-immiscible carrier, such as Armid DM10.

[1320] Copper-based fungicides

[1321] In some embodiments, the copper-based fungicide is selected from the group consisting of copper hydroxide, copper oxychloride (ternary), copper sulfate, copper gluconate, cuprous oxide, and any combination thereof.

[1322] In some embodiments, the copper-based fungicide is copper oxide. In some embodiments, the copper-based fungicide is copper oxychloride.

[1323] In some embodiments, the copper-based fungicide is (Equivalent to 66g / L copper) (Bordeaux mixture).

[1324] Polyelectrolytes

[1325] In the present application, polyelectrolyte refers to polyanions and / or complexes of polyanions and polycations.

[1326] Many different polyanions of both natural origin, for example xanthan gum, alginates, pectins, lignin compounds such as lignin sulfonates, carrageenan, humic acid, fulvic acid, brazil gum, Kondagogu gum, sodium alkylnaphthalene sulfonate, poly-gamma-glutamic acid, maleic acid starch half ester, carboxymethylcellulose, chondroitin sulfate, dextran sulfate and hyaluronic acid, and synthetic sources, for example poly (acrylic acid), polyphosphoric acid and poly (L-lactide). Most preferably, the polyanion comprises or is lignin sulfonate. The term "lignin compound" refers to a chemical compound derived from naturally occurring lignin or lignen by a process including sulfonation. The resulting sulfonic acid is a strong acid, and therefore the lignin compound is negatively charged at a pH value below 7.

[1327] The polyelectrolyte as the polyanion may be a mixture of two or more polyanions.

[1328] The polyelectrolyte as the polyanion may be a mixture of two or more lignin compounds.

[1329] Preferred lignin compounds are selected from Kraft lignin, organosolv lignin and / or lignin sulfonates. Kraft lignin is a polyphenolic product from the Kraft pulping process used to convert wood into wood pulp. Derivatives from Kraft lignin obtained by oxidation or other chemical modifications known to the skilled person are included.

[1330] Organosolv lignin is a polyphenolic product from a delignification process using organic solvents. It includes derivatives from organosolv lignin obtained by oxidation or other chemical modifications known to the skilled person.

[1331] Lignosulfonates (also known as lignosulphonate, lignosulfate, lignin sulfonate, ligninsulfonate, ligninsulfonate, ligninsulfonic acid, lignosulfonic acid, lignosulfuric acid, or LST 7) are water-soluble anionic polymers that are formed, for example, as a by-product in the sulfite pulping process. Lignosulfonates generally have a broad molecular weight distribution, typically in the range of about 500 to about 150,000. Lignosulfonates may contain different metal or ammonium ions as counter cations to the sulfonate group, such as, for example, copper, zinc, calcium, sodium, potassium, magnesium and aluminum. Suitable examples of lignosulfonates include sodium lignosulfonate (e.g., as BORRESPERSE Calcium lignin sulfonate (e.g., sold as BORRESPERSE The invention also includes but is not limited to lignin sulfonates, such as those sold by Borregaard LignoTech Ltd., Germany), ammonium lignin sulfonate, potassium lignin sulfonate, modified lignin sulfonate, derivatives of lignin sulfonate, or mixtures thereof. Modified lignin sulfonate and derivatives of lignin sulfonate are described in U.S. Pat. Nos. 3,639,263, 3,923,532, 4,006,779, 4,017,475, 4,019,995, 4,069,217, 4,088,640, 4,133,385, 4,181,652, 4,186,242, 4,196,777, 4,219,471, 4,236,579, 4,249,606, 4,250, 088, 4267886, 4269270, 4293342, 4336189, 4344487, 4594168, 4666522, 4786438, 5032164, 5075402, 5286412, 5401718, 5446133, 5981433, 6420602 and 7238645, which are incorporated herein by reference. Preferred lignin compounds are lignin sulfonates. Preferred lignin sulfonates are copper lignin sulfonate, zinc lignin sulfonate, calcium lignin sulfonate, sodium lignin sulfonate, potassium lignin sulfonate, ammonium lignin sulfonate, magnesium lignin sulfonate and / or aluminum lignin sulfonate, preferably calcium lignin sulfonate, sodium lignin sulfonate, potassium lignin sulfonate or ammonium lignin sulfonate, most preferably calcium lignin sulfonate.

[1332] The term chitosan relates to linear p-(1→4)-linked glucosamine and N-acetylglucosamine. It can be produced from chitin or its sodium salt (e.g. derived from shrimp) by treatment with aqueous sodium hydroxide solution at elevated temperatures or by enzymatic treatment with, for example, chitin deacetylase (EC 3.5.1.41). Another source of chitin is fungi, including basidiomycetes, ascomycetes and algae fungi, where it is a component of the cell wall and structural membranes of hyphae, stalks and spores. The most preferred chitosan is from or derived from a fungus.

[1333] The preferred MW of chitosan is 10-20 kDa. The use of chitosan with a higher MW of 20-30 kDa may result in differences in the physicochemical properties of the resulting composition, such as increased viscosity or the formation of aggregates.

[1334] In some embodiments in which the polyelectrolyte is a polyanion and polycation complex, the polycation is selected from the group consisting of poly-L-lysine, ε-poly-L-lysine, poly-L-arginine, chitosan oligosaccharides and chitosan. Most preferably, the polycation comprises or is chitosan. Typically, the deacetylation as determined by colloid titration is 50% to 99.9%, preferably 70% to 99.8% and most preferably 90% to 99.7% compared to chitin. Chitosan derivatives can be prepared by reactions at amino groups (e.g., by N-acylation, formation of N-alkylene and N-arylene derivatives, N-alkylation and N-arylation) or at hydroxyl groups, as known to the skilled person.

[1335] The polycation is preferably or comprises cationic starch, poly(allylamine), chitosan, chitosan derivatives such as thiolated chitosan, 5-methyl-pyrrolidone-chitosan and chitosan oligosaccharides, ε-pL-lysine, DEAE-dextran, or a mixture thereof to form a polyelectrolyte complex with a polyanion. Preferably, the polycation is selected from the group consisting of: cationic starch, poly(allylamine), chitosan and chitosan derivatives. Preferably, the polycation is poly(allylamine). Preferably, the non-biologically active polycation is chitosan. In some embodiments, the polycation is chitosan (CTS), ε-poly-L-lysine (ε-PLL), polyallylamine (PAA), or any combination thereof. In some embodiments, the polycation is chitosan (CTS). In some embodiments, the polycation is polyallylamine (PAA). In some embodiments, the polycation is ε-poly-L-lysine (ε-PLL).

[1336] As used herein, the term "chitosan" refers to a linear polysaccharide composed of randomly distributed 6-(l-4)-linked D-glucosamine (deacetylated units) and N-acetyl-D-glucosamine (acetylated units). Chitosan is produced by deacetylation of chitin. The term "chitosan" refers to chitosan, chitosan derivatives, and mixtures of chitosan and chitosan derivatives.

[1337] The polyelectrolyte complex comprises a polyanion, such as a lignin compound, xanthan gum and alginate, and a polycation, such as chitosan, in a relative amount between 1:2 and 60:1 (w / w), more preferably between 1:1 and 50:1, more preferably between 2:1 and 30:1, such as about 6:1; about 5:1, about 4:1, (w / w). The relative amount of polyanion, preferably lignin compound and polycation, preferably chitosan in the polyelectrolyte complex according to the invention is most preferably about 10:1, even more preferably about 5:1 (w / w).

[1338] In aqueous solution at a pH of about 4.5, polycations such as chitosan polymers are positively charged and the cationic amino groups on the glucosamine subunits can electrostatically interact with the anionic groups (usually carboxylic acid groups) of polyanions such as lignin sulfonates to form polyelectrolyte complexes.

[1339] The polyelectrolyte may be a complex of a mixture of two or more polyanions and a mixture of two or more polycations.

[1340] The polyelectrolyte may be a complex of a mixture of two or more lignin compounds and a mixture of two or more chitosans.

[1341] In some embodiments, the composition is different from the SE composition exemplified in PCT International Application No. PCT / IB2021 / 061258.

[1342] In some embodiments, the composition is other than a composition consisting of:

[1343] a) Bordeaux mixture,

[1344] b) picoxystrobin,

[1345] c) propylene glycol,

[1346] d) Metasperse 550S,

[1347] e) Borresperse CA,

[1348] f) Geropon T-77,

[1349] g) Atlox 4894,

[1350] h) SAG 1572,

[1351] i) Proxel GXL,

[1352] j)DM water,

[1353] k) prothioconazole,

[1354] l) Armid DM 10,

[1355] m) Emulsogen TS200,

[1356] n) TEA, and

[1357] o) Rhodopol 23 (2%).

[1358] In some embodiments, the composition is other than a composition consisting of:

[1359] a) 34.29% w / w Bordeaux mixture (9.4 / 27.22),

[1360] b) 2.78% w / w of picoxystrobin (2.7 / 97),

[1361] c) 5% w / w propylene glycol,

[1362] d) 1% w / w Metasperse 550S,

[1363] e) 2.8% w / w Borresperse CA,

[1364] f) 2% w / w of Geropon T-77,

[1365] g) 2% w / w Atlox 4894,

[1366] h) 0.1% w / w SAG 1572,

[1367] i) 0.05% w / w Proxel GXL,

[1368] j) 36.86% w / w DM water,

[1369] k) 3.06% w / w prothioconazole,

[1370] l) 3.06% w / w Armid DM 10,

[1371] m) 1.5% w / w Emulsogen TS200,

[1372] n) 0.5% w / w TEA, and

[1373] o) 5% w / w Rhodopol 23 (2%).

[1374] The present invention provides a suspoemulsion composition comprising (1) a copper-based fungicide, (2) a polyelectrolyte, (3) at least one additional fungicide selected from the group consisting of strobilurin fungicides, azole fungicides, benzamide fungicides, morpholines, QiI fungicides, SDHI and any combination thereof, (4) water and (5) a water-immiscible carrier, wherein the copper-based fungicide is suspended in the water and the at least one additional fungicide is dissolved in the water-immiscible carrier.

[1375] In some embodiments, the compositions comprise two additional fungicides.

[1376] In some embodiments, the composition comprises two or more additional fungicides, at least one dissolved in a water-immiscible carrier and the others suspended in water and / or dissolved in a water-immiscible carrier.

[1377] In some embodiments, the copper-based fungicide is selected from the group consisting of copper oxychloride, copper hydroxide, copper sulfate, and any combination thereof.

[1378] In some embodiments, the copper-based fungicide is copper sulfate.

[1379] In some embodiments, the polyelectrolyte is a complex of a polycation and a polyanion, the polyelectrolyte comprises at least one polyanion, or the polyelectrolyte is a polyanion.

[1380] In some embodiments, the polyanion is selected from the group consisting of: xanthan gum, alginates, pectins, lignin compounds, carrageenan, humic acid, fulvic acid, brazil gum, Kondagogu gum, sodium alkylnaphthalene sulfonate, poly-gamma-glutamic acid, maleic acid starch half ester, carboxymethyl cellulose, chondroitin sulfate, dextran sulfate and hyaluronic acid, as well as synthetic sources such as poly (acrylic acid), polyphosphoric acid, poly (L-lactide) and any combination thereof.

[1381] In some embodiments, the polyelectrolyte comprises a lignin compound.

[1382] In some embodiments, the lignin compound is a lignin sulfonate.

[1383] In some embodiments, the polyelectrolyte is a complex of a polyanion and a polycation.

[1384] In some embodiments, the polycation is selected from the group consisting of poly-L-lysine, ε-poly-L-lysine, poly-L-arginine, polyallylamine, chitosan oligosaccharide, chitosan, and any combination thereof.

[1385] In some embodiments, the polycation is chitosan.

[1386] In some embodiments, the polyelectrolyte is a polyanion and is substantially free of or free of polycations.

[1387] In some embodiments, the weight ratio between polyelectrolyte and metallic copper in the copper-based fungicide is between 1:10 and 1:1.

[1388] In some embodiments, the weight ratio between polyelectrolyte and metallic copper in the copper-based fungicide is 1:3.5.

[1389] In some embodiments, the weight ratio between polyelectrolyte and metallic copper in the copper-based fungicide in the combinations and / or compositions described herein is 1:4.4.

[1390] In some embodiments, the concentration of the copper-based fungicide in the composition is between 20% and 35% by weight based on the total weight of the composition.

[1391] In some embodiments, the concentration of the additional fungicide in the composition is between 3%-8% by weight based on the total weight of the composition.

[1392] In some embodiments, the concentration of the polyelectrolyte in the composition is 0.01% to 10% by weight based on the total weight of the composition.

[1393] In some embodiments, the concentration of the polyelectrolyte in the composition is about 3% by weight based on the total weight of the composition.

[1394] In some embodiments, the composition comprises an agriculturally acceptable additive selected from the group consisting of an agriculturally acceptable carrier, a buffer, an acidulant, an antifoaming agent, a thickener, a drift retardant, a surfactant, a pigment, a wetting agent, a safener, a preservative, and any combination thereof.

[1395] In some embodiments, the compositions comprise 40%-80% water by weight.

[1396] In some embodiments, the composition comprises at least one dispersant.

[1397] In some embodiments, the composition comprises at least one anionic dispersant and at least one nonionic surfactant.

[1398] In some embodiments, the concentration of the one or more dispersants in the composition is 0% to 15% by weight based on the total weight of the composition.

[1399] In some embodiments, the compositions comprise at least one antifoaming agent.

[1400] In some embodiments, the antifoam agent is silicone based.

[1401] In some embodiments, the additional fungicides in the composition are prothioconazole and picoxystrobin fungicides.

[1402] In some embodiments, the composition has a viscosity in the range of 1500-1800 cPs (measured with a Brookfield spindle 63 at 12 rpm).

[1403] In some embodiments, the composition comprises particles having a particle size distribution (d90) of 10 microns or less.

[1404] In some embodiments, the composition has a pH in the range of 5.0-7.5.

[1405] In some embodiments, the composition has a density (g / ml) at 25°C of 1.26 ± 0.05.

[1406] The invention also provides a method of treating a plant, or a part of a plant, against a pathogen, comprising contacting the plant, or a part of a plant, with an effective amount of a combination, composition, or delivery system of the invention to thereby treat the plant, or a part of a plant against a pathogen.

[1407] In some embodiments, treating includes preventing, reducing, and / or eliminating the presence of a pathogen on a plant or a portion of a plant.

[1408] In some embodiments, treating includes controlling a disease caused by a pathogen.

[1409] In some embodiments, treating includes prolonging the control effect of the copper-based herbicide.

[1410] In some embodiments, the combination, composition, or delivery system is applied in an amount between 0.001 g / ha to 1000 g / ha of copper metal.

[1411] In some embodiments, the combination, composition, and / or delivery system is applied in an amount of about 0.0022 g / ha, 0.022 g / ha, 0.22 g / ha, 2.2 g / ha, or 22 g / ha of copper metal.

[1412] In some embodiments, the combination, composition, and / or delivery system is applied in an amount of about 0.0075 g / ha, 0.075 g / ha, 0.75 g / ha, 7.5 g / ha, or 75 g / ha of copper metal.

[1413] In some embodiments, the combination, composition, and / or delivery system is applied in an amount of about 0.0052 g / ha, 0.001 g / ha, 0.059 g / ha, or 0.0095 g / ha of copper metal.

[1414] In some embodiments, the combination, composition, and / or delivery system is applied in an amount of about 15 g / ha, 150 g / ha, 375 g / ha, 450 g / ha, or 750 g / ha of copper metal.

[1415] The invention also provides a method of promoting the growth of a crop plant in the presence of a pathogen, comprising contacting the plant, or a part of a plant, with an effective amount of a combination, composition or delivery system of the invention so as to thereby promote the growth of the treated crop plant compared to if the same type and amount of copper-based fungicide were formulated in the absence of a polyelectrolyte.

[1416] In some embodiments, the method is effective for improving plant vigor and / or increasing crop yield.

[1417] The present invention provides a pesticidal delivery system comprising the combination or composition described herein.

[1418] The present invention provides a method of treating a plant, or a part of a plant, against a pathogen, comprising contacting the plant, or a part of a plant, with an effective amount of any of the combinations, compositions, or delivery systems described herein to thereby treat the plant, or a part of a plant, against the pathogen.

[1419] The present invention provides a method of promoting the growth of a crop plant in the presence of a pathogen, comprising contacting the plant, or a part of a plant, with an effective amount of any of the combinations, compositions, or delivery systems described herein, so as to thereby promote the growth of the treated crop plant compared to if the same type and amount of copper-based fungicide were formulated in the absence of a polyelectrolyte.

[1420] The present invention provides a method for improving the efficacy of a copper-based fungicide comprising interacting the copper-based fungicide with a polyelectrolyte prior to applying the copper-based fungicide to a plant, plant part, and / or soil.

[1421] The present invention provides a method for controlling the release rate of copper cations from a copper-based fungicide, comprising interacting the copper-based fungicide with a polyelectrolyte prior to applying the copper-based fungicide to plants, plant parts, and / or soil.

[1422] The present invention provides a method for (i) increasing the biological activity of a copper-based fungicide on a target, (ii) increasing the persistence of a copper-based fungicide in a target, (iii) increasing the retention of a copper-based fungicide by a target, (iv) increasing the absorption rate of a copper-based fungicide by a target, or (v) increasing or enhancing the bioavailability of a copper-based fungicide to a target, wherein the method comprises interacting the copper-based fungicide with a polyelectrolyte prior to applying the copper-based fungicide to a plant, plant part, and / or soil.

[1423] The present invention provides a method for (i) reducing copper-based fungicide biodrift, (ii) increasing foliar adhesion of copper-based fungicides, (iii) increasing rainfastness of copper-based fungicides, (iv) increasing persistence of copper-based fungicides, and / or (v) reducing phytotoxicity of copper-based fungicides, wherein the method comprises interacting the copper-based fungicide with a polyelectrolyte prior to applying the copper-based fungicide.

[1424] The present invention provides a method for producing a macromolecular complex comprising a copper-based fungicide and a polyelectrolyte, comprising the following steps:

[1425] (a) providing an aqueous polyelectrolyte composition,

[1426] (b) mixing a copper-based fungicide into an aqueous composition, and

[1427] (c) thereby producing a macromolecular complex of the polyelectrolyte and the copper-based fungicide in the aqueous composition.

[1428] The present invention provides a method for preparing the composition described herein, which comprises mixing the macromolecular complex with at least one agriculturally acceptable additive.

[1429] When a list is provided, the list will be considered a disclosure to each member of the list independently.

[1430] The present invention will be better understood by reference to the following experimental details, but those skilled in the art will readily appreciate that the specific experiments detailed are merely illustrative of the present invention as more fully described in the claims that follow.

[1431] Withou...

Claims

1. A combination comprising (1) a certain amount of an azole fungicide and (2) a certain amount of an additive (I).

2. The combination according to claim 1, wherein: The additive (I) is selected from the group consisting of thiourea-based compounds, sodium thiosulfate, alkylamines, thioamide-based compounds, and any combination thereof.

3. The composition according to claim 2, wherein The combination comprises a thiourea-based compound, and the thiourea-based compound has a structure defined by the following formula: R 1 NH-C(=S)-NHR 2 in, (i)R 1 , R 2 All are H; (ii) R 1 is H, and R 2 is an alkyl or alkenyl or alkynyl or aryl or heterocyclic group; (iii) R 1 , R 2 are each independently alkyl, alkenyl or alkynyl; (iv) R 1 , R 2 are each independently aryl or heterocyclic; (v)R 1 is alkyl or alkenyl or alkynyl, and R 2 is an aryl or heterocyclic group, or (vi)R 1 and R 2 may be taken together with the nitrogen atom to which they are attached to form a ring containing 2 to 4 carbon atoms and optionally one additional nitrogen, sulfur or oxygen atom, which ring may be saturated or unsaturated and optionally substituted by 1 to 4 substituents selected from the group consisting of C1-C2 alkyl, halogen, CN, NO2 and C1-C2 alkoxy.

4. The composition according to claim 3, wherein The thiourea-based compound has the structure H2N-C(=S)-NH2(thiourea).

5. The composition according to any one of claims 1 to 4, wherein The combination comprises one or more alkylamines.

6. The composition according to any one of claims 1 to 5, wherein The combination comprises sodium thiosulfate.

7. A combination as claimed in any one of claims 1 to 6, wherein: The azole fungicide is selected from the group consisting of azaconazole, bifenthrin, bromoconazole, cyproconazole, difenoconazole, diniconazole, fluepiconazole, eticonazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imipenem, picroconazole, metconazole, myclobutanil, penconazole, propiconazole, silyconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, trithionazole, prothioconazole and clofoconazole.

8. The combination of claim 7, wherein: The azole fungicide is prothioconazole, fluphenazine, cyproconazole or difenoconazole.

9. The combination of claim 1, wherein: The azole fungicide is prothioconazole and the additive (I) is thiourea.

10. The combination according to any one of claims 1 to 9, wherein: The weight ratio between the azole fungicide and the additive (I) is between about 0.2:1 and 600:

1.

11. A combination as claimed in any one of claims 1 to 10, wherein: The weight ratio between the azole fungicide and the additive (I) is between about 1:60 and 60:

1.

12. A combination as claimed in any one of claims 1 to 11, wherein: The weight ratio between the azole fungicide and the additive (I) is about 11.7:1 or 7.1:

1.

13. A combination as claimed in any one of claims 1 to 12, wherein: The combination further comprises one or more additional fungicides.

14. The combination of claim 13, wherein: The combination comprises a strobilurin fungicide.

15. A combination as claimed in any one of claims 1 to 14, wherein: The combination is a tank mix.

16. A combination as claimed in any one of claims 1 to 14, wherein: The combination is a composition, a premix composition, or a water-dilutable composition.

17. A combination as claimed in any one of claims 1 to 14, wherein: The combination is a composition, a premix composition, or a water-dilutable composition, and wherein the combination does not contain a copper-based fungicide.

18. A composition comprising the combination of any one of claims 1 to 17 and an agriculturally acceptable carrier.

19. The composition of claim 18, wherein The composition is a liquid.

20. The composition of claim 19, wherein The composition is a water-based composition.

21. The composition of claim 20, wherein The water-based compositions are suspension concentrates.

22. The composition of claim 20, wherein The water-based composition is a suspoemulsion.

23. The composition of claim 19, wherein The composition is a non-aqueous based composition.

24. The composition of claim 23, wherein The non-aqueous based composition is an emulsifiable concentrate composition.

25. The composition of claim 23, wherein The non-aqueous composition is an oil dispersion.

26. The composition of claim 18, wherein The composition is a solid composition.

27. The composition of any one of claims 1 to 26, wherein The azole fungicide is in its solid form in the composition.

28. The composition of claim 27, wherein The azole fungicide is suspended in the agriculturally acceptable carrier.

29. The composition of any one of claims 1 to 25, wherein The azole fungicide is dissolved in the agriculturally acceptable carrier.

30. The composition of claim 29, wherein The agriculturally acceptable carrier is water.

31. The composition of claim 29, wherein Agriculturally acceptable carriers are organic carriers.

32. The composition of claim 31, wherein The organic carrier is an oil or water-immiscible carrier.

33. A composition as described in any one of claims 18 to 32, wherein The amount of the azole fungicide in the composition is between 0.1% and 70% by weight based on the total weight of the composition.

34. A composition as described in any one of claims 18 to 33, wherein The amount of the azole fungicide in the composition is between 1% and 50% by weight based on the total weight of the composition.

35. A composition as described in any one of claims 18 to 34, wherein The amount of the additive (I) in the composition is between 0.1% and 5% by weight based on the total weight of the composition.

36. A composition as described in any one of claims 18 to 35, wherein The composition comprises one or more additional fungicides, and the concentration of the one or more additional fungicides in the composition is between 1% and 45% by weight based on the total weight of the composition.

37. A composition as described in any one of claims 18 to 36, wherein The composition further comprises at least one agriculturally acceptable additive.

38. The composition of claim 18, wherein: a. the composition comprises: (1) prothioconazole, (2) thiourea and (3) a water-immiscible carrier, wherein the prothioconazole is dissolved in the water-immiscible carrier, or b. The composition comprises: (1) prothioconazole, (2) thiourea and (3) water, wherein the prothioconazole is suspended in the water.

39. A method of treating a plant or a locus thereof against pathogens comprising contacting the plant, a part of the plant, or the locus with a combination or composition as claimed in any one of claims 1 to 38.

40. The method of claim 39, wherein: The pathogen is a phytopathogenic fungus.

41. The method of claim 39 or 40, wherein: Processing includes: a. controlling diseases caused by said pathogens, b. Control of diseases caused by phytopathogenic fungi in plants or on their propagation material, c. preventing, reducing and / or eliminating the presence of said pathogen on said plant, or a part of said plant, and / or d. protecting the plant, or a part of a plant, against the pathogen.

42. The method of any one of claims 39 to 41, wherein: The additive (I) and the azole fungicide are applied simultaneously as a tank mix.

43. The method of any one of claims 39 to 41, wherein: The additive (I) and the azole fungicide are applied in simultaneous application.

44. A method for increasing the application rate of an azole fungicide to a plant or plant part and / or increasing the frequency of application of an azole fungicide to a plant or plant part without causing increased phytotoxicity to the plant, wherein: The method comprises applying the azole fungicide to the plant or plant part in combination with an additive (I) selected from the group consisting of a thiourea-based compound, sodium thiosulfate, an alkylamine, a thioamide-based compound, and any combination thereof.

45. The method of claim 44, wherein: The method improves pest control without causing increased phytotoxicity to the plants.

46. ​​A method of using an azole fungicide to improve pest control without increasing phytotoxicity, wherein: The method comprises applying to a locus where pest control is desired a combination or composition as claimed in any one of claims 1 to 38.

47. A method of reducing and / or eliminating phytotoxicity to a plant or plant part caused by an azole fungicide applied to the plant or plant part, wherein the method comprises applying the azole fungicide in combination with an additive (I) selected from the group consisting of: thiourea-based compounds, sodium thiosulfate, alkylamines, thioamide-based compounds, and any combination thereof.

48. A method of increasing a plant's tolerance to an amount of an azole fungicide, comprising applying said amount of said azole fungicide in combination with an additive (I) selected from the group consisting of thiourea-based compounds, sodium thiosulfate, alkylamines, thioamide-based compounds, and any combination thereof.

49. A method of treating a plant or locus severely infected or susceptible to fungal diseases, comprising applying to the plant, plant part, or locus an amount of an azole fungicide in combination with an additive (I) selected from the group consisting of thiourea-based compounds, sodium thiosulfate, alkylamines, thioamide-based compounds, and any combination thereof.

50. Use of an additive (I) selected from the group consisting of thiourea-based compounds, sodium thiosulfate, alkylamines, thioamide-based compounds, and any combination thereof, for reducing phytotoxicity associated with the application of azole fungicides.

51. Use of an additive (I) selected from the group consisting of thiourea-based compounds, sodium thiosulfate, alkylamines, thioamide-based compounds, and any combination thereof, for increasing the plant health of a plant when treated with an azole fungicide, wherein: The plant health of plants treated with the azole fungicide in the presence of the additive (I) is increased compared to the plant health of plants treated with the same amount of the same azole fungicide in the absence of the additive (I).

52. Use of an additive (I) selected from the group consisting of thiourea-based compounds, sodium thiosulfate, alkylamines, thioamide-based compounds, and any combination thereof, for reducing or eliminating phytotoxicity associated with the application of azole fungicides, wherein: The phytotoxic effect on the plants treated with the azole fungicide in the presence of the additive (I) is lower than the phytotoxic effect on the plants treated with the same amount of the same azole fungicide in the absence of the additive (I).

53. Use of an additive (I) selected from the group consisting of thiourea-based compounds, sodium thiosulfate, alkylamines, thioamide-based compounds and any combination thereof for reducing or eliminating the phytotoxicity of azole fungicides, wherein: When the azole fungicide is applied in the presence of additive (I), the application rate and / or the extent of phytotoxic effects are reduced compared to the application rate and / or the extent of phytotoxic effects when the azole fungicide is applied in the absence of additive (I).

54. The method or use of any one of claims 44-53, wherein: The azole fungicide is selected from the group consisting of azaconazole, bifenthrin, bromoconazole, cyproconazole, difenoconazole, diniconazole, fluepiconazole, eticonazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imipenem, picroconazole, metconazole, myclobutanil, penconazole, propiconazole, silyconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, trithionazole, prothioconazole and clofoconazole.

55. The method of claim 54, wherein: The azole fungicide is fluphenazine, cyproconazole, difenoconazole, or prothioconazole.

56. The method of claim 54, wherein: The azole fungicide is prothioconazole.

57. A dilution composition comprising an azole fungicide, thiourea and water.

58. A method for producing the composition of claim 18, comprising the steps of: (a) preparing the aqueous composition of the azole fungicide and (b) adding the additive (I) to the aqueous composition to obtain the composition comprising the azole fungicide and the additive (I).

59. The method of claim 58, wherein: Additive (I) is a thiourea-based compound.

60. The method of claim 59, wherein: Additive (I) is thiourea.

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