WO2023233380A1

WO2023233380A1 - Fungicidal compositions

Info

Publication number: WO2023233380A1
Application number: PCT/IB2023/055706
Authority: WO
Inventors: Luiz Fernando COLLA; Silvio Luiz MACHADO
Original assignee: Adama Makhteshim Ltd.
Priority date: 2022-06-02
Filing date: 2023-06-02
Publication date: 2023-12-07

Abstract

The present invention provides oil-based agricultural compositions, typically, pesticide compositions comprising, (a) at least one agrochemical, preferably a combination of copper- based fungicide and azole (triazole), fungicide, (b) one or more water immiscible carrier or solvent (oily carrier) and (c) a triazole compatibilization agent exemplified by triethylamine, and optionally an SC-dispersant additive. The compositions comprise no more than 5% by weight of water and the SC-dispersant additive, is characterized by requiring at least 1,000 parts, and preferably, greater than 10,000 parts of said one or more water immiscible carrier or solvent to dissolve one part of said SC-dispersant additive and said SC-dispersant displays negligible solubility in the non-aqueous oil-based composition. The non-aqueous oil-based compositions maintain a very high proportion of free triazole fungicide. Those non-aqueous oil-based compositions which are OD concentrates comprising SC-dispersant additive, display improved dispersibility when diluted with water in a tank-mix.

Description

FUNGICIDAL COMPOSITIONS

Throughout this application various publications are referenced. The disclosures of specific portions of these documents referred to are hereby incorporated by reference into this application in order to more fully describe the state of the art to which this invention pertains.

TECHNICAL FIELD

The invention is most relevant to the technical field of agricultural, typically pesticide compositions.

The present invention relates to triazole compatibilizing agents, ingredients or additives that enable improved oil-based compositions comprising triazole fungicide. The invention relates to improved non-aqueous, oil-based combinations comprising azole (triazole) fungicide and triazole compatibilizing agents most notably exemplified by tertiary amines such as triethylamine, which allow for improved inventive oil-based compositions of (compatibilized) triazole fungicide combined with copper fungicide to be produced. The improved non-aqueous, oil-based compositions comprising azole (triazole) fungicide and copper fungicide are characterized by a higher proportion of free triazole fungicide and minimized formation of triazole-copper complex formation when analyzed by HPLC analysis, by inclusion of the triazole compatibilizing agents in the non-aqueous, oil-based compositions.

The present invention thus relates to non-aqueous fungicidal compositions comprising copper-based fungicidal compounds and triazole fungicidal wherein the triazole fungicide is one or more of prothioconazole, cyproconazole, hexaconazole, tebuconazole, azaconazole, bromuconazole, diclobutrazol, difenoconazole, diniconazole, diniconazole- M, epoxiconazole, etaconazole, fenbuconazole, fluconazole, fluquinconazole, flusilazole, flutriafol, furconazole, furconazole-cis, imibenconazole, ipconazole, ipfentrifluconazole, mefentrifluconazole, metconazole, myclobutanil, penconazole, propiconazole, quinconazole, simeconazole, tetraconazole, thiabendazole (triazole), triadimefon, triadimenol, triticonazole, uniconazole and uniconazole-P, their salts, esters, isomers and derivatives thereof, wherein triazole-copper complexation is minimized and the free triazole content in the composition is maintained as available for fungicidal efficacy. In several typical embodiments of the invention the triazole is prothioconazole or tebuconazole. The invention thus, relates to non-aqueous oil-based compositions comprising triazole fungicide, copper fungicide and triazole compatibilizing agent which are typically exemplified by tertiary amines such as triethylamine, wherein the compositions are characterized by preserved content of free triazole and prevention of significant triazolecopper complex formation, both as non-aqueous compositions such as OD concentrates as well as aqueous tank mix compositions prepared by diluting or dispersing the inventive oilbased compositions in water. The present invention also relates to the inclusion of non-oil soluble, SC-dispersants in the non-aqueous oil-based OD concentrates comprising triazole fungicide, copper fungicide that improve the dispersion quality and stability of Tank mix prepared by diluting and dispersing the inventive OD concentrates in water. The invention further relates to methods for preparing and using said composition.

The present invention provides improved oil-based, particularly non-aqueous oil concentrate (OD) compositions, of azole fungicides combined with tertiary amines notably triethylamine, which prevents or avoids the reduction of fungicidal azole content (free azole) in the OD composition and diluted Tank-mix, previously encountered due to interaction with other composition components exemplified by copper fungicide where a complex with copper would typically form which reduces the free azole available for fungicidal activity measurable by HPLC analysis.

The invention further relates to methods for preparing and using said compositions.

The invention thus also relates to the preparation of oil dispersion (OD) typically concentrated compositions of azole (triazole), fungicides combined with copper fungicides in non-aqueous commonly immiscible solvent and/or carrier, comprising triazole compatibilizing agent most notably exemplified by tertiary amine, such as triethylamine, and optionally, SC-dispersant components in the OD composition, wherein the SC-dispersant components are characterized by being effective as dispersants when the OD concentrate is eventually diluted with water prior to use but are minimally or negligibly soluble in the OD composition or the non-aqueous oil-based solvent/carrier components of the Oil Dispersion (OD).

Thus, the present invention provides improved non-aqueous compositions, of azole fungicides in admixture or combination with copper compounds which inter alia prevent or avoid, the reduction of fungicidal (free) azole content by preventing and/or reducing azole interaction with the copper compound. The present invention thus provides improved Oil Dispersion (OD) compositions comprising azole (triazole), fungicide such as prothioconazole or tebuconazole, copper compound and at least one triazole compatibilizing agent exemplified by tertiary amine such as triethylamine and a further fungicide such as anilide/carboxamide fungicides, or strobilurin fungicides exemplified by fluxapyroxad, azoxystrobin or picoxystrobin, wherein the percentage of free azole content in the OD is not reduced by significant complex formation with the copper.

The present invention thus provides improved Oil Dispersion (OD) compositions typically as concentrates, comprising azole (triazole), fungicide compound such as prothioconazole or tebuconazole, and copper compound wherein the amount of free azole fungicide in the composition is maintained at levels significantly above 80%, and often above 90%, and in some cases above 95%, compared to the amount of the triazole used in the manufacture, during the process of manufacture and over periods of prolonged storage, measured by HPLC peak area analysis at the same relative retention time (RT) as the azole fungicide used to formulate the composition. The free triazole content is maintained by the inclusion of triazole compatibilizing agent(s) as detailed herein.

The invention provides improved Oil Dispersion (OD) compositions comprising azole (triazole) fungicide compound and copper-based fungicide compound and triazole compatibilizing agent wherein the proportion of the free triazole is greater in the inventive compositions, compared to comparable compositions comprising the copper-based fungicide and the azole fungicide, formulated in the absence of the triazole compatibilizing agent wherein the proportion of the free triazole is an amount calculated when measured by a method such as HPLC analysis of the peak area at the retention time associated with the free azole compound which is the azole fungicide that is used for formulating or preparing the composition.

In some embodiments, the invention provides improved Oil Dispersion (OD) compositions comprising azole (triazole) fungicide compound and copper-based fungicide compound and triazole compatibilizing agent wherein the composition has a percent active content of azole fungicide (free triazole) as measured by HPLC analysis of the peak area at the retention time associated with the free azole compound, in the composition which is greater than the active content of azole fungicide as measured by HPLC in a composition comprising the same amounts of the same copper-based fungicide and the same azole fungicide without triazole compatibilizing agent. In some embodiments, the composition comprises at least 80% of the amount of the azole fungicide which was used for formulating or preparing the composition as free triazole. In some embodiments, the composition comprises at least 85% of the amount of the azole fungicide which was used for formulating or preparing the composition as free triazole. In some embodiments, the composition comprises 80-99% of the amount of the azole fungicide which was used for formulating or preparing the composition as free triazole. In some embodiments, the composition comprises 85-99% of the amount of the azole fungicide which was used for formulating or preparing the composition as free triazole. In some embodiments, the composition comprises 90-99% of the amount of the azole fungicide which was used for formulating or preparing the composition as free triazole. In some embodiments, the composition comprises 95-99% of the amount of the azole fungicide which was used for formulating or preparing the composition as free triazole.

The dispersion quality of a tank mix prepared by diluting the inventive azole (e.g., triazole), OD concentrate compositions, are improved by inclusion of dispersants in the inventive OD composition that are normally encountered only in aqueous (suspension) concentrates in that they do not dissolve in the OD components, such that they are essentially or practically, insoluble in oil based systems. These aqueous-composition-dispersants herein often referred to as SC-Dispersants are illustrated by water soluble anionic polyelectrolytes for example, lignosulfonates and/or polycarboxylic acid polymer and/or a polyelectrolyte copolymer . Notable examples of such “SC dispersants” is a co-polymer of sodium 2-acryloylamino-2- methylpropane-l-sulfonate (AMPS) monomers and ethyl acrylate (EA) monomers (AMPSEA) and/or lignosulphonate, and/or styrene-acrylic dispersants.

BACKGROUND

Copper-based fungicides are well-known but uses of copper-based fungicides are limited due to phytotoxicity to plant and toxicity to the user.

Combination of copper-based fungicide and azole fungicide are effective combinations in controlling different (fungal), diseases in crops.

In compositions comprising copper-based fungicide and azole (triazole), fungicide, the amount of the fungicidally available azole fungicide referred to as free azole in presence of copperbased fungicide is reduced through azole-copper interaction and there is a need to find a method for preventing this phenomena. Previously reported methods of addressing azole-copper interactions in pesticidal compositions would seem to have several drawbacks. It has been reportedly suggested that by chelating the copper compound with chelating agents such as EDTA the triazole-copper complex formation might be avoided.

However, inventors have found by experimental analysis, that in order to ensure that the percentage content of free triazole is acceptable in Copper-Triazole fungicidal oil-based compositions using only chelating agent (EDTA), the entire amount of copper would have to be chelated requiring the addition/incorporation of greater than stoichiometric amounts of chelating EDTA. Besides being expensive and difficult to incorporate, the chelated copper is found to be so much more soluble when chelated that unacceptable phytotoxic effects are encountered when these previously suggested compositions are applied to crop plants.

Some researchers have suggested adding ingredients that were reportedly able to break up previously formed copper-azole complexes. These ”de-complexing” agents have been found to be only partially successful if at all and typically a significant amount of the azole fungicide is not free and/or precipitates indicating that these decomplexants are only partially successful in breaking up previously formed triazole-copper complexes.

Several researchers have proposed solutions to the problem of azole-copper complexes which, according to their proponents, are only relevant to aqueous systems and compositions and are understood to be inapplicable in non-aqueous and/or oil-based compositions such as Oily Dispersion OD concentrates.

There is thus an on-going need to address and/or prevent the reduction of fungicidally available azole due to interaction with copper compounds in non-aqueous systems exemplified by Oily Dispersion (OD) concentrates comprising both azole and copper fungicides.

Additionally, there is an on-going need to improve the dispersion quality and stability of Tankmixes prepared by diluting Oil Dispersions (OD) of triazole and suspended copper fungicides. SUMMARY OF THE INVENTION

The present invention provides a method for preparing oil-based compatibilized triazole fungicide comprising dissolving, a. triazole fungicide, and b. at least one triazole compatibilizing agent, in a non-aqueous and/or immiscible, solvent and/or carrier thus obtaining an oil-based triazole fungicide compatible with copper-based compounds.

The present invention provides a method for preparing oil-based compatibilized triazole fungicide comprising dissolving, a. triazole fungicide, and b. at least one triazole compatibilizing agent in a non-aqueous water-immiscible solvent and/or carrier comprising less than 5% water by weight, and c. dispersing a copper-based fungicide in the oil-based triazole fungicide, to obtain a non-aqueous oil-based composition of compatibilized triazole fungicide and copper-based compound wherein the at least one triazole compatibilizing agent comprises a tertiary amine compound.

The present invention provides a method for preparing oil-based compatibilized triazole fungicide comprising dissolving, a. triazole fungicide, and b. at least one triazole compatibilizing agent in a non-aqueous water-immiscible solvent and/or carrier comprising less than 5% water by weight, and c. dispersing a copper-based fungicide in the oil-based triazole fungicide, to obtain a non-aqueous oil-based composition of compatibilized triazole fungicide and copperbased compound wherein the at least one triazole compatibilizing agent is a selected candidate compound that is able or sufficiently present in the Oil -Based composition of triazole fungicide and Copper-based fungicide to maintain at least 80 percent of the triazole fungicide as free triazole in the tests outlined herein. The general test for candidate selection protocol being exemplified in the experimental section “Prevention or Reversal of Copper-Triazole Complex by Free Triazole Quantification”.

The present invention provides an oily, non-aqueous, composition comprising,

A. at least one water immiscible carrier or solvent, B. azole fungicide, and

C. at least one tertiary amine, such as the alkylamine, triethylamine, and optionally, an SC dispersant. wherein the oily composition comprises less than 5% water and the tertiary amine, prevents significant reduction of amount of fimgicidally available (free), triazole when the oily composition is in the presence of copper-based fungicide or comprises the copper compound. The SC-dispersant is characterized by displaying minimal or negligible solubility in either the water immiscible carrier or solvent or the non-aqueous oily composition.

The oily composition is typically an OD concentrate, and the SC dispersant improves the dispersion quality of aqueous diluted compositions prepared by dispersing the OD concentrate in water prior to use. .

The present invention provides a non-aqueous, oil-based triazole fungicide comprising a combination of, a. azole (triazole), fungicide such as triazole fungicide, b. at least one triazole compatibilizing agent, and c. non-aqueous water-immiscible solvent and/or carrier, wherein the triazole fungicide and the triazole compatibilizing agent are dissolved in the nonaqueous solvent and/or carrier and the oil-based triazole fungicide is compatible with copperbased compounds.

The present invention provides a non-aqueous agricultural, oil dispersion OD concentrate composition comprising, a. at least one copper-based fungicide, b. at least one azole (triazole) fungicide, c. tertiary amine, d. one or more water immiscible, non-aqueous carrier or solvent and e. at least one SC-dispersant, and f. no more than 5% by weight of water, wherein the SC-dispersant, is characterized by requiring at least 1,000 parts of said one or more water immiscible non-aqueous carrier or solvent to dissolve one part of said SC- dispersant and said SC-dispersant is not soluble in the OD concentrate composition.

The present invention provides diluted tank-mix comprising the non-aqueous, oil-based triazole fungicides that are disclosed here particularly agricultural, oil dispersion OD concentrate compositions dispersed and/or diluted in water.

The present invention provides fungicidal oil-based compositions, notably OD concentrates comprising,

A. at least one water immiscible carrier or solvent,

B. azole (triazole), fungicide, and

C. at least one tertiary amine such as the alkylamine, triethylamine,

D. a suspended solid copper fungicide, and optionally

E. an SC dispersant. wherein the oily composition comprises less than 5% water and the tertiary amine prevents any significant reduction of amount of fungicidally available (free), azole in the presence of copperbased fungicide.

Triethylamine is exemplified as the tertiary amine which prevents the formation of copperazole complex and thus avoids the need to add an ingredient which acts as a decomplexation agent.

The SC-dispersant is characterized by displaying minimal or negligible solubility in either the water immiscible carrier or solvent or the non-aqueous OD composition, and yet will act to improve the dispersion quality of aqueous compositions (Tank-mix), prepared by diluting the inventive composition in water.

The stability of Tank-mixes prepared by diluting or dispersing oily dispersions in water for application in the field etc., is often unsatisfactory even though the OD concentrate itself is physically stable.

Thus, the incorporation of SC-dispersants in non-aqueous OD compositions within which they are insoluble, and thus presumably non-active as a dispersants, to improve the eventual dispersion quality of aqueous compositions of the OD concentrate diluted in water, is more generally applicable and surprisingly effective at providing a physically stable aqueous dispersion when at a later time the OD is dispersed in water. It would be counterintuitive to incorporate an apparently superfluous ingredient that would seem to have minimal impact on the quality of an oily dispersion.

Inventors have surprisingly found that these insoluble dispersants not only display their dispersant function when the OD is eventually diluted, they have been found to be superior to the incorporation of dispersants at the time of dilution. The invention thus provides oil-based agricultural compositions, such as OD concentrates comprising,

(1) at least one agrochemical

(2) one or more water immiscible carrier or solvent (oily carrier) and

(3) at least one dispersant additive (SC-dispersant), characterized in that said composition comprises no more than 5% by weight of water and wherein said dispersant additive (SC- dispersant), is characterized by requiring greater than 1,000, typically, more than 10,000 parts of said one or more water immiscible carrier or solvent to dissolve one part of said SC- dispersant and said SC-dispersant displays minimal or negligible solubility in the nonaqueous composition.

In some embodiments, the present invention provides oil based (OD) compositions comprising

(1) copper-based fungicide,

(2) azole (triazole), fungicide

(3) water immiscible carrier or solvent and

(4) tertiary amine (triethylamine), wherein the oil-based composition is characterized by reduced triazole- copper complexation when compared to OD compositions of copper-based fungicide and azole (triazole), fungicides absent the tertiary amine. The level of free azole (triazole) content in the composition is usefully measured by HPLC analysis relative to a reference standard.

In some embodiments the present invention provides 3 -way fungicidal oil based OD compositions comprising

(1) copper-based fungicide,

(2) azole (triazole), fungicide

(3) water immiscible carrier or solvent and

(4) tertiary amine (triethylamine) and

(5) at least one fungicidal agent which is neither a triazole nor a copper compound, exemplified by a strobilurin fungicide such as picoxystrobin or azoxystrobin, or an anilide/carboxamide fungicide, exemplified by fluxapyroxad, wherein the free triazole content in the composition remains greater than 75% of the Triazole active ingredient introduced during preparation of the oil based OD composition, during compounding, during storage over the shelflife, and after dilution with water in preparing a Tank-mix of the OD prior to fungicidal application. In some embodiments the free triazole content in the inventive composition remains equal to or greater than about 80% of the Triazole active ingredient introduced during preparation of the oil based OD composition, during compounding, during storage, over the shelf life, and after dilution with water when preparing a Tank-mix of the OD prior to fungicidal application.

In some embodiments the free triazole content in the composition remains equal to or greater than 85% of the Triazole active ingredient introduced during preparation of the oil based OD composition, during compounding, during storage over the shelf life, and after dilution with water when preparing a Tank-mix of the OD prior to fungicidal application.

In some embodiments the free triazole content in the composition remains equal to or greater than 90% of the Triazole active ingredient introduced during preparation of the oil based OD composition, during compounding, during storage over the shelf life, and after dilution with water in preparing a Tank-mix of the OD prior to fungicidal application.

In some embodiments the free triazole content in the composition remains equal to or greater than 95% of the Triazole active ingredient introduced during preparation of the oil based OD composition, during compounding, during storage over the shelf life, and after dilution with water in preparing a Tank-mix of the OD prior to fungicidal application.

In some embodiments, the present invention provides an oil based composition comprising

(1) copper-based fungicide,

(2) azole fungicide

(3) water immiscible carrier or solvent and

(4) aqueous-composition dispersant (SC-dispersant), characterized by providing improved dispersion quality and/or stability when the oil based composition is diluted and/or dispersed in aqueous liquid media such as when preparing a tank-mix.

The SC-dispersants of the invention display little or minimum solubility in non-aqueous systems and are generally considered to display their dispersant capabilities in water based systems only, it is thus extremely surprising that they have been found to improve these nonaqueous OD compositions of copper-based and azole (e.g., triazole) combination fungicide compositions when they are eventually diluted. In general, the inventive SC-dispersants are those considered insoluble or practically insoluble in oil based compositions. For the purposes of this invention the surprisingly useful dispersants utilized have a solubility typically characterized by requiring at least 1,000, most preferably, greater than 10,000 parts OD/EC liquid components to dissolve 1 part of dispersant and frequently significantly more.

While the triazole compatibilizing agents, ingredient or additive of the invention is exemplified by tertiary amines such as triethylamine, triazole compatibilizing agent candidates may be selected from a group of thiourea-based compound, sodium thiosulfate, alkyl amine, thioamide-based compound and any combination thereof, refer to the testing protocol as herein disclosed for assessing the suitability of each of these candidates in a specific OD composition.

In some embodiments, the triazole compatibilizing agent is selected from group of thioureabased compound, hexamethylene tetra amine, sodium thiosulfate, ethylene diamine and any combination thereof.

In some embodiments, the triazole compatibilizing agent is a mixture of two compounds selected from the group of thiourea-based compound, sodium thiosulfate, alkyl amine and thioamide-based compound.

In some embodiments, the triazole compatibilizing agent is a mixture of two compounds selected from the group of thiourea-based compound, hexamethylene tetra amine, sodium thiosulfate and ethylene diamine.

In some embodiments, the triazole compatibilizing agent is thiourea-based compound.

In some embodiments, the thiourea-based compound is thiourea.

In some embodiments, thiourea refers to the compound with the formula SC(NH2)2 and the structure H2N-C(=S)-NH2 (a.k.a. thiourea material, CAS number: 62-56-6).

Thiourea-based compound refers to a compound having the structure represented by the formula:

R¹NH-C(=S)-NHR² wherein,

(i) R¹, R², are both H;

(ii) R¹ is H and R² is alkyl or alkenyl or alkynyl or aryl or heterocyclic;

(iii) R¹, R² are each, independently, alkyl, alkenyl or alkynyl;

(iv) R¹, R² are each, independently, aryl, or heterocyclic;

(v) R¹ is alkyl or alkenyl or alkynyl and R² is aryl or heterocyclic, or

(vi) R¹ and R² can be taken together with the nitrogens to which they are attached to form a ring containing 2 to 4 atoms of carbon and optionally one additional atom of nitrogen, sulfur or oxygen, said ring may be saturated or unsaturated and optionally substituted with 1 to 4 substituents selected from the group consisting of C1-C2 alkyl, halogen, CN, NO2 and C1-C2 alkoxy.

In some embodiments, alkyl, which may be optionally substituted, denotes a linear or branched or cyclic hydrocarbon group comprising n carbon atoms.

In some embodiments, alkenyl, which may be optionally substituted, denotes a linear or branched or cyclic hydrocarbon group comprising n carbon atoms and at least one double bond.

In some embodiments, alkynyl which may be optionally substituted, denotes a linear or branched hydrocarbon group comprising n carbon atoms and at least one triple bond. In some embodiments, aryl, which may be optionally substituted, denotes carbocyclic aromatic radicals having from 6 to 14 carbon atoms.

In some embodiments, heterocyclic, which may be optionally substituted, denotes saturated, partially saturated, or fully unsaturated cyclic radical, which contains 3 to 6 ring atoms, of which 1 to 4 are from the group consisting of oxygen, nitrogen and sulphur.

In some embodiments, the thiourea-based compound is butyl thiourea, methyl propyl thiourea, phenylthiourea, ethyl phenyl thiourea, or diphenylthiourea.

In some embodiments, the thiourea-based compound is cyclic thiourea.

In some embodiments, triazole compatibilizing agent is not a fungicidally active ingredient.

In some embodiments, triazole compatibilizing agent is selected from thiourea-based compounds which are not pesticidally active.

In some embodiments, the selected triazole compatibilizing agent is a thioamide-based compound.

In some embodiments, the thioamide-based triazole compatibilizing agent may include but is not limited to thioacetamide, thiobenzamide, furan thioamide, pyridine thioamide and polythioamide.

In some embodiments, the thioamide-based compound is selected from the group of thioacetamide, thiobenzamide, furan thioamide, pyridine thioamide and polythioamide. In some embodiments, the triazole compatibilizing agent is sodium thiosulfate.

In some embodiments, the triazole compatibilizing agent is alkylamine. In some embodiments, the triazole compatibilizing agent comprises one or more alkylamines. In some embodiments, the alkylamine comprises one or more mono amines.

In some embodiments, the alkylamine is mono amine.

In some embodiments, the alkylamine is a diamine.

In some embodiments, the alkylamine is a polyamine. In some embodiments, the polyamine is hexamethylene tetra amine.

In some embodiments, the diamine is ethylene diamine.

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

(A) wherein:

(i) R¹ is hydrogen, alkyl, aryl, alkenyl, alkynyl or heterocyclic; R² is hydrogen, alkyl, aryl, alkenyl, alkynyl or heterocyclic; and R³ is hydrogen, alkyl, aryl, alkenyl, alkynyl or heterocyclic; and

(ii) at least one of R¹, R², and R³ is alkyl, aryl , alkenyl, alkynyl or heterocyclic.

In some embodiments, alkyl, which may be optionally substituted, denotes a linear or branched or cyclic hydrocarbon groupcomprising n carbon atoms.

In some embodiments, alkynyl which may be optionally substituted, denotes a linear or branched, hydrocarbon group comprising n carbon atoms and at least one triple bond.

In some embodiments, aryl, which may be optionally substituted, denotes to carbocyclic aromatic radicals having from 6 to 14 carbon atoms.

In some embodiments, heterocyclic, which may be optionally substituted, denotes saturated, partially saturated or fully unsaturated cyclic radical, which contains 3 to 6 ring atoms, of which 1 to 4 are from the group consisting of oxygen, nitrogen and sulfur.

In some embodiments, substituted means that the group (R¹ , R² and/or R³ ) may or may not be further substituted by one or more groups such as C_n alkyl, aryl, halogen, hydroxyl, thio, amino, cyano, oxo, nitro, acyl, amido, Ci-6 alkoxy, Ci-6 alkenyloxy, aryloxy, acyloxy, Ci- 6 alkylamino, arylamino, Ci-6 alkylthio, arylthio, alkylsulfonyl, arylsulfonyl, alkylsulfmyl, arylsulfmyl, Ci-8 alkylamido, and carboxyl.

In some embodiments, two or more of, R¹, R², R³ are the same.

In some embodiments, each of R¹, R², R³ are different.

In some embodiments where one or more of R¹, R², R³ is alkyl, one or more alkyl is linear. In some embodiments, an alkyl is cyclic.

In some embodiments, an alkyl is an alkyl fatty chain.

In some embodiments, R¹, R² and R³ are methyl.

In some embodiments, R¹, R² and R³ are ethyl.

In some embodiments, the R¹ and R² are H and R³ is C12 alkyl.

In some embodiments, the R¹ and R² are H and R³ is Cis alkenyl.

In some embodiments, the selected triazole compatibilizing agent is an alkyl amine which is oleyl amine.

In some embodiments, the alkylamine is dodecyl amine.

In some embodiments, the alkylamine is benzyl amine.

In some embodiments, triazole compatibilizing agent is hexamethylene tetra amine.

In some embodiments, triazole compatibilizing agent is sodium thiosulfate.

In some embodiments, triazole compatibilizing agent is ethylene diamine.

In some embodiments, alkylamine is Butylamine.

In some embodiments, alkylamine is Diethyl amine.

In some embodiments, alkylamine is Triethylamine as herein exemplified.

In some embodiments, triazole compatibilizing agent comprises thiourea.

In some embodiments, triazole compatibilizing agent comprises thioamide-based compound.

In some embodiments, triazole compatibilizing agent comprises sodium thiosulfate.

In some embodiments, triazole compatibilizing agent comprises alkylamine

In some embodiments, triazole compatibilizing agent comprises ethylene diamine.

In some embodiments, alkylamine comprises Butylamine.

In some embodiments, alkylamine comprises Diethyl amine.

In some embodiments, alkylamine comprises Triethylamine

In some embodiments, triazole compatibilizing agent is mixture of two compounds (I) and the weight ratio between them is from 10: 1 to 1:10.

In some embodiments, triazole compatibilizing agent is a mixture of thiourea and sodium thiosulfate.

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

In some embodiments, triazole compatibilizing agent is a mixture of hexamethylene tetra amine and thiourea. In some embodiments, the weight ratio between the thiourea and hexamethylene tetra amine is from 10: 1 to 1: 10.

In some embodiments, triazole compatibilizing agent is a mixture of hexamethylene tetra amine and sodium thiosulfate.

In some embodiments, the weight ratio between the hexamethylene tetra amine and sodium thiosulfate is from 10: 1 to 1: 10

In some embodiments, triazole compatibilizing agent is a mixture of sodium thiosulfate and ethylene diamine.

In some embodiments the weight ratio between the sodium thiosulfate and ethylene diamine is from 10: 1 to 1: 10.

In some embodiments, triazole compatibilizing agent is a mixture of thiourea and ethylene diamine.

In some embodiments, the weight ratio between the thiourea and ethylene diamine is from 10: 1 to 1: 10.

In some exemplary embodiments the inventive triazole compatibilizing agent (additive), is a tertiary and/or alkylamine and particularly exemplified by triethylamine. The addition or inclusion of triethylamine during the preparation of non-aqueous, oil-based combinations of copper-based and azole (e.g., triazole) fungicides has astonishingly provided unexpectedly improved non-aqueous compositions, where the improvement does not appear to be related to the usual activity of ethylamine in pesticidal formulations. The amount of free triazole available for fungicidal efficacy contained in the compositions is maintained and the amount of complexed triazole fungicide is minimized, and thus the addition of compounds whose function might be described as de-complexing agents is not needed, as the formation of these complexes has been avoided when the composition is non- aqueous rather than reversed at the time of aqueous dilution.

This aforementioned prevention of azole-copper complex is particularly surprising where the copper-based fungicide is present as solid suspended insoluble particles, and the interaction with triazoles might have a different character.

In some embodiments, the aqueous-composition-dispersant (SC-Dispersant) useful for inclusion in the oil-based compositions, is a water soluble anionic polyelectrolyte exemplified by lignosulfonates and/or a polycarboxylic acid polymer and/or a polyelectrolyte copolymer (providing they are essentially or practically, insoluble in oil based systems), exemplified by the random and block copolymers as exemplified in WO2017/098325, W02020/049433.

The styrene-acrylic dispersants exemplified by Atlox® Metasperse 500L are perhaps a further example of dispersants that would have heretofore appeared to be only useful in aqueous compositions.

In some embodiments, the SC-dispersing agent is a block or random co-polymer of sodium 2- acryloylamino-2-methylpropane-l-sulfonate (AMPS) monomers and ethyl acrylate (EA) monomers.

In some embodiments, the SC-dispersing agent is a block co-polymer of sodium 2- acryloylamino-2-methylpropane-l-sulfonate (AMPS) monomers and ethyl acrylate (EA) monomers.

In some embodiments, the SC-dispersing agent is a block co-polymer comprising 77% of sodium 2-acryloylamino-2-methylpropane-l-sulfonate (AMPS) monomers and 23% of the ethyl acrylate (EA) monomers.

In some embodiments, the SC-dispersing agent is provided as a solution of a block polymer comprising 77% of sodium 2-acryloylamino-2-methylpropane-l-sulfonate (AMPS) monomers and 23% of ethyl acrylate (EA) monomers, which may be prepared as described in Example 1 of WO2017/098325.

In some embodiments the dispersing agent is provided as a solution in water such as e.g., 30% by weight, with the proviso that the SC-dispersing agent solution is incorporated into the inventive oil-based compositions in an amount such that the water within which they were dissolved, does not increase the water content of the complete oil-based composition to equal or greater than 5% w/w. In many embodiments the water that is incorporated together with the dissolved SC-dispersant is considerably less than 5% w/w of the complete oil-based composition.

In some embodiments, the SC-dispersant is in solid undissolved particulate form in the oilbased concentrate composition and only dissolve when the oil-based concentrate is dispersed in and/or diluted with water.

The invention provides a process for producing non-aqueous oil based compatibilized triazole fungicide by dissolving triazole fungicide in a non-aqueous solvent and/or carrier and combining with triazole compatibilizing agents most notably tertiary amines such as triethylamine. The compatibilized triazole fungicide obtained are useful to prepare improved inventive oil-based compositions of (compatibilized) triazole fungicide and copper fungicide.

The present invention provides a process for producing an oil based composition comprising a copper-based fungicide and azole (triazole), fungicide. A typical general process might comprise the following steps although clearly other process steps are contemplated, in general the process steps need not be in the order below, but for practical formulation reasons a particular order of steps may be more useful.

(a) dissolve the azole fungicide (e.g., prothioconazole, Tebuconazole etc.), in immiscible solvent(s) such as aromatic hydrocarbons and/or dialkyl decanamide);

(b) Add

(i) immiscible carrier such as Methyl Soyate;

(ii) at least one SC-dispersant(s) such as AMPS-Ethyl Acrylate copolymer, and/or lignosulphonate;

(iii) surfactant(s) and optionally antifoam agent;

(c) add, a. Triethylamine, b. Copper fungicide e.g., Copper Oxychloride, and optionally c. a thickening agent exemplified by colloidal or fumed, silicon dioxide;

(d) homogenize & sieve.

In some embodiments the process continues with a packaging step, particularly where the packaging provides enhanced stability of the contained composition when stored at conditions exemplified by 54°C for 2 weeks.

It should be clear that the order of the steps in the above general process for preparing one embodiment of the oil-based Cu-Azole fungicide composition, is not absolutely critical although in particular instances a particular order of steps may be easier to process than others. This type of process optimization including the choice of additional or alternative excipients is well within the capability of those ordinarily skilled in the pesticide formulation arts.

In many embodiments the process for producing an oil based composition comprising a copper-based fungicide and azole (triazole), fungicide intrinsically includes the formation of compatibilized triazole fungicide as part of the preparation rather than as a separate process, without departing from the invention. In many embodiments the process steps are completed by a packaging step wherein the oil based composition is packaged in a container or package that ensures stability of the composition over the intended shelf life.

An example of a process for producing a specific 3 -way example of the inventive composition may include the following steps, although clearly this is only illustrative and several of the ingredients other than those required for the inventive function can be changed for others as described herein without departing from the general teaching provided.

The following method is given as a merely illustrative example for preparing a composition within the scope of the invention comprising the following ingredients, aromatic hydrocarbons, such as Solvesso® 150, dimethyl decanamide, triazole fungicide such as prothioconazole, and strobilurin fungicide such as picoxystrobin, block copolymer such as polyalkoxylated butyl ether (ATLAS® G-5002), tristyrylphenol ethoxylate, polyoxyethylene (20) sorbitan monolaurate such as tween®24, antifoam such as polydimethylsiloxanes, dodecylbenzene sulfonic acid calcium salt, SC-dispersant such as block copolymer of AMPS and ethyl acrylate, sodium lignosulfonate, triethylamine, methyl soyate, copper oxychloride (copper fungicide) and silica.

In a tank with agitation, add aromatic hydrocarbons such as Solvesso® 150, dimethyl decanamide, triazole fungicide such as prothioconazole and strobilurin such as picoxystrobin, mix at a rate such as 300 - 400 rpm until the triazole (and other fungicide active ingredient), are completely dissolved, applying heat if needed. Under stirring add, block copolymer such as polyalkoxylated butyl ether (ATLAS® G-5002), tristyrylphenol ethoxylate, Tween®24, antifoam such as polydimethylsiloxanes, dodecylbenzene sulfonic acid calcium salt, SC-dispersant such as block copolymer of AMPS and ethyl acrylate, methyl soyate, and sodium lignosulfonate. When the mixture is less than about 35°C (cooling if needed), add triethylamine, copper oxychloride (copper fungicide) and silica (Cab-o-Sil® M5), increasing the agitation if needed to a higher rate exemplified by between 1000 to 1500 rpm. The product is filtered, typically through 100 mesh sieves, before packaging.

In some embodiments the invention provides oil-based compositions of triazole and copper fungicides and a tertiary amine such as triethylamine optionally comprising a fungicide other than a triazole or copper compound, the compositions characterized by comprising less than 25% of the triazole in a complex with the copper. In noted embodiments the oil-based composition of the invention comprises less than 20% of the triazole content as triazole-copper complex.

In many embodiments the oil based composition of the invention comprises less than 20% of the triazole content as triazole-copper complex.

In certain embodiments the oil based composition of the invention comprises less than 15% of the triazole content as triazole-copper complex.

In several embodiments the oil based composition of the invention comprises less than 10% of the triazole content as triazole-copper complex.

In some embodiments the invention provides packaged stable oil-based compositions of triazole and copper fungicides and a tertiary amine such as triethylamine, optionally comprising a fungicide other than a triazole or copper compound, wherein the compositions are characterized by comprising less than 25% of the contained triazole fungicide in a complex with the copper, wherein the triazole is compatibilized by the tertiary amine (triethylamine) acting as compatibilizing agent/ingredient/additive.

In some embodiments the inventive oil-based composition of triazole and copper fungicides is adapted for dilution with and/or dispersion in, water prior to use, wherein, the adaptation comprises including in the oil -based composition, an SC dispersant that is not soluble in the oil-based composition and only activated as an effective dispersant when the oil-based composition (such as OD concentrate) is diluted with and/or dispersed in, water prior to use.

In some embodiments the inventive oil-based composition of triazole and copper fungicides and triethylamine, is adapted for dilution with and/or dispersion in, water prior to use, wherein, the adaptation comprises including in the oil-based composition, an SC dispersant that is not soluble in the oil-based composition and only activated as an effective dispersant when the oil-based composition (such as OD concentrate) is diluted with and/or dispersed in, water prior to use.

In some embodiments the inventive packaged stable oil-based composition of triazole and copper fungicides is adapted for dilution with and/or dispersion in, water prior to use, wherein, the adaptation comprises including in the oil-based composition, an SC dispersant that is not soluble in the oil-based composition and only activated as an effective dispersant when the oil-based composition such as OD concentrate, is diluted with and/or dispersed in, water prior to use.

The present invention also provides a method for controlling pathogenic, especially, fungicidal disease comprising applying an effective amount of any one of the herein described combinations and/or composition and/or diluted composition to a plant, a locus thereof, propagation material thereof, or an area infested with the unwanted pathogen so as to thereby control the pathogen disease, or to protect or prevent infestation of a plant, a locus thereof, or propagation material thereof.

DETAILED DESCRIPTION

Inventors have surprisingly found that by inclusion of tertiary amines exemplified by triethylamine, oil-based (OD) compositions of triazole (azole) fungicides together with copper fungicides can be formulated without significant triazole-copper complex formation. This is important because often triazole-copper complexes precipitate and/or the triazole fungicide that is complexed with copper is no longer available to act as a fungicide.

Thus, the inventors identify a group of triazole compatibilizing agent or ingredient or additive, most notably tertiary amines such as triethylamine which when combined with triazole fungicides provide compatibilized triazole fungicide compound. The compatibilized triazole fungicide compound can be formulated as non-aqueous, oil-based compositions together with copper fungicides wherein the compositions are characterized by less than significant levels of triazole-copper complex formation and highly preserved content of free triazole fungicide, as compared to comparable compositions absent the triazole compatibilizing agent.

The tertiary amines in the inventive oil-based (OD) composition prevents the formation of triazole-copper complex and maintains a high proportion of free triazole, available for fungicidal efficacy. The tertiary amines in the inventive oil-based (OD) composition can be referred to as triazole compatibilizing agent simply because they allow triazole to be compatible with ingredients, most notably copper compounds with which they would otherwise have complexed and reduced the amount of free triazole. However, it should be clear that using the term “triazole compatibilizing agent” does not imply that the activity by which these agents achieve their effect is necessarily by affecting some chemical or physical change in the triazole compound itself but rather the term triazole compatibilizing agent is simply an acknowledgment that the effect of inclusion of these agents in a composition comprising a triazole fungicide results in the triazole in the composition being protected from complex formation when the composition is combined with compounds such as copper-based fungicides. Thus, the corresponding term “compatibilized triazole” does not necessarily imply that a comparison between a solution of triazole compound in the same solvent absent the “triazole compatibilizing agent”, would reveal any measurable difference in the triazole compound other than the property that the solution of triazole fungicide is to some extent compatible with a copper-based fungicide, as regards the loss of free triazole by complex formation when that solution is combined with the copper compound.

Inventors have found that the inclusion of triethylamine in oil-based compositions of triazole and copper fungicides, promotes multiple improvements and advantages in the characteristics of compositions of triazole and copper fungicides. These aforementioned advantages might include the function of triethylamine in preventing reduction of Cu²⁺ ions to copper and assisting in achieving stable and high quality oil-based OD dispersions, in addition to their other surprising function as compatibilizing agents for triazole fungicides.

While inventors highlight the triazole compatibilizing activity of the tertiary amines (triethylamine), the use of the term “triazole compatibilizing agent” should in no way be viewed as limiting, but rather as a convenient way of labelling the triethylamine ingredient and no limitation is intended or implied that would limit the invention to any specific level of content or use simply based on the level of compatibilizing ability separate from other important functions and advantages obtained by their inclusion.

The invention relates to the prevention of triazole -copper complex formation rather than (or in addition to), the breaking or decomplexation of a complex that had already formed. Inventors have found that the prevention of triazole-copper formation with tertiary amines, exemplified by triethylamine is a much more useful solution the identified problem than either the use of de-complexing agents, or the use of chelating agents to pre-chelate the copper compound.

Inventors have shown experimentally, that the previously reported so-called, de-complexation agents are woefully inadequate to release enough free triazole once the triazole-copper complex has already formed. Additionally, while chelating agents such as EDTA may theoretically prevent triazole-copper complex formation to some degree, in practical situations they cannot really be used in agricultural fungicide concentrates for this purpose, because in order for the triazole fungicide to be protected from complexation, as shown in the experimental examples, all the copper contained in the composition must be chelated which requires more than a stoichiometric amount of EDTA, and this amount of EDTA content is impractical. Further, if a large proportion of the copper compound in the triazole and copper OD fungicidal composition is chelated copper, then the copper has a level of solubility that results in severe phytotoxicity in plants upon which it is applied.

As will be detailed later, in experiments comparing various candidates as triazole compatibilizing agent ingredients or components and their ability to maintain high a proportion of the triazole as “free triazole” as measured by HPLC recovery by absorbance peak area comparison, at the RRT of the triazole used, in the OD compositions tested after comparing compositions having the same general composition with the tested candidate ingredient being the only variant, inventors reached the following conclusions in the experiments where only one candidate, triethylamine was within the scope of inventive ingredients. For illustrative purposes the triazole fungicide chosen was prothioconazole.

Only in the samples containing triethylamine of the candidates tested in the experiments, the recovery results were able to be higher than 98%.

All other candidate components of the composition formula in those experiments, previously reported to be considered as “decomplexants”, used at the concentrations described , did not adequately prevent the complexation of prothioconazole.

When testing the compositions comprising triethylamine the components previously considered decomplexants in compared formulations were shown to be not acting as decomplexant agents in the test composition containing triethylamine as the complex formation was shown to have been prevented thus obviating the need for decomplexation. No breaking (reversing), of a triazole complex was found as no complex was formed, these ingredients just performed their regular formulation function.

It was only found possible to prevent some degree of the complexation of copper with prothioconazole by using a previously reported “decomplexant” copper chelating agent if a stoichiometric volume or excess in relation to the copper concentration is added

In one test it was found that, even using a stoichiometric amount of disodium EDTA, (98 g/L) could not achieve the same result as when triethylamine was used. This indicates that a greater than stoichiometric (excess), content of chelating agent (EDTA) would be needed to avoid complexation

By using tertiary amine (triethylamine, and other candidates to be tested), it is possible to avoid the complexation of Prothioconazole even with low concentrations of amine (triethylamine) , and without the need to generate chelated copper which in high concentrations is phytotoxic to plants.

However, despite what is detailed above regarding previous insufficient attempts to relieve the problems herein identified, inventors stress that they do not imply and in no way limit their invention to compositions or combinations where ingredients previously identified as de- complexation agents are absent. Inventors have no intention to imply that compositions comprising ingredients previously identified as de -complexation agents are outside the scope of protection, quite the reverse is true as inventors are well aware that many of these reported “de-complexation agents” are previously well known ingredients useful for formulating and preparing agricultural compositions and especially oil-based fungicidal compositions.

Similarly, inventors do not limit their invention to compositions or combinations where chelating agents are absent and have no intention to imply that compositions comprising chelating agents are outside the scope of protection. Quite the reverse is true as inventors foresee advantages obtainable where a small portion of the copper contained in the inventive compositions is chelated copper, for example, to allow a small portion of the copper to permeate and/or penetrate after application to provide non-phytotoxic levels of copper nutrients etc., but importantly the amount of chelated copper as compared to non-chelated copper in the composition should not be such that application of the composition causes phytotoxicity in crop plants. The small portion of chelated copper might be up to 5% of the total copper in the composition. In some embodiments the small portion of chelated copper might be up to 4% of the total copper in the composition. In some embodiments the small portion of chelated copper might be up to 3% of the total copper in the composition. In some embodiments the small portion of chelated copper might be up to 2% of the total copper in the composition. In some embodiments the small portion of chelated copper might be up to 1% of the total copper in the composition. In some embodiments none of the copper in the composition is chelated copper.

The inventive oil-based compositions are generally formulated as OD concentrates intended to be diluted and/or dispersed in water, typically as a tank -mix. Inventors have found that the usual dispersants included in compositions did not result in sufficiently stable dispersions when the OD concentrates of triazole and copper were diluted/dispersed in a tank mix with water.

Inventors found that stable high quality tank-mix dispersions were achievable when the oilbased (OD) concentrates were dispersed in water by including SC-dispersant additives in the formulation of the oil-based compositions. These SC-dispersants are so-called because they were heretofore considered to be unsuitable ingredients for non-aqueous systems. These SC- dispersants are characterized as having little or no discernable solubility in the components of the oil-based composition and thus only act as dispersants at the point when the oil-based concentrate (OD) is dispersed in water prior to use.

Several formulation additives, heretofore considered as appropriate dispersants, excipients, and carriers etc. only useful for aqueous systems exemplified by dispersants for Suspension Concentrates (SC) or water-dispersible powder or granules, have surprisingly been found to be particularly useful as advantageous and/or effective excipients in oil-based dispersion (OD) compositions of copper fungicides combined with azole-type (triazole), fungicides and water immiscible carrier. To be absolutely clear, although the inventive additives herein disclosed have very disparate and different characteristics and/or activities from each other in aqueous systems, they have been found to be advantageously beneficial in these water-free non-aqueous oil-based compositions, and no inference should be assumed that these individual additives have a common activity outside of this specific invention relating to non-aqueous compositions, or that the advantage of including these additives is necessarily related to their activity in aqueous systems.

Without being bound by any theory, inventors wonder if by introducing relatively small amounts of these water soluble dispersants first in non-aqueous oily systems in which they are insoluble as aqueous solutions, the insoluble SC-dispersant compounds are present in the oilbased composition as highly dispersed finely divided solid or colloidal particles and that when the OD concentrate is diluted with water the dispersants are much more homogeneously distributed in the aqueous dilute system providing improved dispersant function.

These inventive dispersants are referred to here as SC-Dispersants, as a convenient label, generally characterized by minimal or negligible solubility or practically insoluble, in OD compositions,

The inventive SC-dispersant additives are best combined in the oil-based composition comprising triazole fungicide, copper fungicide and triazole compatibilizing alkylamines, in particular triethylamine. The OD compositions of the invention that contain SC-Dispersants typically comprise a water immiscible solvent and the compositions are essentially water-free or contain negligible amounts of water, typically significantly below 5% by weight of the total composition.

4.1 Definitions

Unless defined otherwise, all technical and scientific terms used herein have the meaning commonly understood by persons of ordinary skill in the art to which this subject matter pertains.

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

As used herein, the term “about” when used in connection with a numerical value includes ±10% from the indicated value. All numerical values are intended to be preceded by the term “about” unless the context clearly dictates otherwise, thus a numerical value of “10”, by definition includes all values between 9 and 11 unless the text indicates a different meaning. In addition, all ranges directed to the same component or property herein are inclusive of the endpoints, are independently combinable, and include all intermediate points and ranges. It is understood that where a parameter range is provided, all integers within that range, and tenths thereof, are also provided by the invention including accepted rounding principles. For example, a range described as “30-45%” includes all values of 29.5% 29.6%, 29.7%, 29.8%, 29.9%, 30%, 30.1%, 30.2%, etc. up to 45.4%.

As used herein, the term the term “essentially non-aqueous” in the composition and/or combination embodiments refers to a combination or composition wherein the content of water is 5%or less. Commonly the % water content in oil-based concentrated embodiments, is significantly lower than 5%.

While every effort has been expended to avoid the error, if a numerical value disclosed herein has been mistakenly recorded as having more than one numeral after the decimal point, it should be considered to have been an inadvertent error and the figure should be understood to be that value rounded up or down, to a maximum of a single numeral after the decimal point, e.g., within this disclosure, a typographical error that records a figure of “147.4821”, should be understood that inventors intention was to refer to a correct value of “148”, unless the context makes clear that 147.5 is required. However, from the context it should be clear that values below “0.5” having more than one digit after the decimal point such as 0.02 should not be rounded down to zero as clearly these relate to actual values.

The term “crop”, as is used herein, include for example, cereals such as wheat, barley, rye, oats, sorghum and millet, rice, cassava and maize, and crops that produce, for example, peanut, sugar beet, cotton, soya, oilseed rape, potato, tomato, peach and vegetables, although omission of a particular crop in this disclosure is in no way indicative of an intention to exclude.

The term “metallic copper” when referring to a copper-based fungicidal compound is in reference to content of the part of the copper-based compound which is elemental copper ion such as a Cu²⁺ cation and will only refer to actual copper metal when it is clear from the context that copper metal is being referred to.

The term “part of a plant”, as is used herein, indicates a part of a plant including, but not limited to, pollen, ovule, leaf, root, flower, fruit, stem, bulb, com, branch, seedling and seed.

It was surprisingly found that incorporating alkyl amines especially triethylamine (azole compatibilizing agent), and aqueous-composition-dispersants (SC-Dispersants), in an oilbased composition comprising copper-based fungicide and azole fungicide provides superior oil-based compositions exemplified by Oily Dispersion (OD) concentrate compositions.

The present invention provides a non-aqueous oil based compatibilized triazole fungicide, comprising,

(1) azole fungicide (triazole),

(2) triazole compatibilizing agent, especially triethylamine, and

(3) water immiscible carrier and/or solvent.

The present invention provides an oil based composition, OD, comprising

(1) copper-based fungicide,

(2) azole fungicide,

(3) tertiary alkylamine, especially triethylamine

(4) water immiscible carrier and/or solvent.

The present invention provides a non-aqueous oil based fungicidalcomposition, comprising,

(1) compatibilized azole fungicide (triazole),

(2) copper based fungicide and

(3) water immiscible carrier and/or solvent, wherein the azole fungicide has been compatibilized for combination with copper fungicides by contacting the azole with triazole compatibilizing agent, especially triethylamine.

The present invention provides an oil based composition, OD, comprising

(1) copper-based fungicide,

(2) azole fungicide,

(3) SC-dispersant,

(4) tertiary alkylamine, especially triethylamine

(4) water immiscible carrier and/or solvent.

In some embodiments, the tertiary alkylamine (triethylamine), is mixed with the triazole (azole), fungicide prior to combining with the copper fungicide.

In some embodiments the triazole fungicide is fully dissolved in the water immiscible carrier and/or solvent prior to combining with the tertiary alkylamine (triethylamine).

In some embodiments, the SC-dispersant and/or alkylamine is mixed with the copper-based fungicide prior to combining with the azole fungicide.

In some 3 -way embodiments, the composition comprises additional oil-soluble fungicide(s) other than copper-based fungicide and azole fungicide. In some embodiments the additional fungicide is a strobilurin such as picoxystrobin and/or azoxystrobin

In some embodiments, when preparing the oil-based compositions of the invention, each of the copper-fungicide and the azole fungicide components are combinations comprising a combination with a water-immiscible carrier or solvent before the two types of fungicide component are combined into a single oil-based composition.

In some embodiments, when preparing the oil-based compositions of the invention, the azole fungicide component is a combination comprising a combination with a triazole compatibilizing agent and water-immiscible carrier or solvent forming non-aqueous oil based compatibilized triazole fungicide before the two types of fungicide components are combined into a single oil-based composition.

In some embodiments, the invention provides a composition comprising any one of the combinations described herein and at least one agriculturally acceptable additive suitable for inclusion in oil-based pesticidal compositions. In some embodiments, the agriculturally acceptable additive is any, some or all of anti-foam agent; anionic or cationic surfactant; thickening agent; emulsifier. Persons normally skilled in formulation of agricultural pesticide compositions will undoubtedly be aware of the formulation considerations that will determine optimal additives, other than the inventive triazole compatibilizing agents and SC-dispersants.

In some embodiments, the immiscible carrier/solvent is selected from the group of materials exemplified by the classes of compounds that include, aromatic hydrocarbons; dimethyl decanamide; methyl soyate (soybean oil methyl ester); and any and all combinations thereof.

In some embodiments, the composition comprises a solution of compatibilized azole fungicide in one or more immiscible carriers, tertiary alkylamine (triethylamine) and suspended particles of copper-based fungicide with a particle size distribution such that the completed composition can be sieved through a 100 mesh screen without removing any copper fungicide from the composition. Typical particle size distribution of the suspended particles is characterized by a D90 of 10 microns or less by volume or weight, as measured by a light scattering method. In some embodiments, the completed oil-based composition comprises copper-based fungicide particle size distribution (PSD) characterized by a D90 of 7 microns or less. In some embodiments, the particle size distribution characterized by a D90 of of 4 microns or less.

A composition according to the invention is most notably in the form of an oil-based liquid, most typically an Oily Dispersion (OD) concentrate, Concentrate, where the liquid phase is non-aqueous comprising less than 5% water. A noted composition is an Oily Dispersion concentrate. While the compositions of the invention are decidedly oil-based, it is often necessary to add the SC-dispersants in the form of aqueous solutions or colloids, for ease of processing and homogeneity. The small amounts of water introduced into the compositions of the invention that are associated with the commercially available aqueous-composition dispersants in no way detracts from their being oil-based compositions and being included within the contemplated scope of this invention, with the proviso that the SC-dispersants are insoluble to any discernable degree in the liquid components of the oil-based composition and the water content of the oil -based composition comprises no more than 5% water by weight.

In some embodiments, the concentration of the copper-based fungicide (typified by copper oxychloride), is up to or about 50%, more typically up to or about 35% and particularly up to or about 25% by weight based on the total weight of the composition. In some embodiments, the concentration of the copper-based fungicide is about 10% by weight based on the total weight of the composition and in noted examples 25%±10% (22.5 - 27.5%). In some embodiments, the concentration of the copper-based fungicide in the composition is between about 100 and 650 g/L (90 - 715 g/L), typically 300 g/L ±10% (270 - 330 g/L).

In some embodiments, the copper-based fungicide is Copper Oxychloride in which metallic copper represents approximately 60% by weight thus, in some embodiments, the concentration of the metallic copper (as component of non-metallic copper compounds) in the formulation comprising the copper-based fungicide is up to 30% ±10%, more typically up to 20% ±10%, and particularly up to 15% ±10%, by weight based on the total weight of the composition. In some embodiments the oil-based compositions comprise between 10 g/L to 400 g/L±10%, metallic copper. In some embodiments, the concentration of the metallic copper in the formulation comprising the copper-based fungicide is between about 50 g/L to about 300 g/L. In some embodiments, the concentration of the metallic copper in the formulation comprising the copper-based fungicide is 180 g/L ±10%.

In some embodiments, the concentration of the metallic copper in the formulation comprising the copper-based fungicide is about 1-25% by weight based on the total weight of the formulation. In some embodiments, the concentration of the metallic copper in the formulation comprising the copper-based fungicide is about 5-25% by weight based on the total weight of the formulation. In some embodiments, the concentration of the metallic copper in the formulation comprising the copper-based fungicide is about 5-15% by weight based on the total weight of the formulation. In some embodiments, the concentration of the metallic copper in the formulation comprising the copper-based fungicide is about 10% by weight based on the total weight of the formulation. In some exemplified embodiments, the concentration of the metallic copper in the formulation comprising the copper-based fungicide is 14% ±10%, by weight based on the total weight of the formulation which translates to approximately 23% Copper Oxychloride. Similar calculations are immediately apparent when the copper fungicidal compound has a different metallic copper content by adjusting the above example.

In some embodiments, the concentration of the metallic copper in the formulation comprising the copper-based fungicide is up to 25% by weight based on the total weight of the formulation. In some embodiments, the concentration of the metallic copper in the formulation comprising the copper-based fungicide is 10% by weight based on the total weight of the formulation. “Metallic copper” in the above discussion regarding copper compounds exemplified by copper oxychloride, refers to the portion of the copper compound which is the copper ion e.g., Cu²⁺ cation, or element and does not imply that the copper is in the form of metallic particles unless considering actual copper metal.

In some embodiments, the concentration of the metallic copper in the formulation comprising the copper-based fungicide is between about 100 and about 500 g/L, typically, 300 g/L ±10%.

In some embodiments, the concentration of the copper-based fungicide in the composition is between about 15% to about 45% 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 about 20% to about 35% 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 about 25% to about 30% by weight based on the total weight of the composition. In some embodiments, the concentration of the copper-based fungicide in the composition is 28.8% ±10% by weight based on the total weight of the composition.

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. In some embodiments, the copper-based fungicide is Bordeaux mixture. In some embodiments, the copper-based fungicide is comprised at least in part of a copper complex or chelate for example Copper(II) bis-alginate, Copper(II) glycinate, Cu(II)-EDTA and similar copper-based compounds. While water soluble copper compounds can be included, as mentioned above, the proportion of the copper content in chelated or soluble complexed form is perhaps better limited to a small proportion to minimize copper mediated phytotoxicity.

In some embodiments, the concentration of aqueous-composition dispersant (SC-dispersant), in the composition is between about 0.01% to 15% ±10% by weight based on the total weight of the composition. In some embodiments, the concentration of the SC-dispersants in the composition is between 0.01% to 10% ±10% by weight based on the total weight of the composition. In some embodiments, concentration of the SC-dispersant in the composition is between 0.1% to 8% ±10% by weight based on the total weight of the composition.

In noted embodiments the SC-dispersants in the composition are lignosulphonate salts and/or acrylic based co-polymers best exemplified by block copolymers of AMPS and Ethyl acrylate. It must be noted and made very clear that, outside of the instant invention related to oil-based compositions, this group of materials are not necessarily similar or comparable to each other and are perhaps only appropriately grouped together when their activity in non-aqueous systems are discussed. There should be no inference that in other systems they are comparable simply by having the inventive utility in non-aqueous systems disclosed herein.

In one group of noted embodiments the compositions of the invention comprise lignosulphonate salts and block copolymers of AMPS and ethyl acrylate as well as triethylamine, aromatic hydrocarbons and methyl soyate, in addition to a combination of copper-based fungicide and azole fungicide.

It should be clear that the addition of further processing aids and additives, e.g., surfactants, antifoam, thickeners etc., appropriate for oil-based compositions are definitely contemplated by the inventors and decidedly within the scope of the inventive compositions.

In some OD concentrate embodiments, the concentration of the triethylamine in the composition is between 0. 1% and 8% ±10%, more typically 0.5%to 5%± 10%, and particularly noted between 0.8 - 1.8% ±10% by weight based on the total weight of the composition. In some concentrate composition embodiments of the invention the concentration of the triethylamine in the composition is between 0.5% and 1.6% ±10%.In some exemplified OD concentrate embodiments the concentration of the triethylamine in the composition is 0.75%±10% and in others the concentration of the triethylamine in the composition is 1.2% ±10%.

Inventors note that while a range of concentrations of the triethylamine component in a particular OD composition of a copper-based fungicide and triazole fungicide is useful across the whole range, often formulation considerations seemingly unconnected with the inventive compatibilizing function will determine the optimal triethylamine concentration for that particular OD concentrate.

In some cases, a formulator might wish to control the pH of an aqueous composition obtained by diluting or dispersing the non-aqueous OD concentrate in water, perhaps to provide the most chemically or physically stable environment for one or more of the components of the inventive composition or the quality of the whole composition. As can now clearly be understood, a range of triethylamine concentrations that are equally useful in compatibilizing the azole (triazole) fungicide provides the scope for a formulator to adjust the triethylamine content to provide both the azole compatibilization required for the OD and tank mix obtained therefrom, as well as the optimal pH of the tank mix obtained by diluting/dispersing the OD concentrate in water.

In all events when wishing to determine the acceptable triazole compatibilizing agent identity and percentage content in a non-aqueous Oily composition of a copper-based fungicide and triazole fungicide that has not been specifically exemplified herein.

The methodology used in the experimental section as herein disclosed later should also be seen as a general method to determine whether a particular candidate for use as a triazole compatibilization agent and the percentage of that candidate content that is suitable for that composition.

In essence a very simple protocol for assessing the acceptability of a formulated composition as is exemplified later herein.

The test to assess a candidate as a triazole compatibilizing agent, can be performed with the objective to confirm that the inclusion of the candidate triazole compatibilizing agent, is able to prevent significant triazole complexation with copper, or alternatively to show that a candidate compound component is unable to adequately avoid the triazole-copper complexation.

A candidate compound that is able or sufficiently present in the Oil-Based composition of triazole fungicide and Copper-based fungicide to maintain at least 80 percent of the triazole fungicide as free triazole in the above outlined tests, is to be seen as an acceptable triazole compatibilizing agent/ingredient/additive .

The percent active content of azole fungicide of the triazole fungicide as free triazole is usefully measured by HPLC analysis comparing the peak area at the retention time associated with the amount of triazole fungicide compound, used to formulate the composition..

To establish the optimal triazole compatibilizing compound or the optimal content, prepare samples with the only difference being test component/ingredient variation.

The analyses may be performed after storage 12 hours at room temperature.

While the triazole compatibilizing agents, ingredient or additive of the invention is herein exemplified by tertiary amines such as triethylamine, candidate triazole compatibilizing agents for the above tests may be selected from a group of thiourea-based compound, sodium thiosulfate, alkyl amine, thioamide-based compound and any combination thereof.

Issues related to e.g., solubility of the candidate triazole compatibilizing agents in the specific non-aqueous solvent or carrier being tested, may reasonably be expected to play a role as regards the suitability of a particular candidate compatibilizing agent.

In some embodiments, a candidate as the triazole compatibilizing agent is selected from group of thiourea-based compound, hexamethylene tetra amine, sodium thiosulfate, ethylene diamine and any combination thereof.

In some embodiments, the triazole compatibilizing agent candidate is a mixture of two compounds selected from the group of thiourea-based compound, sodium thiosulfate, alkyl amine and thioamide-based compound.

In some embodiments, the triazole compatibilizing agent candidate is a mixture of two compounds selected from the group of thiourea-based compound, hexamethylene tetra amine, sodium thiosulfate and ethylene diamine.

In some embodiments, the triazole compatibilizing agent candidate is thiourea-based compound.

In some embodiments, the thiourea-based compound is thiourea.

R¹NH-C(=S)-NHR² wherein,

(vi) R¹, R², are both H;

(vii) R¹ is H and R² is alkyl or alkenyl or alkynyl or aryl or heterocyclic;

(viii) R¹, R² are each, independently, alkyl, alkenyl or alkynyl;

(ix) R¹, R² are each, independently, aryl, or heterocyclic;

(x) R¹ is alkyl or alkenyl or alkynyl and R² is aryl or heterocyclic, or

(vii) R¹ and R² can be taken together with the nitrogens to which they are attached to form a ring containing 2 to 4 atoms of carbon and optionally one additional atom of nitrogen, sulfur or oxygen, said ring may be saturated or unsaturated and optionally substituted with 1 to 4 substituents selected from the group of C1-C2 alkyl, halogen, CN, NO2 and C1-C2 alkoxy. In some embodiments, alkyl, which may be optionally substituted, denotes a linear or branched or cyclic hydrocarbon group comprising n carbon atoms.

In some embodiments, heterocyclic, which may be optionally substituted, denotes saturated, partially saturated, or fully unsaturated cyclic radical, which contains 3 to 6 ring atoms, of which 1 to 4 are from the group of oxygen, nitrogen and sulphur.

In some embodiments, the thiourea-based compound is cyclic thiourea.

In some embodiments, the selected triazole compatibilizing agent candidate selected after testing is a thioamide-based compound.

In some embodiments, the thioamide-based triazole compatibilizing agent candidate may include but is not limited to thioacetamide, thiobenzamide, furan thioamide, pyridine thioamide and polythioamide.

In some embodiments, the thioamide-based compound is selected from the group of thioacetamide, thiobenzamide, furan thioamide, pyridine thioamide and polythioamide. In some embodiments, the triazole compatibilizing agent candidate is sodium thiosulfate. In some embodiments, the triazole compatibilizing agent candidate is alkylamine. In some embodiments, the triazole compatibilizing agent candidate comprises one or more alkylamines.

In some embodiments, the alkylamine comprises one or more mono amines.

In some embodiments, the alkylamine is mono amine.

In some embodiments, the alkylamine is a diamine.

In some embodiments, the alkylamine is a polyamine.

In some embodiments, the polyamine is hexamethylene tetra amine. In some embodiments, the diamine is ethylene diamine.

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

(A) wherein:

(iii) R¹ is hydrogen, alkyl, aryl, alkenyl, alkynyl or heterocyclic; R² is hydrogen, alkyl, aryl, alkenyl, alkynyl or heterocyclic; and R³ is hydrogen, alkyl, aryl, alkenyl, alkynyl or heterocyclic; and

(iv) at least one of R¹, R², and R³ is alkyl, aryl , alkenyl, alkynyl or heterocyclic.

In some embodiments, two or more of, R¹, R², R³ are the same.

In some embodiments, each of R¹, R², R³ are different.

In some embodiments where one or more of R¹, R², R³ is alkyl, one or more alkyl is linear. In some embodiments, an alkyl is cyclic. In some embodiments, an alkyl is an alkyl fatty chain.

In some embodiments, R¹, R² and R³ are methyl.

In some embodiments, R¹, R² and R³ are ethyl.

In some embodiments, the R¹ and R² are H and R³ is C12 alkyl.

In some embodiments, the R¹ and R² are H and R³ is Cis alkenyl.

In some embodiments, the alkylamine is dodecyl amine.

In some embodiments, the alkylamine is benzyl amine.

In some embodiments, triazole compatibilizing agent is sodium thiosulfate.

In some embodiments, triazole compatibilizing agent is ethylene diamine.

In some embodiments, alkylamine is Butylamine.

In some embodiments, alkylamine is Diethyl amine.

In some embodiments, alkylamine is triethylamine as herein exemplified.

In some embodiments, triazole compatibilizing agent comprises thiourea.

In some embodiments, triazole compatibilizing agent comprises alkylamine

In some embodiments, triazole compatibilizing agent comprises ethylene diamine.

In some embodiments, alkylamine comprises Butylamine.

In some embodiments, alkylamine comprises Diethyl amine.

In some embodiments, alkylamine comprises Triethylamine

In some embodiments, the concentration of the azole (triazole), fungicide in the composition is between 1% to 10% ±10% 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% to 8% ±10% by weight based on the total weight of the composition. In some embodiments, the concentration of the azole fungicide in the composition is between 2.5% to 6% ±10% by weight based on the total weight of the composition. In some embodiments, the concentration of the azole fungicide in the composition is 3% ±10% by weight based on the total weight of the composition.

In some exemplified embodiments, the compositions comprise one or more additional fungicide which is soluble in the immiscible solvents/carriers of the composition and typically characterized by poor water solubility, having atypical solubility of less than about 25mg/L in water at 20°C. Typical instances of the additional fungicide are anilide or carboxamide fungicides, exemplified by fluxapyroxad and strobilurin fungicides exemplified by azoxy strobin and picoxystrobin. the concentration of the additional fungicide in the composition is between 1% to 10% ±10% by weight based on the total weight of the composition. In some embodiments, the concentration of the additional fungicide in the composition is between 2% to 8 ±10% by weight based on the total weight of the composition. In some embodiments, the concentration of the additional fungicide in the composition is between 2.5% to 7 ±10% by weight based on the total weight of the composition. In some exemplified embodiments, the concentration of the additional fungicide in the composition is 5.6 ±10% % by weight based on the total weight of the composition

The addition of an additive often affects the chemical and physical quality of the compositions.

In some embodiments, in addition to the inventive ingredients, the agriculturally acceptable additive is selected from, agriculturally acceptable, additional carriers; buffers; acidifiers; antifoaming agents; anti-freeze agents; solvents, co-solvents, light protecting agents, UV absorbers, radical scavengers and antioxidants, adhesives, neutralizers, thickeners, binders, sequestrates, biocides, drift retardants, surfactants, dispersants, pigments, wetting agents, safeners, and preservatives. Said additives include, but are not limited to, surfactants, pigments, wetting agents, as well as safeners, or such preservatives as bacteriostats or bactericides.

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

While the compositions of the invention are completely or essentially free of water, as mentioned previously, some of the inventive additives are supplied as aqueous solutions which account for a small content of water without detracting from the invention. In the majority of embodiments, the composition comprises no more than 10% by weight of water. In the great majority of embodiments, the composition comprises no more than 5% by weight of water, particularly selected from, less than 4%; less than 3%; less than 2% water; most notably, less than 1% water. In some embodiments, the composition comprises 0.01-3% by weight of water. In some embodiments, the composition comprises no more than 1% by weight of water.

In some most noted embodiments, the oil-based inventive OD composition comprises no added water and the only measurable water in the composition is due to the water associated or bound with individual ingredients before incorporation into the compositions.

In typical embodiments, the azole fungicide is dissolved in the water-immiscible carrier and/or solvent and the copper-based fungicide is suspended therein. In common embodiments, the azole (triazole), fungicide is dissolved in the water-immiscible (non-aqueous), carrier and/or solvent, compatibilized by the triazole compatibilizing agent, triethylamine and the copper-based fungicide is suspended therein.

In some embodiments, the additional fungicide is selected from the group of strobilurin fungicides, benzamide fungicide, morpholines, Qil fungicide, SDHI and any combination thereof.

In the following embodiments “essentially non-aqueous” indicates a water content below about 5% and typically much lower.

In an embodiment, the composition comprises an essentially non-aqueous combination of:

(1) copper-based fungicide,

(2) prothioconazole,

(3) picoxystrobin

(4) at least one water immiscible carrier and/or solvent, and

(5) triethylamine.

In some embodiments the composition is an OD concentrate.

(1) copper-based fungicide,

(2) prothioconazole,

(3) azoxy strobin

(4) at least one water immiscible carrier and/or solvent, and

(5) triethylamine.

In some embodiments the composition is an OD concentrate.

(1) copper-based fungicide,

(2) prothioconazole,

(3) fluxapyroxad

(4) at least one water immiscible carrier and/or solvent, and

(5) triethylamine. In some embodiments the composition is an OD concentrate.

(1) copper-based fungicide,

(2) tebuconazole,

(3) fluxapyroxad

(4) at least one water immiscible carrier and/or solvent, and

(5) triethylamine.

In some embodiments the composition is an OD concentrate.

(1) copper-based fungicide,

(2) Tebuconazole,

(3) picoxystrobin

(4) at least one water immiscible carrier and/or solvent, and

(5) triethylamine

In some embodiments the composition is an OD concentrate.

(1) copper-based fungicide,

(2) prothioconazole,

(3) picoxystrobin

(4) at least one water immiscible carrier and/or solvent, and

(5) lignosulfonate (SC-Dispersant).

(1) copper-based fungicide,

(2) prothioconazole,

(3) azoxy strobin

(4) at least one water immiscible carrier and/or solvent, and

(5) lignosulfonate (SC-Dispersant).

(1) copper-based fungicide,

(2) prothioconazole, (3) fluxapyroxad

(4) at least one water immiscible carrier and/or solvent, and

(5) lignosulfonate (SC-Dispersant).

(1) copper-based fungicide,

(2) tebuconazole,

(3) fluxapyroxad

(4) at least one water immiscible carrier and/or solvent, and

(5) lignosulfonate (SC-Dispersant).

(1) copper-based fungicide,

(2) Tebuconazole,

(3) picoxystrobin

(4) at least one water immiscible carrier and/or solvent, and

(5) lignosulfonate (SC-Dispersant).

(1) copper-based fungicide,

(2) prothioconazole,

(3) picoxystrobin

(4) at least one water immiscible carrier and/or solvent, and

(5) AMPS-ethylacrylate copolymer (SC-Dispersant).

(1) copper-based fungicide,

(2) prothioconazole,

(3) azoxy strobin

(4) at least one water immiscible carrier and/or solvent, and

(5) AMPS-ethylacrylate copolymer (SC-Dispersant). In an embodiment, the composition comprises an essentially non-aqueous combination of:

(1) copper-based fungicide,

(2) prothioconazole,

(3) fluxapyroxad

(4) at least one water immiscible carrier and/or solvent, and

(5) AMPS-ethylacrylate copolymer (SC-Dispersant).

(1) copper-based fungicide,

(2) tebuconazole,

(3) fluxapyroxad

(4) at least one water immiscible carrier and/or solvent, and

(5) AMPS-ethylacrylate copolymer (SC-Dispersant).

(1) copper-based fungicide,

(2) Tebuconazole,

(3) picoxystrobin

(4) at least one water immiscible carrier and/or solvent, and

(5) AMPS-ethylacrylate copolymer (SC-Dispersant).

(1) copper-based fungicide,

(2) prothioconazole,

(3) picoxystrobin,

(4) at least one water immiscible carrier and/or solvent,

(5) AMPS-ethylacrylate copolymer (SC-Dispersant), and

(6) lignosulfonate (SC-Dispersant).

(1) copper-based fungicide,

(2) prothioconazole,

(3) azoxy strobin

(4) at least one water immiscible carrier and/or solvent, (5) AMPS-ethylacrylate copolymer (SC-Dispersant), and

(6) lignosulfonate (SC-Dispersant).

(1) copper-based fungicide,

(2) prothioconazole,

(3) fluxapyroxad

(4) at least one water immiscible carrier and/or solvent,

(5) AMPS-ethylacrylate copolymer (SC-Dispersant), and

(6) lignosulfonate (SC-Dispersant).

(1) copper-based fungicide,

(2) tebuconazole,

(3) fluxapyroxad

(4) at least one water immiscible carrier and/or solvent,

(5) AMPS-ethylacrylate copolymer (SC-Dispersant), and

(6) lignosulfonate (SC-Dispersant).

(1) copper-based fungicide,

(2) Tebuconazole,

(3) picoxystrobin

(4) at least one water immiscible carrier and/or solvent,

(5) AMPS-ethylacrylate copolymer (SC-Dispersant), and

(6) lignosulfonate (SC-Dispersant).

(1) copper-based fungicide,

(2) prothioconazole,

(3) picoxystrobin,

(4) at least one water immiscible carrier and/or solvent,

(5) AMPS-ethylacrylate copolymer (SC-Dispersant), (6) lignosulfonate (SC-Dispersant), and

(7) triethylamine.

(1) copper-based fungicide,

(2) prothioconazole,

(3) azoxy strobin

(4) at least one water immiscible carrier and/or solvent,

(5) AMPS-ethylacrylate copolymer (SC-Dispersant),

(6) lignosulfonate (SC-Dispersant), and

(7) triethylamine.

(1) copper-based fungicide,

(2) prothioconazole,

(3) fluxapyroxad

(4) at least one water immiscible carrier and/or solvent,

(5) AMPS-ethylacrylate copolymer (SC-Dispersant),

(6) lignosulfonate (SC-Dispersant), and

(7) triethylamine.

(1) copper-based fungicide,

(2) tebuconazole,

(3) fluxapyroxad

(4) at least one water immiscible carrier and/or solvent,

(5) AMPS-ethylacrylate copolymer (SC-Dispersant),

(6) lignosulfonate (SC-Dispersant), and

(7) triethylamine.

(1) copper-based fungicide,

(2) Tebuconazole,

(3) picoxy strobin (4) at least one water immiscible carrier and/or solvent,

(5) AMPS-ethylacrylate copolymer (SC-Dispersant),

(6) lignosulfonate (SC-Dispersant), and

(7) triethylamine.

In the above exemplified embodiments, the copper-based fungicide is suspended in the at least one water immiscible carrier and/or solvent; and the triazole fungicide and additional fungicides are dissolved in the at least one water immiscible carrier or solvent, wherein the triazole fungicide has been compatibilized with the tri ethylamine.

In the above exemplified embodiments, the copper-based fungicide is suspended in the at least one water immiscible carrier and/or solvent; and the compatibilized triazole fungicide and additional fungicides are dissolved in the at least one water immiscible carrier or solvent.

As is usual in all agricultural composition formulation, care must be taken to choose components that are compatible with the other ingredients of the compositions being formulated. That being said, in each of the above embodiments the at least one water immiscible carrier and/or solvent can usefully be selected from any one, or a mixture of more than one, selected from the group of aromatic hydrocarbons (e.g. toluene, o-, m-, p-xylene, ethylbenzene, isopropylbenzene, tert-butylbenzene, naphthalenes, mono- or polyalkylsubstituted naphthalenes), paraffins (e.g. octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, hepta-decane, octa-decane, nona-decane, eicosane, heneicosane, docosane, tricosane, tetracosane, pentacosane, and branched chain isomers thereof), petroleum, ketones (e.g. acetophenone, cyclohexanone), vegetable oil (e.g. olive oil, kapok oil, castor oil, papaya oil, camellia oil, palm oil, sesame oil, com oil, rice bran oil, peanut oil, cotton seed oil, soybean oil, rapeseed oil, linseed oil, tung oil, sunflower oil, safflower oil, tall oil), alkyl ester of vegetable oils, (e.g. rapeseed oil methyl ester or rapeseed oil ethyl ester, rapeseed oil propyl esters, rapeseed oil butyl esters, tall oil fatty acids esters etc...), diesel, mineral oil, fatty acid amides (e.g. C1-C3 amines, alkylamines or alkanolamines with G, - Cis carboxylic acids), dimethylamide of fatty acid, N,N- dimethyl alkylamide (N,N-dimethyl decanamide, N,N- dimethyl octanamide, N, N-dimethyl dodecanamide, N,N-dialkyl alkanamide), N-alkyl alkanamide, fatty acids, tall oil fatty acids, alkyl esters of fatty acids (e.g. C1-C4 monohydric alcohol esters of Cx to C22 fatty acids such as methyl oleate, ethyl oleate), modified vegetable oils and combinations thereof.

To be clear, compositions that include destabilizing ingredients that damage, reverse or otherwise function to lessen or remove some if not all of the advantages attributable to the invention, are not favored. However, inventors can foresee specific formulation constraints which may require a formulator to include these less than optimal ingredients, and thus inventors point out that simply adding a less favored ingredient to the inventive oil-based composition will not exclude that composition from the scope of the invention and may be within the scope of protection being sought. This is especially (though not exclusively), the case where the less-favored ingredient, has been added in an amount that does not adversely affect the invention.

Oil-based compositions comprising all the inventive components that have been “sabotaged” or compromised by the inclusion of known damaging ingredients so that all the inventive advantages have been “lost”, are to be considered as outside the scope of the invention and not any indication that some of the claimed compositions are “non-working”. Inventors consider this disclosure as being directed to skilled formulators who would make reasonable efforts to prepare useful compositions, a composition that ignored the basic principles of the art of formulation are not preferred embodiments.

In a particular embodiment, the water immiscible carrier may include but is not limited to aromatic hydrocarbons, fatty acid amides, alkyl ester of vegetable oils and vegetable oils.

In some embodiments, water immiscible carrier is exemplified by acetophenone.

In some embodiments, water immiscible carrier is exemplified by fatty acid amides.

In some embodiments, water immiscible carrier is exemplified by N,N-

Dimethyldecanamide .

In some embodiments, water immiscible carrier is exemplified by methyl soyate.

In some embodiments, water immiscible carrier is exemplified by aromatic hydrocarbons.

In some embodiments, water immiscible carrier is exemplified by vegetable oil.

In an embodiment, the oil-based composition comprises an essentially non-aqueous combination of:

(1) copper-based fungicide,

(2) prothioconazole, (3) picoxystrobin,

(4) aromatic hydrocarbons CAS 64742-94-5,

(5) methyl soyate CAS 67784-80-9,

(6) dimethyl decanamide CAS 14433-76-2

(7) AMPS-ethylacrylate copolymer (SC-Dispersant),

(8) lignosulfonate (SC-Dispersant), and

(9) triethylamine.

(1) copper-based fungicide,

(2) prothioconazole,

(3) azoxy strobin

(4) aromatic hydrocarbons CAS 64742-94-5,

(5) methyl soyate CAS 67784-80-9,

(6) dimethyl decanamide CAS 14433-76-2

(7) AMPS-ethylacrylate copolymer (SC-Dispersant),

(8) lignosulfonate (SC-Dispersant), and

(9) triethylamine.

(1) copper-based fungicide,

(2) prothioconazole,

(3) fluxapyroxad

(4) aromatic hydrocarbons CAS 64742-94-5,

(5) methyl soyate CAS 67784-80-9,

(6) dimethyl decanamide CAS 14433-76-2

(7) AMPS-ethylacrylate copolymer (SC-Dispersant),

(8) lignosulfonate (SC-Dispersant), and

(9) triethylamine.

(1) copper-based fungicide,

(2) tebuconazole,

(3) fluxapyroxad (4) aromatic hydrocarbons CAS 64742-94-5,

(5) methyl soyate CAS 67784-80-9,

(6) dimethyl decanamide CAS 14433-76-2

(7) AMPS-ethylacrylate copolymer (SC-Dispersant),

(8) lignosulfonate (SC-Dispersant), and

(9) triethylamine.

(1) copper-based fungicide,

(2) tebuconazole,

(3) picoxystrobin,

(4) aromatic hydrocarbons CAS 64742-94-5,

(5) methyl soyate CAS 67784-80-9,

(6) dimethyl decanamide CAS 14433-76-2,

(7) AMPS-ethylacrylate copolymer (SC-Dispersant),

(8) lignosulfonate (SC-Dispersant), and

(9) triethylamine (triazole compatibilizing agent).

In an embodiment, the oil-based composition comprises an essentially non-aqueous combination of

(1) copper-based fungicide, suspended in a solution of compatibilized prothioconazole and picoxystrobin, in aromatic hydrocarbons, methyl soyate dimethyl decanamide,

(2) AMPS-ethyl acrylate copolymer and lignosulfonate (SC-Dispersants), and

(3) triethylamine (triazole compatibilizing agent), wherein the prothioconazole has been compatibilized by the triethylamine.

(1) copper-based fungicide, suspended in a solution of compatibilized prothioconazole and azoxystrobin, in aromatic hydrocarbons, methyl soyate dimethyl decanamide,

(2) AMPS-ethyl acrylate copolymer and lignosulfonate (SC-Dispersants), and

(3) triethylamine (triazole compatibilizing agent), wherein the prothioconazole has been compatibilized by the triethylamine. In an embodiment, the oil-based composition comprises an essentially non-aqueous combination of

(1) copper-based fungicide, suspended in a solution of compatibilized prothioconazole and fluxapyroxad, in aromatic hydrocarbons, methyl soyate dimethyl decanamide,

(2) AMPS-ethyl acrylate copolymer and lignosulfonate (SC-Dispersants), and

(1) copper-based fungicide, suspended in a solution of compatibilized tebuconazole and fluxapyroxad, in aromatic hydrocarbons, methyl soyate dimethyl decanamide,

(2) AMPS-ethyl acrylate copolymer and lignosulfonate (SC-Dispersants), and

(3) tertiary amine (triazole compatibilizing agent), wherein the tebuconazole has been compatibilized by the triazole compatibilizing agent.

(1) copper-based fungicide, suspended in a solution of compatibilized tebuconazole and picoxystrobin, in aromatic hydrocarbons, methyl soyate dimethyl decanamide,

(2) AMPS-ethyl acrylate copolymer and lignosulfonate (SC-Dispersants), and

(1) copper-based fungicide,

(2) prothioconazole,

(3) picoxystrobin,

(4) aromatic hydrocarbons CAS 64742-94-5,

(5) methyl soyate CAS 67784-80-9,

(6) dimethyl decanamide CAS 14433 -76-2, and

(7) triethylamine. In an embodiment, the oil-based composition comprises an essentially non-aqueous combination of:

(1) copper-based fungicide,

(2) prothioconazole,

(3) azoxy strobin

(4) aromatic hydrocarbons CAS 64742-94-5,

(5) methyl soyate CAS 67784-80-9,

(6) dimethyl decanamide CAS 14433-76-2, and

(7) triethylamine.

(1) copper-based fungicide,

(2) prothioconazole,

(3) fluxapyroxad

(4) aromatic hydrocarbons CAS 64742-94-5,

(5) methyl soyate CAS 67784-80-9,

(6) dimethyl decanamide CAS 14433-76-2, and

(7) triethylamine.

(1) copper-based fungicide,

(2) tebuconazole,

(3) fluxapyroxad

(4) aromatic hydrocarbons CAS 64742-94-5,

(5) methyl soyate CAS 67784-80-9,

(6) dimethyl decanamide CAS 14433-76-2, and

(7) triethylamine.

(1) copper-based fungicide, (2) tebuconazole,

(3) picoxystrobin,

(4) aromatic hydrocarbons cas 64742-94-5,

(5) methyl soyate cas 67784-80-9,

(6) dimethyl decanamide cas 14433-76-2, and

(7) triethylamine (triazole compatibilizing agent). in an embodiment, the oil-based composition comprises an essentially non-aqueous combination of:

1) copper oxychloride

2) picoxystrobin

3) prothioconazole

4) polydimethylsiloxanes

5) oxirane, monobutyl ether (Atlas g-50021-1 q-(cq))

6) fumed silica (cab-o-sil® m5)

7) co-polymer of 2-acrylamido-2 -methylpropane sulfonic acid (amps) monomers and ethyl acrylate monomers (AMPS-EA)

8) n,n-dimethyl decanamide, (Hallcomid m-10)

9) lignosulfonic acid, sodium salt, sulfomethylated (Reax 88a)

10) benzenesulfonic acid, cio-i3-(linear)alkyl derivatives, calcium salt, (Rhodacal 60/BE)

11) hydrocarbons, cio, aromatics (Solvesso 150)

12) tri styrylphenol ethoxylated (Soprophor bsu)

13) tri ethylamine

14) polyoxyethylene (20) sorbitan monolaurate (Tween 24-lq-(ap))

15) methylated soybean oil

The term “essentially non-aqueous” in the composition and/or combination embodiments including those mentioned above refers to a combination or composition wherein the content of water is 5% or less. Commonly the % water content in oil-based concentrated embodiments, is significantly lower than 5%.

In an embodiment, the amount of the one or more water immiscible earner or solvent may be 2-60 wt.% ±10%, 10-50wt. % ±10%„ or 12-40wt.% ±10%„ or 20-40% ±10%, based on the total weight of the composition. In several exemplified embodiments, the non-aqueous liquid carrier/solvent may be present in a concentration of about 35% ±10%, by weight based upon the total weight of the composition and typically comprised of a mixture of more than one nonaqueous liquid carrier/solvent.

In some embodiments, the composition comprises - excipients in addition to the above detailed inventive ingredients, bearing in mind that as in all agricultural composition formulation, care must be taken to choose components that are compatible with the other ingredients of the compositions being formulated.

In some embodiments, the excipients which may be referred to as adjuvants, additives or excipients in the composition may include but are not limited to alkoxylated sorbitan esters such as for example sorbitan monolaurate alkoxylates such as for example polyoxyethylene (16) sorbitan monolaurate (Tween™ 24), polyoxyethylene (20) sorbitan monolaurate (Tween™ 20; Alkamuls® PSML-20), polyoxyethylene (4) sorbitan monolaurate (Tween™ 21), polyoxyethylene (8) sorbitan monolaurate (Tween™ 22), polyoxyethylene (12) sorbitan monolaurate (Tween™ 23), sorbitan monolaurate (Alkamuls® S/20, Glycomul® LK, Glycomul® LC, Span® 20), polyoxyethylene (20) sorbitan monostearate alkoxylates such as for example_polyoxyethylene (20) sorbitan monostearate (Tween™ 60), polyoxyethylene (4) sorbitan monostearate (Tween™ 61), sorbitan monostearate (Alkamuls® S/90, Glycomul® S, Span® 60), sorbitan monooleate alkoxylates such as for example polyoxyethylene (20) sorbitan monooleate (Tween™ 80, Emulgin® SMO 20, T-Maz® 80, Agnique® SMO 20U), polyoxyethylene (5) sorbitan monooleate (Tween™ 81), sorbitan monooleate (Alkamuls® S/80, Span® 80), polyalkylene oxide polymer, polyalkylene oxide block copolymer, polyalkoxylated alkyl ether exemplified by butyl polyethylene oxide-polypropylene block copolymer e.g., Atlas™ G5002L, Synergen SOC, Ethoxylated C12-C15 fatty alcohol ± butyl end-capped EO-PO Block copolymer, Atlox® 4894, biocide (preservative); anti-foaming agents, thickeners, drift retardants, pH adjuster or buffering agent such as organic or inorganic bases and/or organic or inorganic acids, biocide (preservative), defoaming agents, thickeners, drift retardants, wetting agents e.g., di-octylsulphosuccinate, polyoxyethylene/polypropylene oxide, ethoxylated tristyrylphenol, ethoxylated tristyrylphenol sulphate, ethoxylated tristyrylphenol phosphate, ethoxylated propoxylated tristyryl phenol, and. A composition of the invention may also comprise two or more different wetting agents and combinations thereof. The above list is clearly illustrative and in no way even close to exhaustive and inadvertent omission of a common ingredient or even a class of excipient has no intended significance. By the same token, inadvertent inclusion of an unsuitable common ingredient or even a class of excipient has no intended significance as the above list is merely intended to illustrate the wide range of additives, excipients etc. that are available for formulating, while some of these have been successfully used in embodiments of the inventive compositions and combinations, it is expected that a formulator will first check the compatibility of a chosen additive before use and not consider the above list as recommending each and every ingredient for all possible permutations of the inventive combinations and compositions.

In some embodiments, the composition comprises one or commonly at least two surface active materials.

In some embodiments, wetting agent is alkoxylated alcohol and a di-block EO/PO block copolymer exemplified by Atlox® 4894.

In some embodiments, the dispersant is an anionic polymeric surfactant exemplified by Atlox® Metasperse 500L.

In some embodiments, the excipient is an anionic dispersant exemplified by Geropon® T-77.

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

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

A thickening agent, when present, is preferably selected from agar, alginic acid, alginate, carrageenan, gellan gum, xanthan gum, succinoglycan gum, guar gum, acetylated distarch adipate, acetylated oxidised starch, arabinogalactan, ethyl cellulose, methyl cellulose, locust bean gum, starch sodium octenylsuccinate, and triethyl citrate. A composition of the invention may also comprise two or more different thickening agents.

In some embodiments, the thickener is xanthan gum. In some embodiments, the rheology modifier is Agrhopol 23, Rhodopol® 23 (sold by Solvay). In some embodiments, the rheology modifier is xanthan gum.

In some embodiments, the antifoaming agent is SAG 1572.

In some embodiments, the composition comprises at least one thickener and at least one biocide.

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

In some embodiments, the preservative is a biocide. In some embodiments, the composition comprises at least one biocide. In some embodiments, the preservative is Acticide® MBS, Proxel®, 2-methyl-4-isothiazolin-3-one (MIT) and/or l,2-benzisothiazolin-3-one .

As previously alluded to, compositions according to the invention may comprise another bioactive ingredient, such as a growth regulator, a bio-stimulant, a fungicide, a herbicide, an insecticide, an acaricide, a molluscicide, a miticide, a rodenticide; and/or an bactericide.

Various agrochemicals may be used as additional bioactive ingredient. Exemplary among such agrochemicals without limitation are crop protection agents, for example pesticides, safeners, plant growth regulators, repellents, bio-stimulants and preservatives such as bacteriostats or bactericides.

In some embodiments, the composition comprises at least one additional bioactive ingredient, commonly, an additional insecticide, fungicide and/or herbicide.

Additional agrochemicals that may be used with the combination and composition of the present invention are described below.

The present invention inter aha provides typical non-aqueous compositions comprising combinations of ingredients containing at least one member of each of,

(i) at least one Copper Al component;

(ii) at least one Azole (triazole) Al component

(iii) at least one non-aqueous carrier or solvent, and (iv) tertiary alkylamine especially triethylamine. The present invention inter alia provides typical non-aqueous compositions comprising combinations of ingredients containing at least one member of each of,

(i) at least one copper Al component;

(ii) at least one azole (triazole) Al component

(iii) at least one non-aqueous carrier or solvent,

(iv) SC-dispersant which is typically insoluble or often no more soluble than O.Olg/L in the non-aqueous carrier or solvent and/or

(v) alkylamine especially triethylamine.

Typical, essentially non-aqueous (<5% water) compositions of the invention may for example contain representative ingredients chosen from these classes, exemplified by,

(1) Copper oxychloride tech (Invention Copper Al component)

(2) Prothioconazole or Tebuconazole (Invention Azole Al component)

(3) Acetophenone (Invention non-aqueous carrier/solvent)

(4) Dimethyl Decanamide (Invention non-aqueous carrier/solvent)

(5) Fatty acid alkyl esters, Methyl Soyate etc (Invention non-aqueous carrier/solvent)

(6) Aromatic hydrocarbons (Invention non-aqueous carrier/solvent)

(7) Lignosulfonate salt e.g., Ca or Na salt (Inventive SC-dispersant)

(8) Co-polymer of 2-Acrylamido-2 -methylpropane sulfonic acid (AMPS) monomers and ethyl acrylate monomers (Inventive SC-dispersant)

(9) copolymers of styrene and methacrylic acid monomers (Inventive SC-dispersant).

As previously alluded to, OD compositions of the invention may also contain any of the ingredients below or similar alternatives without in any way departing from the invention,

(10) picoxystrobin, azoxystrobin, or fluxapyroxad (optional additional ai component)

(11) Acetic Acid (Optional acidifying additive)

(12) Agnique BP 420 (Optional additive)

(13) Agsolex 8 (Optional additive)

14Chitosan (Optional additive)

(15) Propylene glycol (Optional antifreeze additive)

(16) Proxel GXL (Optional preservative additive) (17) SAG 1572 (Optional antifoaming agent)

(18) sodium acetate (Optional buffer additive)

(19) Soprophor TS/16 (Optional surfactant additive)

(20) Synergen SOC (Optional additive)

(21) smectite clay, silicon Dioxide (Optional thickener additive)

(22) Polydimethylsiloxane(Optional antifoam additive)

Method and uses

The present invention provides methods of preparing superior non-aqueous compositions of combinations of and copper-based fungicide(s) and azole fungicide, in immiscible carriers/solvents. the method comprises adding a compound selected from the group of SC- dispersant additives and/or alkylamine, especially triethylamine and any combination thereof to the composition. A preference is noted for the addition of both, at least one SC-dispersant and triethylamine.

To be clear in some embodiments, the term “adding” refers to causing the ingredient in question to be in a combined state with others rather than necessitating a physical addition-activity such as pouring and can sometimes be replaced with “introducing” no specific inference should be taken from this textural convenience. It will be obvious to those skilled in these formulation arts, that in many cases the exact order in which components of the inventive compositions are combined will not negate the advantages realized by the inventive compositions. However, it is equally clear that some order of addition steps will be more optimal than others, often simply because of processing considerations, but also inventors have contemplated different levels of advantages might be realized comparing a composition produced using one order of addition than another.

Process

The present invention provides process for producing superior non-aqueous compositions comprising a copper-based fungicide and azole fungicide in at least one water immiscible carrier and/or solvent. Below is presented an example of the process comprising the following steps using some typical ingredients simply for illustrative purposes:

(a) In a tank with agitation, add

(i) Aromatic hydrocarbons, (ii) Dimethyl Decanamide,

(iii) Prothioconazole and

(iv) Picoxystrobin,

(b) agitate, optionally with heating until complete Al solubilization.

(c) add,

(v) Polyethylene-Polypropylene Glycol butyl ether Block polymer,

(vi) Tristyrylphenol ethoxylate,

(vii) Tween 20

(viii) Antifoam,

(ix) Dodecylbenzene sulfonic acid calcium salt

(x) AMPS-Ethylacrylate block co-polymer

(xi) Methyl Soyate

(xii) Sodium lignosulfonate and if needed, cool down to below 35°C

(d) add

(xiii) Triethylamine

(xiv) Copper Oxychloride and/or Chelated Copper

(xv) Fumed Silicon Dioxide and agitate at high speed exemplified by greater than 1000 rpm to homogenize,

(xi) sieve to remove excessively large solids through a 100 mesh screen.

In some embodiments, the process includes a step of milling or grinding the solid suspended particles of copper-based fungicide to reduce their particle size typically during the above mentioned homogenization step or size reduction occurs due to the intensity of the homogenization action.

In some embodiments, the resultant suspended copper-based fungicide particles size distribution is characterized by a D90 of 10 microns or less and a D50 of 5 microns or less.

In some embodiments, the ingredients are incorporated in a different order of addition, without any departure from the invention

In some embodiments, the composition is in the form of a non-aqueous concentrate comprising a non-aqueous solution of azole and strobilurin combined with suspended copper-based fungicide in a water immiscible carrier and SC-dispersant insoluble in the carrier and triethylamine. These concentrated compositions are often indistinguishable from Oil Dispersion concentrates for all practical purposes, as they contain less than 5% water, preferably less than 1% water, and especially in the absence of measurable amounts of water even if some active components are in dissolved form in the water immiscible carrier.

In some embodiments, the water immiscible carrier is fatty acid amide exemplified by N,N- dimethyldecanamide .

In some embodiments, the organic phase includes at least one water immiscible carrier/solvent/co-solvent such as N,N-Dimethyldecanamide, and/or methyl soyate, and/or aromatic hydrocarbons.

Azole fungicide

In some embodiments, azole (triazole) fungicide may include but is not limited to climbazole, clotrimazole; imazalil; oxpoconazole; prochloraz; triflumizole; viniconazole; azaconazole; bromuconazole; cyproconazole; diclobutrazol; difenoconazole; diniconazole; diniconazole-M; epoxiconazole; etaconazole; fenbuconazole; fluconazole; fluoxytioconazole; fluquinconazole; flusilazole; flutriafol; furconazole; furconazole-cis; hexaconazole; imibenconazole; ipconazole; ipfentrifluconazole; mefentrifluconazole; metconazole; myclobutanil; penconazole; propiconazole; prothioconazole; quinconazole; simeconazole; tebuconazole; tetraconazole; triadimefon; triadimenol; triticonazole; uniconazole; uniconazole-P their salts, esters, isomers and derivatives thereof.

In some embodiments, the azole fungicide is tebuconazole

In some embodiments, the azole fungicide is prothioconazole

In some embodiments, the azole fungicide is cyproconazole In some embodiments, the azole fungicide is difenoconazole

Additional fungicide

In some embodiments, the additional fungicide is selected from the group of strobilurin fungicides, benzamide fungicide, morpholines, Qil fungicide, SDHI and any combination thereof In some embodiments, strobilurin fungicide may include but is not limited to azoxystrobin, coumoxystrobin, enoxastrobin, flufenoxystrobin, picoxystrobin, pyraoxystrobin, mandestrobin, pyraclostrobin, pyrametostrobin, triclopyricarb, kresoxim-methyl, trifloxystrobin, dimoxystrobin, fenaminstrobin, metominostrobin, orysastrobin, metyltetraprole and fluoxastrobin.

In some embodiments, the strobilurin fungicide is selected from group of picoxystrobin, trifloxystrobin, azoxystrobin, pyraclostrobin, metominostrobin, metyltetraprole, mandestrobin and a combination thereof.

In some embodiments, the strobilurin fungicide is picoxystrobin

In some embodiments, the strobilurin fungicide is azoxystrobin

In some embodiments, the SDHI may include but is not limited to penthiopyrad, boscalid, flutolanil, fluxapyroxad, inpyrfluxam , fluopyram, fluindapyr, benzodiflupyr, bixafen and pydiflumetofen

In some embodiments, the SDHI fungicide is selected from group of bixafen; fluxapyroxad, fluindapyr; inpyrfluxam, benzodiflupyr and pydiflumetofen.

In some embodiments, the SDHI fungicide is fluxapyroxad

In some embodiments, Qil fungicide may include but is not limited to cyazofamid, amisulbrom and fenpicoxamid.

In some embodiments, Qil is fenpicoxamide.

In some embodiments, morpholines may include but is not limited to aldimorph, fenpropimorph, tridemorph, dodemorph, spiroxamine, piperalin, fenpropidin.

Copper-based fungicide

In some embodiments, the copper-based fungicide is selected from the group of cupric acetate, cupric chloride, cupric chlorate, cupric formate, cupric hexafluoro silicate, cupric nitrate, cupric chromate, copper sulfate pentahydrate, Bordeaux mixture, copper hydroxide, cuprous oxide, copper oxychloride, copper oxychloride sulfate (COCS), tribasic copper sulfate such as cupric sulfate, tricupric hydroxide, hemihydrate, complexed or chelated copper compounds, and any combination thereof. When the copper-based fungicidal compound comprises chelated copper the chelated copper comprises no more than 5% by weight of the total copper in the composition. In some embodiments, the copper-based fungicide may be but not limited to cupric acetate, cupric chloride, cupric chlorate, cupric formate, cupric hexafluorosilicate, cupric nitrate, cupric chromate, copper sulfate pentahydrate, bordeaux mixture, copper hydroxide, cuprous oxide, copper oxychloride, copper oxychloride sulfate (COCS), tribasic copper sulfate such as cupric sulfate, tricupric hydroxide, hemihydrate, or any combination thereof.

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

In some embodiments, the copper-based fungicide is bordeaux mixture.

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

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

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

As used herein, the term “copper-based fungicide" refers to copper salt such as copper sulfate, copper hydroxy chloride, and copper oxide, copper oxychloride, copper oxychloride sulfate. As used herein, the term "metallic copper" typically refers to Cu²⁺ cation as was previously described.

Methods of Use

The present invention also provides method for controlling fungicidal disease comprising applying an effective amount of any one of the herein described combination and/or composition to a plant, a locus thereof, propagation material thereof, or an area infested with the unwanted insects so as to thereby control the pathogen disease.

Controlling refer to preventing curative and persistence.

The present invention also provides a method for controlling plant disease caused by pathogen comprising applying an effective amount of any one of the herein described combination and/or composition and/or diluted composition to a plant, a locus thereof, propagation material thereof, or an area infested with the unwanted insect so as to thereby control the plant disease caused by pathogen.

In some embodiments, the locus of the plant is the vicinity of the plant.

In some embodiments, the area infested with the pathogen. In some embodiments the present invention provides a method for controlling pathogen infection comprising applying a OD composition (typically after dilution/dispersion in water), comprising (1) an amount of copper-based fungicide, (2) an amount of azole fungicide and (3) at least one immiscible carrier/solvent, wherein the composition is formulated with at least one additive selected from a group comprising tertiary amines exemplified by triethylamine.

In some embodiments the present invention provides a method for controlling pathogen infection comprising applying a OD composition (typically after dilution/dispersion in water), comprising (1) an amount of copper-based fungicide, (2) an amount of azole fungicide (3) at least one water immiscible carrier/solvent, and (4) at least one additive selected from a group comprising oil insoluble SC-dispersant(s) wherein the composition is formulated withat least one additive selected from a group comprising tertiary amines exemplified by triethylamine.

In some embodiments the present invention provides a method for controlling pathogen infection comprising applying a OD composition (typically after dilution/dispersion in water), comprising (1) an amount of copper-based fungicide, (2) an amount of azole fungicide (3) at least one water immiscible carrier/solvent, and (4) at least one additive selected from a group comprising oil insoluble SC-dispersant(s) wherein the composition is formulated with triethylamine.

In some embodiments the present invention provides a method for controlling pathogen infection comprising applying a OD composition (typically after dilution/dispersion in water), comprising (1) an amount of copper-based fungicide, (2) an amount of azole fungicide (3) at least one water immiscible carrier/solvent, and (4) at least one additive selected from a group comprising oil insoluble SC-dispersant(s).

When discussing combinations compositions mixtures etc. the term “oil insoluble SC- dispersant” as herein disclosed is generally characterized by requiring at least 1,000 parts, and preferably, greater than 10,000 parts of said one or more water immiscible carrier or solvent to dissolve one part of said SC-dispersant and said SC-dispersant displays minimal or negligible solubility in the non-aqueous composition,

The present invention also provides use of the combination and/or composition, described herein for treating a plant, or a part of a plant, against a pathogen or preventing or delaying infection by a pathogen. The present invention provides a method of treating a plant, or a part of a plant, against a pathogen or preventing or delaying infection or infestation by a pathogen, comprising contacting the plant, or part of the plant, with any one or any combination and/or composition described herein.

In some embodiments, treating comprises preventing, reducing and/or eliminating the presence of the pathogen on the plant, or part of the plant. In some embodiments, treating comprises controlling diseases caused by the pathogen.

As alluded to, in some embodiments, the method of treating the plant, or the part of a plant against a pathogen comprises protecting the plant, or a part of a plant, against the pathogen, comprising contacting the plant, or part of the plant, with any one of any combination, and/or composition, described herein.

In some embodiments, the method of treating the plant, or the part of a plant against a pathogen comprises preventing, reducing and/or eliminating the presence of the pathogen on the plant, or part of the plant, comprising contacting the plant, or part of the plant, with any one of any combination and/or composition described herein.

In some embodiment, the method of treating the plant, or the part of a plant against a pathogen comprises controlling diseases caused by phytopathogenic fungi in plants or on propagation material thereof, which method comprises contacting the plants, or propagation material thereof, with any one of any combination and/or composition described herein.

In some embodiments, the method of treating the plant, or the part of a plant against a pathogen comprises improving pest control comprising applying any one of any combination and/or composition described herein to a plant/or soil.

In some notable embodiments, the pathogen is phytopathogenic fungi and the method comprises controlling diseases caused by phytopathogenic fungi in the plant or on propagation material thereof comprising contacting the plant, or propagation material thereof, with any one of any combination and/or composition described herein.

In some embodiments, the method of treating the plant, or the part of a plant against a pathogen comprises preventing, reducing and/or eliminating the presence of the pathogen on the plant, or part of the plant, or areas intended for the cultivation of plants, comprising contacting the plant, or part of the plant, or said area, with any one of any combination and/or composition, described herein The invention further provides a method of controlling diseases caused by phytopathogenic fungi in plants or on propagation material thereof, which method comprises contacting the plants, or propagation material thereof, with a composition according to the invention.

Rates of application may refer to application rates of the additional fungicide (when included in the composition) exemplified by anilide/carboxamide fungicides, exemplified by fluxapyroxad and strobilurin fungicides exemplified by azoxystrobin and picoxystrobin, selected from any of, between about 22 g a.i./ha (a.i.)/ha to about 2.2 g a.i./ha; 0.22g a.i./ha ±10%; 0.022g a.i./ha ±10%; 0.0022g a.i./ha ±10%; 750 g a.i./ha ±10%; 450g a.i./ha ±10%; 375 g a.i./ha ±10%; 150 g a.i./ha ±10%; 15 g a.i./ha ±10%; 2.9g a.i./L ±10%, 11.6g a.i./L, 0.0022 g a.i./ha ±10%, to 0.75 kg a.i./ha ±10%. Rate of application may refer to an application rate of 22 g a.i./ha to 2.2 g a.i./ha of the additional fungicide. In some embodiments, the copper-based fungicide is applied at a rate of 750 g a.i./ha ±10%„ 605 g a.i./ha ±10%„ or 500 g a.i./ha ±10%.

In some embodiments, the combination and/or composition is applied at an amount of 0.01- 5 g/ha ±10%, of the copper-based fungicide. In some embodiments, the combination and/or composition, is applied at an amount of 0.01-3 g/ha ±10%, of the copper-based fungicide. In some embodiments, the combination and/or composition, is applied at an amount of 0.01-2 g/ha ±10%, of the copper-based fungicide. In some embodiments, the combination and/or composition, is applied at an amount of 0.01 - Ig/ha ±10%, of the copper-based fungicide.

In some embodiments, the combination and/or composition, is applied at an amount , of 0.018 g/ha ±10% of copper-based fungicide. In some embodiments, the combination and/or composition, is applied at an amount of 0.97 g/ha ±10% of copper-based fungicide. In some embodiments, the combination and/or composition, is applied at an amount of 0.39 g/ha ±10% of copper-based fungicide. In some embodiments, the combination and/or composition, is applied at an amount of 1 .56 g/ha ±10% of copper-based fungicide.

In some embodiments, the combination and/or composition, is applied at amounts with a range of ±10% (“about”), of between 0.00 Ig/ha to 1000 g/ha of copper metal. In some embodiments, the combination and/or composition, is applied at an amount between lOOg/ha to 1000 g/ha of copper metal. In some embodiments, the combination and/or composition, is applied at an amount between 100 g/ha to 500 g/ha of copper metal. In some embodiments, the combination and/or composition, is applied at an amount between 500 g/ha to 1000 g/ha of copper metal. In some embodiments, the combination and/or composition, is applied at an amount between O.OOlg/ha to 100 g/ha of copper metal. In some embodiments, the combination and/or composition, is applied at an amount between O.OOlg/ha to 50 g/ha of copper metal. In some embodiments, the combination and/or composition, is applied at an amount between O.OOlg/ha to 25 g/ha of copper metal. In some embodiments, the combination and/or composition, is applied at an amount between O.OOlg/ha to 10 g/ha of copper metal all values, as alluded to previously, being understood to include ±10% (i.e., about), of that value.

In some embodiments, the combination and/or composition, is applied at 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, all values, as alluded to previously, being understood to include ±10% (i.e., about)

In some embodiments, the combination and/or composition, is applied at 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.

In some embodiments, the combination and/or composition, is applied at an amount of about 0.0052 g/ha of copper metal. In some embodiments, the combination and/or composition, is applied at an amount of about 0.001 g/ha of copper metal. In some embodiments, the combination and/or composition, is applied at an amount of about 0.059 g/ha of copper metal. In some embodiments, the combination and/or composition, is applied at an amount of about 0.0095 g/ha of copper metal.

In some embodiments, the combination and/or composition, is applied at an amount of about 15 g/ha of copper metal. In some embodiments, the combination and/or composition, is applied at an amount of about 150 g/ha of copper metal. In some embodiments, the combination and/or composition, is applied at an amount of about 375 g/ha of copper metal. In some embodiments, the combination and/or composition, is applied at an amount of about 450 g/ha of copper metal. In some embodiments, the combination and/or composition, is applied at an amount of about 750 g/ha of copper metal.

A composition and/or combination according to the invention is suitable for the control of pests that are encountered in horticulture, agriculture, and forestry. The compositions are active against normally sensitive and resistant pest species and during all or individual stages of development. Prior to use, a composition comprising a copper-based fungicide and azole fungicide according to the invention is diluted to provide ready-for-application composition comprising between 0.001 and 10 w/v% of the copper-based fungicide. If required, agriculturally acceptable carriers such as a sticking agent is added to the ready-for-application composition. A composition according to the invention is often diluted 2-5000 times, typically about 200 times, often about 100 times, to contain between about 0.0001 and 10 % (w/v) of the copperbased fungicide, prior to contacting a plant, plant part or soil (area or locus) with the composition.

To control agricultural pests, the invention provides a use of a composition comprising a copper-based fungicide and azole fungicide according to the invention for the protection of a plant, or a part of a plant, or locus (e.g., soil) against a pathogen. In order to achieve this effect, said plant or plant part, or a soil, is contacted with said composition, including any ready-for- application composition.

Said 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 sod farms. Further use, for example, is to control scab, including common scab, apple scab and black scab on potatoes, pear scab, and powdery scab, brown rot of peaches, currant and gooseberry leaf spot, peanut leafspot, and mildew on roses. Other uses include protection of greenhouse grown flowers and ornamentals, home vegetable gardens and residential turf. In addition, said composition, including a diluted ready-for-application composition, may be contacted with isolated crops, fruits, nuts, vegetables, and/or flowers.

For said use and said methods, the composition, including a ready-for-application diluted composition, is preferably sprayed over a plant, or part thereof. Spraying applications using automatic systems are known to reduce labor costs and are cost-effective. Methods and equipment well-known to a person skilled in the art can be used for that purpose. The composition, including diluted aqueous composition, can be regularly sprayed, when the risk of infection is high. When the risk of infection is lower, spray intervals may be longer.

Other methods understood to be suitable for contacting plants or parts thereof, soil etc. with a composition of the invention are clearly a part of the present invention. These include, but are not limited to, dipping, drenching, introduction into a dump tank, vaporizing, atomizing, fogging, fumigating, painting, brushing, misting, dusting, foaming, spreading-on, packaging and coating (e.g., by means of wax or electrostatically). In addition, the compositions , may be injected into the soil.

A plant of part thereof may be coated with a diluted ready-for-application composition comprising a copper-based fungicide and azole (e.g., triazole) and tertiary alkylamine (triethylamine), according to the invention by submerging the plant or part thereof in a diluted ready-for-application composition to protect the plant of part thereof against a pathogen and/or to prevent, reduce and/or eliminate the presence of a pathogen on a plant, or a part of a plant or in soil, growing medium etc. A typical part of a plant that is coated with a composition according to the invention, or with a dilution thereof, is seed. A further common part of a plant that is coated with a composition according to the invention, or with a dilution thereof, is leaf. A further commonly encountered part of a plant that is coated with a composition according to the invention, or with a dilution thereof, is a fruit, typically a post-harvest fruit such as, for example, a citrus fruit such as orange, mandarin and lime, a pome fruit such as apple and pear, a stone fruit such as almond, apricot, cherry, damson, nectarine, tomato, watermelon, a tropical fruit such as banana, mango, lychee and tangerine. A noted fruit is a citrus fruit, such as orange and/or a tropical fruit such as banana. In addition, when lists are provided, the list is to be considered as a disclosure of each member in the list, independently.Each embodiment disclosed herein is contemplated as being applicable to each of the other disclosed embodiments. Thus, all combinations of the various elements described herein are within the scope of the invention. In addition, the elements recited in the composition embodiments can be used in the process, method and use embodiments described herein and vice versa.

This invention will be better understood by reference to the Experimental Details which follow, but those skilled in the art will readily appreciate that the specific experiments detailed are only illustrative of the invention as described more fully in the claims which follow thereafter.

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

Table 1. Copper Oxychloride 300/ Picoxystrobin 70/ Prothioconazole 80 OD (1000 L)

Table 2. Copper Oxychloride 300/ Picoxystrobin 70/ Tebuconazole 80 OD

Table 3. Copper Oxychloride 300/ Fluxapyroxad 70/ Prothioconazole 80 OD

Table 4. Copper Oxychloride 300/ Azoxystrobin 70/ Prothioconazole 80 OD

Table 5. Copper Oxychloride 300/ Fluxapyroxad 70/ Tebuconazole 80 OD

Table 6. Copper Oxychloride + Chelated Copper / Picoxystrobin / Tebuconazole OD

Exemplified Method of Preparation Useful for The Above Composition Examples

In a tank with agitation, add Solvesso 150, Decanamide, Prothioconazole (triazole), and Picoxystrobin (additional a.i.), heat at 70°C, keeping under agitation (300 - 400 rpm) until complete Al solubilization. Then, turn off the heating and under stirring add: ATLAS G- 5002L-LQ-(CQ), Tristyrylphenol ethoxylate, Tween, Antifoam, Dodecylbenzene sulfonic acid calcium salt, AMPS-EA copolymer, Methyl Soyate, and lignosulfonate. Cool down until getting temperature less than 35°C, add Copper compound and silica (Cab-o-Sil M5), increasing the agitation between 1000 to 1500 rpm e.g., using agitator type Cowles. After finishing, filter the product through a 100 mesh sieve before packaging into closed container.

Stability studies:

Table 7. COC (metallic ion) 171 Fluxapyroxad 70 Prothioconazole 80 OD

Table 8. COC (metallic ion) 171 Azoxystrobin 70 Prothioconazole 80 OD

Table 9. COC 171 (metallic ion) Fluxapyroxad 70 Tebuconazole 80 OD

Table 10. Stability results

Prevention or Reversal of Copper-Triazole Complex by Free Triazole Quantification Including General Method for Assessing Compatibilizing Agents for prevention of complexation

OBJECTIVE:

A series of tests were performed with the objective to confirm that the inclusion of the exemplified triazole compatibilizing agent, triethylamine is able to prevent the exemplified triazole, prothioconazole complexation with copper, as well as, to show that other tested component is unable to adequately avoid the Prothioconazole complexation other than the impractical inclusion of at least stoichiometric amounts of chelators to chelate all the copper in the composition which would render the composition phytotoxic. The SC-dispersants of the invention were also tested to evaluate their decomplexation capability.

The tests comprised preparing nine comparable samples with the only difference being test component/ingredient variation. Each sample contained 80 g/L of Prothioconazole, 70 g/L of Picoxystrobin and 300 g/L of Copper oxychloride.. The samples were prepared with the addition of copper oxychloride during the last compounding step, and at room temperature. The analyses were each performed after storage 12 hours at room temperature.

A second though less favoured HPLC analytical methodology was used to validate a selection of sample results. The different HPLC methods produced different numerical results but the same pattern of relative effects confirming that the effect was not an artifact of analysis methodology. OD Concentrate Test Sample preparation:

#1 Control:

Copper Oxychloride 300 g/L

Picoxystrobin 70 g/L

Prothioconazole 80 g/L

N,N-dimethyl decanamide 40 g/L

Solvesso 150 g/L

Methyl soyate to complete 1000 ml.

#2 Sample 1 plus triethylamine 10 g/L

#3 Sample 1 plus EDTA 3.3 g/L

#4 Sample 1 plus lignosulfonate 30 g/L

#5 Sample 1 plus AMPS-EA 15 g/L

#6 Sample 1 plus Block copolymer 15 g/L

#7 Sample 1 plus EDTA, lignosulfonate, AMPS-EA, Block copolymer without triethylamine

#8 Sample 1 plus EDTA, lignosulfonate, AMPS-EA, Block copolymer with triethylamine

# 9 Sample 1 plus EDTA 98 g/L stoichiometric to chelate all the copper.

Analytical Results of Free Prothioconazole and Percentage Recovery in OD Concentrate Each Sample Compounded With 80 g/L Prothioconazole.

Validation results for 80 g/L OD concentrate with second HPLC method

Analytical Results of Free Prothioconazole and Percentage Recovery in Diluted Composition Each Sample With 0.7 g/L Prothioconazole.

Validation results - diluted Composition Prothioconazole 0.7 g/L with second HPLC method

Claims

CLAIMS:

1. A method for preparing oil-based compatibilized triazole fungicide comprising dissolving, a. triazole fungicide, and b. at least one triazole compatibilizing agent, in a non-aqueous solvent and/or carrier thus obtaining an oil -based triazole fungicide compatible with copper-based compounds.

2. The method as claimed in claim 1 comprising dissolving, a. triazole fungicide, and b. at least one triazole compatibilizing agent in a non-aqueous water-immiscible solvent and/or carrier comprising less than 5% water by weight, and c. dispersing a copper-based fungicide in the oil-based triazole fungicide, to obtain a non-aqueous oil-based composition of compatibilized triazole fungicide and copper-based compound wherein the at least one triazole compatibilizing agent comprises a tertiary amine compound.

3. The method as claimed in claim 1 wherein the at least one triazole fungicide is one or more of prothioconazole, cyproconazole, hexaconazole, tebuconazole, azaconazole, bromuconazole, diclobutrazol, difenoconazole, diniconazole, diniconazole- M, epoxiconazole, etaconazole, fenbuconazole, fluconazole, fluquinconazole, flusilazole, flutriafol, furconazole, furconazole-cis, imibenconazole, ipconazole, ipfentrifluconazole, mefentrifluconazole, metconazole, myclobutanil, penconazole, propiconazole, quinconazole, simeconazole, tetraconazole, thiabendazole (triazole), triadimefon, triadimenol, triticonazole, uniconazole and uniconazole-P their salts, esters, isomers and derivatives thereof.

4. The method as claimed in claim 1 wherein the at least one triazole compatibilizing agent comprises triethylamine.

5. The method as claimed in claim 2 wherein the obtained non-aqueous oil-based composition of compatibilized triazole fungicide and copper-based compound comprises a greater proportion of free triazole fungicide compound and a smaller proportion of triazole complexed with the copper-based fungicide, as compared to a composition comprising the same amount of the same triazole fungicide dissolved in the same non-aqueous solvent and/or carrier, and the same amount of the same dispersed copper-based fungicide absent the triazole compatibilizing agent compound. The method as claimed in claim 2 wherein the obtained non-aqueous oil-based composition of compatibilized triazole fungicide comprises greater than 80% of the triazole compound as free triazole fungicide and less than 20% of the triazole compound as triazole complexed with the copper-based fungicide after the copperbased fungicide is dispersed in the in the oil-based triazole fungicide. The method as claimed in claim 2 comprising dissolving, a. triazole fungicide, and b. at least one triazole compatibilizing agent in a non-aqueous solvent and/or carrier comprising less than 5% water by weight, c. dispersing a copper-based fungicide and at least one SC-dispersant additive, to obtain a non-aqueous oil-based composition of compatibilized triazole fungicide and copper-based compound, wherein said SC-dispersant, is characterized by requiring at least 1,000 parts of said non-aqueous solvent and/or carrier to dissolve one part of said SC-dispersant and said SC-dispersant is not soluble in the obtained non-aqueous oil-based composition. The method as claimed in claim 7 wherein the obtained non-aqueous oil-based composition of compatibilized triazole fungicide and copper-based compound is an oil dispersion (OD) concentrate, the method comprising the further steps of d. dispersing the OD concentrate in water to obtain an aqueous diluted tank-mix of the OD concentrate, wherein the SC-dispersant, is characterized by requiring at least 10,000 parts of the non-aqueous carrier or solvent to dissolve one part of the SC-dispersant and said SC- dispersant is fully soluble in the aqueous diluted tank-mix of the non-aqueous oil dispersion (OD) composition. A non-aqueous, oil-based triazole fungicide comprising a combination of, a. azole fungicide such as triazole fungicide, b. at least one triazole compatibilizing agent, and c. non-aqueous water-immiscible solvent and/or carrier, wherein the triazole fungicide and the triazole compatibilizing agent are dissolved in the non-aqueous solvent and/or carrier and the oil-based triazole fungicide is compatible with copper-based compounds. The triazole fungicide as claimed in claim 9 wherein the fungicide is a non-aqueous oil-dispersion (OD) composition comprising a dispersed copper-based fungicidal compound, the triazole compatibilizing agent comprises a tertiary amine compound and the composition comprises no more than 5% water. The non-aqueous, oil-based triazole fungicide claimed in claim 9 wherein the at least one triazole fungicide is one or more of prothioconazole, cyproconazole, hexaconazole, tebuconazole, azaconazole, bromuconazole, diclobutrazol, difenoconazole, diniconazole, diniconazole- M, epoxiconazole, etaconazole, fenbuconazole, fluconazole, fluquinconazole, flusilazole, flutriafol, furconazole, furconazole-cis, imibenconazole, ipconazole, ipfentrifluconazole, mefentrifluconazole, metconazole, myclobutanil, penconazole, propiconazole, quinconazole, simeconazole, tetraconazole, thiabendazole (triazole), triadimefon, triadimenol, triticonazole, uniconazole and uniconazole-P their salts, esters, isomers and derivatives thereof. The triazole fungicide as claimed in claim 9 wherein the at least one triazole compatibilizing agent comprises triethylamine. The non-aqueous, oil-based triazole fungicide as claimed in claim 10 wherein the nonaqueous oil-dispersion (OD) composition comprises a greater proportion of the triazole fungicide as free triazole fungicide compound and a smaller proportion of triazole complexed with the copper-based fungicide, as compared to a composition comprising the same amount of the same triazole fungicide dissolved in the same nonaqueous solvent and/or carrier, and the same amount of the same dispersed copperbased fungicide absent the tertiary amine compound. The method as claimed in claim 10 wherein the non-aqueous oil-based dispersion composition of compatibilized triazole fungicide and dispersed copper-based fungicidal compound comprises greater than 80% of the triazole compound as free triazole fungicide and less than 20% of the triazole compound as triazole complexed with the copper-based fungicide when measured by comparing the peak area at the same retention time of the triazole compound. The non-aqueous, oil-based triazole fungicide as claimed in claim 10 wherein the nonaqueous oil-dispersion (OD) composition comprises at least one SC-dispersant additive, wherein said SC-dispersant, is characterized by requiring at least 1,000 parts of said non-aqueous solvent and/or carrier to dissolve one part of said SC-dispersant and said SC-dispersant is not soluble in the non-aqueous oil-dispersion (OD) composition. An aqueous diluted tank-mix comprising the oil dispersion (OD) as claimed in claim 15, dispersed in water, wherein the OD is a concentrate, wherein the SC-dispersant, is characterized by requiring at least 10,000 parts of the non-aqueous, water-immiscible carrier or solvent to dissolve one part of the SC-dispersant and said SC-dispersant is fully soluble in the aqueous diluted tank-mix of the non-aqueous oil-dispersion (OD) composition. The non-aqueous, oil-based triazole fungicide as claimed in claim 15 wherein the at least one SC-dispersant additive is selected from the group of a water soluble anionic polyelectrolyte such as a lignosulfonate; a polycarboxylic acid polymer; a polyelectrolyte copolymer; random and block copolymers of sodium 2- acryloylamino-2-methylpropane-l-sulfonate (AMPS) monomers and ethyl acrylate (EA) monomers; and copolymers of styrene and methacrylic acid monomers. A non-aqueous agricultural, oil dispersion OD concentrate composition comprising, a. at least one copper-based fungicide, b. at least one azole (triazole) fungicide, c. tertiary amine, d. one or more water immiscible, non-aqueous carrier or solvent and e. at least one SC-dispersant, and f. no more than 5% by weight of water, wherein the SC-dispersant, is characterized by requiring at least 1,000 parts of said one or more water immiscible non-aqueous carrier or solvent to dissolve one part of said SC-dispersant and said SC-dispersant is not soluble in the OD concentrate composition.

19. The non-aqueous agricultural, oil dispersion OD concentrate composition of claim 18, comprising, a. at least one copper-based fungicide, b. at least one azole (triazole) fungicide, c. tertiary amine, d. one or more water immiscible, non-aqueous carrier or solvent and e. at least one SC-dispersant, and f. no more than 5% by weight of water, wherein the SC-dispersant, is characterized by requiring greater than 10,000 parts of said one or more water immiscible non-aqueous carrier or solvent to dissolve one part of said SC-dispersant.

20. The non-aqueous agricultural, oil dispersion OD concentrate composition as claimed in claim 18, comprising, a. copper-based fungicide, b. triazole fungicide, c. triethylamine, d. one or more water immiscible, non-aqueous carrier or solvent, e. a third fungicide which is neither a triazole nor a copper-based fungicide, f. at least one SC-dispersant, and g. no more than 5% by weight of water, wherein the third fungicide selected from the group of strobilurin fungicides, benzamide fungicide, morpholines, Qil fungicide, SDHI and any combination thereof. The triazole fungicide as claimed in claim 10 wherein, the azole fungicide is selected from one or more of, climbazole, clotrimazole; imazalil; oxpoconazole; prochloraz; triflumizole; viniconazole; azaconazole; bromuconazole; cyproconazole; diclobutrazol; difenoconazole; diniconazole; diniconazole-M; epoxiconazole; etaconazole; fenbuconazole; fluconazole; fluoxytioconazole; fluquinconazole; flusilazole; flutriafol; furconazole; furconazole-cis; hexaconazole; imibenconazole; ipconazole; ipfentrifluconazole; mefentrifluconazole; metconazole; myclobutanil; penconazole; propiconazole; prothioconazole; quinconazole; simeconazole; tebuconazole; tetraconazole; triadimefon; triadimenol; triticonazole; uniconazole; uniconazole-P their salts, esters, isomers and derivatives thereof, and/or the non-aqueous water-immiscible solvent and/or carrier is selected from one or more of, aromatic hydrocarbons, fatty acid alkyl amides; N,N-dimethyl octanamide; N,N dimethyl decanamide; acetophenone; fatty acids alkyl esters and methylated vegetable oil; and/or the SC-dispersant additive is exemplified by any of anionic polyelectrolytes; lignosulfonates; polycarboxylic acid polymer; random or block polyelectrolyte copolymer; styrene -acrylic dispersants; co-polymers of sodium 2-acryloylamino-2- methylpropane-l-sulfonate (AMPS) monomers and ethyl acrylate (EA) monomers, wherein the tertiary amine compound is triethylamine. The non-aqueous agricultural, oil dispersion OD concentrate composition as claimed in claim 20 wherein the non-aqueous solvent and/or carrier comprises two or more water immiscible carriers or solvents selected from the group of aromatic hydrocarbons, fatty acid alkyl amides; N,N-dimethyl octanamide; N,N dimethyl decanamide; acetophenone; fatty acids alkyl esters and methylated vegetable oil. The non-aqueous agricultural, oil dispersion OD concentrate composition as claimed in claim 20 wherein the third fungicide selected from the group of azoxystrobin; coumoxystrobin; enoxastrobin; flufenoxystrobin; picoxystrobin; pyraoxystrobin; mandestrobin; pyraclostrobin; pyrametostrobin; triclopyricarb; kresoxim-methyl; trifloxystrobin; dimoxystrobin; fenaminstrobin; metominostrobin; orysastrobin; metyltetraprole; fluoxastrobin; penthiopyrad, boscalid, flutolanil, fluxapyroxad, inpyrfluxam , fluopyram, fluindapyr, benzodiflupyr, bixafen and pydiflumetofen; cyazofamid, amisulbrom and fenpicoxamid; aldimorph, fenpropimorph, tridemorph, dodemorph, spiroxamine, piperalin, fenpropidin. The non-aqueous agricultural, oil dispersion OD concentrate composition as claimed in claim 20 wherein the third fungicide selected from the group of fluxapyroxad; azoxy strobin and picoxystrobin.

25. The non-aqueous, oil-based triazole fungicide as claimed in claim 9 comprising a combination of, a. one or more triazole fungicide compounds selected from prothioconazole and tebuconazole, b. at least one triazole compatibilizing agent selected from the group of tertiary amines, c. a copper-based fungicidal compound d. non-aqueous water-immiscible solvent and/or carrier, selected from one or more selected from the group of, of aromatic hydrocarbons; fatty acid alkyl amides; N,N-dimethyl octanamide; N,N dimethyl decanamide; acetophenone; fatty acids alkyl esters and methylated vegetable oil, e. and a third fungicide which is neither a triazole nor a copper-based fungicide selected from one or more of the group of, fluxapyroxad; azoxystrobin and picoxystrobin. wherein the triazole fungicide and the triazole compatibilizing agent are dissolved in the non-aqueous solvent and/or carrier and the copper-based fungicidal compound is dispersed in the non-aqueous solvent and/or carrier characterized in that the oil-based triazole fungicide is compatible with the copper-based compound dispersed therein.

26. The non-aqueous, oil-based triazole fungicide as claimed in claim 25 wherein the third fungicide is dissolved in the non-aqueous solvent and/or carrier.

27. The triazole fungicide as claimed in claim 10, wherein the dispersed copper-based fungicidal compound is selected from one or more selected from the group of cupric acetate, cupric chloride, cupric chlorate, cupric formate, cupric hexafluorosilicate, cupric nitrate, cupric chromate, copper sulfate pentahydrate, bordeaux mixture, copper hydroxide, cuprous oxide, copper oxychloride, chelated copper, complexed copper, copper oxychloride sulfate (COCS), tribasic copper sulfate such as cupric sulfate, tricupric hydroxide, hemihydrate, and any combination thereof, wherein when the copper-based fungicidal compound comprises chelated copper the chelated copper comprises no more than 5% by weight of the total copper in the composition. a. The non-aqueous agricultural, oil dispersion OD concentrate composition as claimed in claim 20 comprising a combination selected from the group of, a combination of:

(1) copper-based fungicide,

(2) prothioconazole,

(3) picoxystrobin

(4) at least one water immiscible carrier and/or solvent, and

(5) triethylamine; b. a combination of:

(1) copper-based fungicide,

(2) prothioconazole,

(3) azoxy strobin

(4) at least one water immiscible carrier and/or solvent, and

(5) triethylamine; c. a combination of:

(1) copper-based fungicide,

(2) prothioconazole,

(3) fluxapyroxad

(4) at least one water immiscible carrier and/or solvent, and

(5) triethylamine; d. a combination of:

(1) copper-based fungicide,

(2) tebuconazole,

(3) fluxapyroxad

(4) at least one water immiscible carrier and/or solvent, and

(5) triethylamine; e. a combination of:

(1) copper-based fungicide, (2) Tebuconazole,

(3) picoxystrobin

(4) at least one water immiscible carrier and/or solvent, and

(5) triethylamine; f. a combination of:

(1) copper-based fungicide,

(2) prothioconazole,

(3) picoxystrobin

(4) at least one water immiscible carrier and/or solvent, and

(5) lignosulfonate; g. a combination of:

(1) copper-based fungicide,

(2) prothioconazole,

(3) azoxy strobin

(4) at least one water immiscible carrier and/or solvent, and

(5) lignosulfonate (SC-Dispersant); h. a combination of:

(1) copper-based fungicide,

(2) prothioconazole,

(3) azoxy strobin

(4) at least one water immiscible carrier and/or solvent, and

(5) lignosulfonate (SC-Dispersant); i. a combination of

(1) copper-based fungicide,

(2) prothioconazole,

(3) fluxapyroxad

(4) at least one water immiscible carrier and/or solvent, and

(5) lignosulfonate (SC-Dispersant); j . a combination of

(1) copper-based fungicide,

(2) tebuconazole, (3) fluxapyroxad

(4) at least one water immiscible carrier and/or solvent, and

(5) lignosulfonate ; k. a combination of

(1) copper-based fungicide,

(2) Tebuconazole,

(3) picoxystrobin

(4) at least one water immiscible carrier and/or solvent, and

(5) lignosulfonate; l. a combination of

(1) copper-based fungicide,

(2) prothioconazole,

(3) picoxystrobin

(4) at least one water immiscible carrier and/or solvent, and

(5) AMPS-ethyl acrylate block copolymer; m. a combination of,

(1) copper-based fungicide,

(2) prothioconazole,

(3) azoxy strobin

(4) at least one water immiscible carrier and/or solvent, and

(5) AMPS-ethyl acrylate block copolymer; n. a combination of,

(1) copper-based fungicide,

(2) prothioconazole,

(3) fluxapyroxad

(4) at least one water immiscible carrier and/or solvent, and

(5) AMPS-ethyl acrylate block copolymer; o. a combination of,

(1) copper-based fungicide,

(2) tebuconazole,

(3) fluxapyroxad (4) at least one water immiscible carrier and/or solvent, and

(5) AMPS-ethyl acrylate copolymer (SC-Dispersant); p. a combination of,

(1) copper-based fungicide,

(2) Tebuconazole,

(3) picoxystrobin

(4) at least one water immiscible carrier and/or solvent, and

(5) AMPS-ethyl acrylate block copolymer (SC-Dispersant); q. a combination of,

(1) copper-based fungicide,

(2) prothioconazole,

(3) picoxystrobin,

(4) at least one water immiscible carrier and/or solvent,

(5) AMPS-ethyl acrylate block copolymer, and

(6) lignosulfonate; r. a combination of,

(1) copper-based fungicide,

(2) prothioconazole,

(3) azoxy strobin

(4) at least one water immiscible carrier and/or solvent,

(5) AMPS-ethylacrylate copolymer, and

(6) lignosulfonate; s. a combination of,

(1) copper-based fungicide,

(2) prothioconazole,

(3) fluxapyroxad

(4) at least one water immiscible carrier and/or solvent,

(5) AMPS-ethyl acrylate block copolymer, and

(6) lignosulfonate; t. a combination of,

(1) copper-based fungicide,

(2) tebuconazole, (3) fluxapyroxad

(4) at least one water immiscible carrier and/or solvent,

(5) AMPS-ethyl acrylate block copolymer, and

(6) lignosulfonate; u. a combination of,

(1) copper-based fungicide,

(2) Tebuconazole,

(3) picoxystrobin

(4) at least one water immiscible carrier and/or solvent,

(5) AMPS-ethyl acrylate copolymer, and

(6) lignosulfonate; v. a combination of,

(1) copper-based fungicide,

(2) prothioconazole,

(3) picoxystrobin,

(4) at least one water immiscible carrier and/or solvent,

(5) AMPS-ethyl acrylate block copolymer,

(6) lignosulfonate, and

(7) triethylamine; w. a combination of,

(1) copper-based fungicide,

(2) prothioconazole,

(3) azoxy strobin,

(4) at least one water immiscible carrier and/or solvent,

(5) AMPS-ethyl acrylate copolymer,

(6) lignosulfonate, and

(7) triethylamine; x. a combination of,

(1) copper-based fungicide,

(2) prothioconazole,

(3) fluxapyroxad

(4) at least one water immiscible carrier and/or solvent, (5) AMPS-ethyl acrylate block copolymer,

(6) lignosulfonate, and

(7) triethylamine; y. a combination of,

(1) copper-based fungicide,

(2) tebuconazole,

(3) fluxapyroxad

(4) at least one water immiscible carrier and/or solvent,

(5) AMPS-ethyl acrylate block copolymer,

(6) lignosulfonate, and

(7) triethylamine; and z. a combination of,

(1) copper-based fungicide,

(2) Tebuconazole,

(3) picoxystrobin

(4) at least one water immiscible carrier and/or solvent,

(5) AMPS-ethyl acrylate block copolymer,

(6) lignosulfonate, and

(7) triethylamine.

28. A diluted tank-mix comprising the non-aqueous agricultural, oil dispersion OD concentrate composition as claimed in claim 20 dispersed in water.

29. A tank mix comprising, a. the non-aqueous, oil-based triazole fungicide as claimed in any one of claims 9-13, and b. Water, wherein the non-aqueous, oil-based triazole fungicide is dispersed, diluted or dissolved in the water.