Shielded copper oil-based compositions

Abstract

The present invention relates to improved copper-shielding triazole compatibilizing agents, ingredients, or additives, that enable preparation of improved oil-based compositions comprising triazole fungicide in combination with copper-based ingredients exemplified by copper-based fungicidal compounds, as shielded copper fungicidal oil-based triazole fungicide compositions. The invention relates to improved non-aqueous, oil-based combinations comprising azole (triazole) fungicide and copper-shielding azole (triazole)-compatibilizing agents with copper-based compounds most notably exemplified by agents which are often amine-type compounds having the ability to hinder or interfere with the interaction between the triazole and copper compounds so as avoid, or reduce the formation of copper-triazole complex thus ensuring a higher percentage of the triazole as "free" or uncomplexed triazole, and thus maintaining its fungicidal efficacy.

Description

[0001] SHIELDED COPPER OIL-BASED COMPOSITIONS

[0002] 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. 5

[0003] This application claims priority of U.S. Provisional Application No. 63 / 606,909, filed December 6, 2023, the contents of which are hereby incorporated by reference.

[0004] TECHNICAL FIELD

[0005] The invention is most relevant to the technical field of agricultural, typically pesticide compositions. 10

[0006] The present invention relates to improved copper-shielding triazole compatibilizing agents, ingredients or additives that enable preparation of improved oil-based compositions comprising triazole fungicide in combination with copper-based ingredients exemplified by copper-based fungicidal compounds, as shielded copper fungicidal oil-based triazole fungicide compositions. The invention relates to improved non-aqueous, oil-based combinations comprising azole 15 (triazole) fungicide and copper shielding azole (triazole), compatibilizing agents with copperbased compounds most notably exemplified by copper-shielding or interfering compatibilizing agents which are often amine-type compounds having the ability to hinder or interfere with the interaction between the triazole and copper compounds so as avoid, or reduce the formation of copper-triazole complex thus ensuring a higher percentage of the triazole as “free” or 20 uncomplexed triazole, and thus maintaining its fungicidal efficacy. The more useful compatibilizing agents will not themselves form strong complexes with the typically high content of copper compounds, in the compositions, which might result in the agents themselves being unavailable to prevent the triazole-copper complexes.

[0007] Exemplary copper-shielding compatibilizing agents will thus have a greater affinity with 25 copper compounds than the azole or triazole compounds but lacking the tendency to be able to form full stable, strong and / or irreversible complexes with copper. Examples of such compatibilizing agent may include tertiary amines such as tributylamines, tripentyl amines, trihexyl amines, or tertiary amines wherein each substituent is a different alkyl or olefin, or for that matter only two of the substituents are the same but also primary and secondary organic 30 (alkyl, olefin, aryl etc.) amines wherein the alkyl groups are such that a copper-compatibilizing agent complex is unable to form or is hindered from forming. The suitable primary and secondary amines may include alkyl and dialkyl groups which make the compatibilizing agent sterically hindered thus avoiding stable, strong and / or irreversible copper-compatibilizing agent complex formation while still interfering the copper-azole complexation by having a greater affinity with copper than the triazole (azole) compound. These suitable primary and 5 secondary hydrocarbon amines may include alkyl or olefin amines wherein the hydrocarbon groups are long or fatty alkyl or olefin chains or be substituted with sterically hindered substituents that achieve the required hindrance to copper-compatibilizing agent complex formation.

[0008] These improved, copper shielding triazole compatibilizing agents allow for improved inventive 10 oil-based compositions of (compatibilized) free 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 both triazole-copper complex, and copper- compatibilizing agent complex formation by inclusion of the triazole compatibilizing agents in 15 the non-aqueous, oil-based compositions.

[0009] The improved non-aqueous oil-based dispersion compositions are characterized in that the amount of dispersed copper-based compounds is in excess of the amount of copper shielding triazole compatibilizing agent.

[0010] One way of assessing the fungicidal availability of the triazole in the non-aqueous, oil-based 20 triazole compositions is by HPLC analysis, of the composition wherein the HPLC method can distinguish free triazole for example by resulting in a different retention time compared with bound or complexed triazole.

[0011] The present invention thus relates to non-aqueous fungicidal compositions comprising copperbased fungicidal compounds and triazole fungicidal wherein the triazole fungicide is one or 25 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, 30 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 while at the same time avoiding copper-based complexes that might deactivate the compatibilizing nature of the compatibilizing agent as well as reduce the amount of free fimgicidally active copper. In several typical embodiments of the invention the triazole is prothioconazole or tebuconazole. 5

[0012] The invention thus, relates to improved non-aqueous oil-based compositions, and aqueous dilutions thereof, comprising triazole fungicide, copper fungicide and improved triazole compatibilizing amine-type agent which are typically exemplified by tertiary amines such as tributylamine, mixed trialkyl amines, or sterically hindered primary or secondary organic amines wherein the substituents of the amine agent are such as to hinder or prevent the 10 formation of deactivating agent-copper complexes.

[0013] The compositions of the invention are characterized by preserved content of free triazole and free copper compounds due to the prevention of both significant triazole-copper complex formation as well as preventing formation of unwanted copper complexes formed by the interaction of the copper compound with the agent that prevents the triazole-copper complex 15 formation.

[0014] The advantages enabled by the inventive as non-aqueous compositions such as OD concentrates are often appreciated or realized once the concentrated compositions are diluted prior to fungicidal agricultural application and thus the invention is embodied both by the nonaqueous oil-based compositions as well as aqueous tank mix compositions prepared by diluting 20 or dispersing the inventive oil-based compositions in water.

[0015] The present invention provides improved oil-based, particularly non-aqueous oil concentrate (OD) compositions, of azole fungicides combined with a triazole compatibilizing agent typified by one or more organic amines such as alkylamine or arylamine represented by the structure A; 25 wherein: (i) R1is hydrogen, Cn alkyl, aryl, Cn alkenyl, Cn alkynyl or heterocyclic; R2is hydrogen, Cn alkyl, aryl, Cn alkenyl, Cn alkynyl or heterocyclic; and R3is hydrogen, Cn alkyl, aryl, Cn alkenyl, Cn alkynyl or heterocyclic; and

[0016] (ii) at least one of R1, R2, and R3is alkyl, aryl , alkenyl, alkynyl or heterocyclic,

[0017] (iii) when all of R1, R2, and R3are alkyl or alkenyl or alkynyl groups, then Cn is Ci-26, 5 commonly CJ-C24, or often C1-C22, sometimes C3-C18, such as butyl, pentyl, hexyl, and including alkyl fatty chains exemplified by, C12 or dodecyl (lauryl), saturated

[0018] Cis (stearyl) or unsaturated Cis (oleyl),

[0019] (iv) when the alkylamine (including olefinic amines alkenyl alkynyl), represented by the structure A is a primary or secondary amine then at least one of R1, R2, and R3are 10 aromatic, or alkyl or alkenyl or alkynyl groups, wherein Cn is Ce- 26, commonly Cs~

[0020] C24, often C8-C22 or C10-C22, such as alkyl fatty chains exemplified by, C12 or dodecyl (lauryl), saturated Cis (stearyl) or unsaturated Cis (oleyl).

[0021] While compounds represented by structure A above are exemplary or typical copper shielding triazole compatibilizing agents, it is important to emphasize that it is the ability of these 15 compatibilizing agents to interfere with both triazole-complex formation as well as avoiding any strong, stable or irreversible complexes of the compatibilizing agents themselves with the copper, that is more important than the specific chemical structure of the agent. Thus, while a particular molecule might fall within the definition of Structure A above, it will not be considered a suitable triazole compatibilizing agent if its inclusion in a composition of triazole 20 and copper-based compounds results in either lower free triazole content or less fiingicidally efficacious copper-based components.

[0022] In some embodiments, alkyl, which may be optionally substituted, denotes a linear or branched or cyclic hydrocarbon group comprising n carbon atoms.

[0023] In some embodiments, alkenyl, which may be optionally substituted, denotes a linear or 25 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.

[0024] In some embodiments, aryl, which may be optionally substituted, denotes to carbocyclic aromatic radicals having from 6 to 14 carbon atoms. 30

[0025] Tributylamine. 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 copper-shielding triazole compatibilizing agent (or “Copper Shielding Agent”), most notably organic amines exemplified by either Ci- 26 tertiary amines, such as tributylamine etc., or primary or secondary 5 organic amines, substituted with Ce- 26 organic groups having a structure that sterically hinders formation of strong complexes with the copper-based fungicidal compounds.

[0026] 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 10 with the copper compound, while simultaneously do not display significant content of stable, irreversible or strong copper-compatibilizing agent complexes that might reduce the amount of fungicidally available copper.

[0027] Clearly, aqueous diluted compositions prepared by diluting the improved non-aqueous compositions of the invention are equally within the scope of the invention particularly as the 15 advantageous preservation of free triazole in the non-aqueous oil-based compositions are realized when these oil-based compositions are applied as aqueous emulsions of free triazole and uncomplexed copper as agricultural pesticides.

[0028] The azole fungicides are typically the triazole fungicides such as one or more of, prothioconazole, cyproconazole, hexaconazole, tebuconazole, azaconazole, bromuconazole, 20 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- 25 P, their salts, esters, isomers and derivatives thereof.

[0029] 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 copper-shielding triazole compatibilizing agent exemplified by tertiary amine such as tributylaminetributylamine, N-methyl-N-propyl-hexylamine, or sterically hindered primary or 30 secondary amines such as fatty alkyl amines or fatty dialkyl amines and optionally 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 azole-copper complex formation with the copper and the compatibilizing efficacy of the agent is not compromised by significant complex formation with the copper compound.

[0030] The present invention thus provides improved Oil Dispersion (OD) compositions typically as 5 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 10 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. Significantly, the amount of the copper-shielding triazole compatibilizing agent is not reduced by complex interaction with the copper.

[0031] The invention provides improved Oil Dispersion (OD) compositions comprising azole 15 (triazole) fungicide compound and copper-based fungicide compound and copper-shielding 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 20 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.

[0032] In some embodiments, the invention provides improved Oil Dispersion (OD) compositions comprising azole (triazole) fungicide compound and copper-based fungicide compound and 25 copper-shielding 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 30 copper-shielding triazole compatibilizing agent or with amines that form strong interactions with copper. In some embodiments, the composition comprises at least 70% 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 75% 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 80% of the amount of the azole fungicide which was used for formulating or preparing the composition as free triazole . In some 5 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 10 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. 15

[0033] BACKGROUND

[0034] Copper-based fungicides are well-known but uses of copper-based fungicides are limited due to phytotoxicity to plant and toxicity to the user.

[0035] Combination of copper-based fungicide and azole fungicide are effective combinations in 20 controlling different (fungal), diseases in crops.

[0036] 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. 25

[0037] 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.

[0038] However, inventors have found by experimental analysis, that in order to ensure that the 30 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. 5

[0039] 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. 10

[0040] More recently, exciting insights were gained when some researchers found that several compounds might prevent the formation of triazole-copper complexes by using inter alia, amines. However, when the content of the triazole compatibilizing agent is much less than the amount of the dispersed copper compound, or the copper is in molar excess of the agent, the particular structural attributes of the amine-type compatibilizing agent as detailed herein this 15 disclosure, becomes more important if they are to successfully compatibilize the triazole without being “neutralized” by deactivating agent-compatibilizing agent complex formation with the copper.

[0041] 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 20 understood to be inapplicable in non-aqueous and / or oil-based compositions such as Oily Dispersion OD concentrates.

[0042] 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. 25

[0043] 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

[0044] The present invention provides a method for preparing oil-based compatibilized triazole fungicide comprising dissolving, a. triazole fungicide, and b. copper-shielding triazole compatibilizing agent, 5 in a non-aqueous and / or immiscible, solvent and / or carrier thus obtaining an oil-based triazole fungicide compatible with copper-based compounds wherein the copper-shielding triazole compatibilizing agent is characterised by both a greater chemical affinity for copper-based compounds than the triazole fungicide and minimal capacity to form stable, strong, or irreversible complexes with copper. 10

[0045] In common embodiments of the compositions enabled by compatibilizing the triazole fungicide, solid particulate copper-based compound is dispersed and suspended in the nonaqueous oil-based solution of copper-shielding triazole compatibilizing agent and triazole. These oil dispersion compositions are characterized in that greater than 80% of the triazole fungicide remains uncomplexed with copper as free triazole, even after periods of storage. 15

[0046] The present invention provides a method for preparing oil-based compatibilized triazole fungicide composition comprising dissolving, a. triazole fungicide, and b. copper-shielding triazole compatibilizing agent in a non-aqueous water-immiscible solvent and / or carrier comprising less than 5% water by 20 weight, and c. dispersing a copper-based fungicide compound 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 copper-shielding triazole compatibilizing agent 25 comprises a tertiary amine or sterically hindered organic amine compound such that the copperbased fungicide compound is shielded from interacting with the triazole fungicide and wherein the copper-shielding triazole compatibilizing agent is characterized in that it does not form stable, strong, or irreversible complexes with the copper-based fungicide compound in the composition. 30

[0047] The present invention provides a method for preparing oil-based compatibilized triazole fungicide comprising dissolving, a. triazole fungicide, and b. copper-shielding 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- 5 based compound wherein the at least one copper-shielding triazole compatibilizing agent is a selected candidate compound that is capable or present in sufficient quantity in the Oil-Based composition of triazole fungicide and Copper-based fungicide to maintain at least 70 percent and advantageously greater than 80 percent of the triazole fungicide as free triazole in the tests outlined herein, in notable examples greater than 90% and greater than 95% of the triazole 10 remains free.

[0048] A general test for candidate selection protocol being exemplified by use of a general platform composition such as in the illustrative example detailed elsewhere or in general format below, but replacing the illustrated copper-shielding agent with one or several concentrations of the candidate compound and measuring the amount of free uncomplexed triazole (azole) by HPLC 15 after storage of the composition for two weeks at 54°C. A composition comprising greater than 70% of the azole as free triazole indicates that the candidate is a suitable copper-shielding triazole compatibilizing agent candidate for selection. A composition comprising greater than 80%, greater than 85%, greater than 90% or greater than 95% of the azole as free triazole indicates that the candidate is even more suitable copper-shielding triazole compatibilizing 20 agent candidate for selection.

[0049] Example of Non-Limiting Illustration Copper + triazole OD selection platform composition

[0050] The present invention provides a method for selecting a preferred copper-shielding triazole compatibilizing agent compound for use in compositions of the invention, from a group of 5 candidate amine compounds. A series of tests are performed with the objective to select a preferred copper-shielding triazole compatibilizing agent typically from a group of potential candidates. To be suitable, the inclusion of the tested triazole compatibilizing agent candidatetributylamine must be able to prevent the model triazole, prothioconazole from complexation with a model copper-based fungicide compound. 10

[0051] While many amine-based compounds have a greater affinity for copper compounds than triazole compounds, some theoretically shielding compound are not found to be useful because they form strong complexes with copper themselves and thus they are “consumed” or removed from the system in their compatibilizing role because of the large amount of “deactivating” copper in the system which is often included in very large amounts in typical copper-based 15 fungicidal compositions, and thus cannot perform their function to hinder triazole-copper complex formation.

[0052] The useful copper-shielding triazole compatibilizing agents are often organic amine compounds which have a greater affinity than the triazole for the cooper-based compounds in a triazole and copper oil-based composition, while simultaneously being unable to actually form strong complex structures with the copper.

[0053] In some embodiments useful copper-shielding triazole compatibilizing agents are tertiary organic amines with three nitrogen substituents typically having a carbon chain length (or cyclic structures) of Ci-26 . In some embodiments useful copper-shielding triazole 5 compatibilizing agents are primary or secondary organic amines with substituents that give characteristics to the shielding agent that prevent or hinder the formation of stable, irreversible, or strong copper-agent complexes with the copper components of the oily dispersion compositions. In some embodiments the primary or secondary organic amines which are useful copper-shielding triazole compatibilizing agents are those that have nitrogen substituents with 10 a carbon chain length (or cyclic structures) of Ce-26 .

[0054] In some embodiments the primary or secondary organic amines which are useful copper- shielding triazole compatibilizing agents are those amines that have nitrogen substituents such that they are fatty alkyl amines or similarly hindering unsubstituted groups.

[0055] While some simple or small, primary or secondary organic amines are unable to prevent 15 copper-triazole complex formation because of their strong interaction with the copper compounds, many large or otherwise sterically hindered amines are found to be useful at shielding copper compounds from complexing with co-formulated triazole fungicide compounds while at the same time are not “deactivated” or otherwise removed from the system by forming strong / stable or irreversible complexes with the copper. 20

[0056] In a method for selecting useful copper-shielding triazole compatibilizing agents a model composition might be used. An illustration of useful tests comparing the compatibilizing efficacy of a group of candidate compounds comprises preparing several comparable samples with the only difference being each being the identity of the candidate compound to be tested. While being in no way limited, a illustrative test Oily Dispersion composition for including 25 and then evaluating candidate compounds might contain 80 g / L of Prothioconazole, 70 g / L of Picoxystrobin and 300 g / L of Copper oxychloride in a non-aqueous carrier or vehicle suitable for agricultural compositions.

[0057] The compositions are prepared and analyses of each composition is performed after storage 12 hours at room temperature, as well as after storage at controlled conditions. The percentage of 30 free triazole is quantified and the results of Free triazole (Prothioconazole), and Percentage Recovery from the model OD Concentrates are calculated for example by comparing HPLC peak area and only compositions wherein the free triazole content in the composition remains equal to or greater than about 70% of the Triazole active ingredient introduced during preparation of the oil based OD composition, might be considered possible candidate copper- shielding triazole compatibilizing agents for further evaluation and selection.

[0058] 5

[0059] Importantly, the ability of a potential copper-shielding triazole compatibilizing agent compound to hinder triazole-copper complexes is not the only factor that will decide whether it will be of practical use, as clearly formulation considerations have to be considered. While two candidate copper-shielding triazole compatibilizing agents may have a similar level of shielding efficacy, one compound may be more soluble in the oily carrier or composition, one 10 of the candidates might be characterised by acidity / alkalinity that might destabilize one or more of the composition. It is reported for example that some amine compounds are corrosive or otherwise difficult to handle and these too will factor into the decision as to which candidate copper-shielding agent will be chosen.

[0060] Researchers skilled in formulation arts will of course be aware of many more considerations 15 that might make some candidate copper-shielding triazole compatibilizing agent compounds more suitable for a particular composition than others.

[0061] While a free triazole content in the composition remaining equal to or greater than about 75% of the Triazole active ingredient introduced during preparation of an oil based OD composition 20 after 12 hours may be a minimum acceptance criteria, in some embodiments the tests are conducted after storage for periods of time up to and including the proposed shelf life of the Oily Dispersion compositions and then again in diluted tank-mixes prepared by diluting the Oily Dispersion in aqueous medium such as, at a dilution of 1% in water, as would be prepared prior to pesticidal (fungicidal), application. 25

[0062] In some embodiments acceptable free triazole content in the inventive composition remains equal to or greater than about 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 when preparing a Tank-mix of the OD prior to fungicidal 30 application.

[0063] In some embodiments acceptable 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 shelflife, and after dilution with water when preparing a Tank-mix of the OD prior to fungicidal application.

[0064] 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 5 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.

[0065] 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 10 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.

[0066] 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 15 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.

[0067] In common composition embodiments the prevention of triazole -copper complex formation also prevents degradation of the physical quality attributes of the inventive oil-based 20 compositions.

[0068] The color of the oil-based compositions have been found be stable to changing color during storage, whereas comparable oil dispersion compositions absent the copper shielding triazole compatibilizing agent have been observed to change unacceptably when complex formation has occurred. In some illustrated examples the compositions changed from a turquoise color to 25 a dark brown color over storage for two weeks at 54°C.

[0069] Suspension stability and the size of suspended particles can also be advantages of the use of these copper-shielding agents.

[0070] The present invention provides oily, non-aqueous, compositions adapted to enable combination 30 with copper-based fungicides comprising,

[0071] A. a water immiscible carrier or solvent,

[0072] B. azole (triazole), fungicide, and

[0073] C. copper-shielding triazole compatibilizing agent, such as tributylamine. wherein the oily composition comprises less than 5% water and the copper-shielding triazole compatibilizing agent, 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.

[0074] 5 In many embodiments the composition is an oil dispersion concentrate adapted for dilution in aqueous media prior to fungicidal application.

[0075] In many embodiments the composition is an oil dispersion concentrate comprising a further pesticidal active ingredient, such as an additional fungicide. 10

[0076] Wherein, the copper-shielding triazole compatibilizing agent may have been one selected by a test based on a model composition as illustrated above, but the prior testing for selection is in no way a limit on which copper-shielding agent is used so long as it is able to maintain at least 70% of the triazole as free uncomplexed triazole. 15

[0077] Practitioners skilled in these fields after having this invention illustrated will often understand which compounds will be “good” copper shielding agents and which are likely to be deactivated in a composition through complexation with copper-based composition components or constituents. For these practitioner, the testing protocol above is perhaps superfluous, however this invention is designed to be simple even for the less skilled 20 researchers for whom the selection protocol may prove useful.

[0078] The present invention provides a non-aqueous, oil-based triazole fungicide comprising a combination of, a. azole (triazole), fungicide such as triazole fungicide, 25 b. copper-shielding triazole compatibilizing agent, and c. non-aqueous water-immiscible solvent and / or carrier, wherein the triazole fungicide and the copper-shielding 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. 30

[0079] Please note, the term copper-shielding triazole compatibilizing agent is sometimes herein referred to as copper-shielding agent, there is no intention to differentiate the compounds and they have the same meaning for the purposes of this invention. The present invention provides a non-aqueous agricultural, oil dispersion OD concentrate composition comprising, a. copper-based fungicide, b. azole (triazole) fungicide, c. copper-shielding agent, 5 d. water-immiscible, non-aqueous carrier or solvent, e. dispersant, and f. no more than 5% by weight of water,

[0080] In some embodiments, the dispersant, is of a type that is active only once concentrated oil 10 dispersion compositions of the invention are eventually diluted in water. These dispersants arecharacterized by requiring at least 1,000 parts of said water-immiscible non-aqueous carrier or solvent to dissolve one part of said dispersant and said SC-dispersant is not soluble in the OD concentrate composition. The utility of including dispersants with this characteristic in the oily dispersion concentrate is only fully realized once the oil dispersion concentrate is diluted 15 in an aqueous medium to improve the eventual aqueous dilute spray mix or tank-mix, and as such is counterintuitive. Surprisingly these oil-insoluble dispersants improve the dispersion quality of aqueous diluted compositions prepared by dispersing the OD concentrate in water prior to use but appear to have no role in the non-aqueous OD concentrate.

[0081] 20

[0082] 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.

[0083] 25 The present invention provides fungicidal oil-based (oily), compositions, notably OD concentrates comprising,

[0084] A. water-immiscible carrier or solvent,

[0085] B. azole (triazole), fungicide,

[0086] C . a copper-compatibilizing tertiary amine-type agent such as tributylaminetributylamine, 30 tri pentylamine, N-methyl-N-propyl -hexylamine, or tri hexylamine, a fatty alkyl amine or fatty dialkyl amine such as dodecyl (lauryl), stearyl or oleyl amines or otherwise sterically hindered primary or secondary amines,

[0087] D. suspended solid copper fungicide, and E. dispersant. wherein the oily composition comprises less than 5% water and the amine prevents any significant reduction of amount of fimgicidally available (free), azole in the presence of copperbased fungicide.

[0088] References to alkylamines, dialkylamines and trialkyl amines should be seen as referring 5 equally to tri-alkenyl amines and tri-alkynyl amines etc., the central feature being the ability of the compound to shield the copper-based component of the oil-based composition from complexing with the triazole component of the composition without forming a strong or stable and / or irreversible copper- agent complex.

[0089] 10 Tributylamine is exemplified as one of the copper-compatibilizing tertiary amines-type agent which prevents the formation of copper-azole complex and thus avoids the need to add an ingredient which acts as a decomplexation agent as was reported in the literature.

[0090] However, it is stressed that the useful tertiary amines need not have all three substituents being the same hydrocarbon group as it is the ability to function to prevent azole-copper complexes 15 forming and maintaining a high proportion of free azole in a non-aqueous dispersion composition, that will determine the suitability of any agent.

[0091] A dispersant that may be a useful optional ingredient in OD concentrates according to the invention is characterized by displaying minimal or negligible solubility in either the water 20 immiscible carrier or solvent or the non-aqueous OD composition, and yet will only act to improve the dispersion quality of aqueous compositions (Tank-mix), prepared by diluting the inventive composition in water.

[0092] In some embodiments, the present invention provides oil based (OD) compositions comprising 25

[0093] (1) copper-based fungicide,

[0094] (2) azole (triazole), fungicide

[0095] (3) water immiscible carrier or solvent and

[0096] (4) tertiary amine compatibilizer agent (tributyl amine), wherein the oil-based composition is characterized by reduced triazole- copper complexation 30 analyzed by measuring the percentage of free azole remaining in the composition, when compared to OD compositions of copper-based fungicide and azole (triazole), fungicides absent the tertiary amine or compared with simple small primary or secondary amines that readily form strong complexes with copper. The level of free azole (triazole) content in the composition is usefully measured by HPLC analysis relative to a reference standard.

[0097] In some embodiments the present invention provides 3 -way fungicidal oil based OD compositions comprising

[0098] (1) copper-based fungicide, 5

[0099] (2) azole (triazole), fungicide

[0100] (3) water immiscible carrier or solvent and

[0101] (4) copper shielding agent such as tertiary amine (tributylamine) or sterically hindered amines, and

[0102] (5) a fungicidal agent which is neither a triazole nor a copper compound, exemplified by a 10 strobilurin fungicide such as picoxystrobin or azoxystrobin, or an anilide / carboxamide fungicide, exemplified by fluxapyroxad, wherein the free triazole content in the composition remains equal to, or greater than about 75% 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 15 application.

[0103] 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. 20

[0104] 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.

[0105] In some embodiments the free triazole content in the composition remains equal to or greater 25 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.

[0106] 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 30 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. Amine-type copper-compatibilizing agents,

[0107] Some illustrative non-limiting long chain amines to be assessed as candidate copper-shielding agents might include, hexadecyldimethylamine; octadecylamine; cocoamine; bis(hydrogenated tallow alkyl) amines (BHTAA); hydrogenated tallow alkyl amines acetates (HTAAA); tallow alkyl amines acetates (TAAA); N-tallow alkyltrimethylenediamines 5 (TAPDA); 1,3-propanediamine, N-[3-(tridecyloxy)propyl]-, branched (DPDAB); and, N,N,N'- trimethyl-N'-tallow alkyltrimethylenediamines (TMTADA), tri-n-benzylamine, methyl di-n- octylamine.

[0108] In some embodiments, the alkylamine comprises one or more sterically hindered mono amines which can be selected based on their inability to form strong, stable, or irreversible complexes 10 with the copper-based compounds of the non-aqueous compositions.

[0109] In some embodiments, the alkylamine comprises one or more long chain mono amines.

[0110] In some embodiments, the alkylamine comprises one or more fatty mono amines.

[0111] In some embodiments, the alkylamine comprises one or more sterically hindered di-amines.

[0112] In some embodiments, the alkylamine comprises one or more long chain di -amines. 15

[0113] In some embodiments, the alkylamine comprises one or more fatty di-amines.

[0114] In some embodiments, the alkylamine is represented by the structure A;

[0115] (A) 20 wherein:

[0116] (i) R1is hydrogen, alkyl, aryl, alkenyl, alkynyl or heterocyclic; R2is hydrogen, alkyl, aryl, alkenyl, alkynyl or heterocyclic; and R3is hydrogen, alkyl, aryl, alkenyl, alkynyl or heterocyclic;

[0117] (ii) at least one of R1, R2, and R3is alkyl, aryl , alkenyl, alkynyl or heterocyclic. 25

[0118] (iii) when all of R1, R2, and R3are alkyl or alkenyl or alkynyl groups, then Cn is Ci-26, commonly C1-C24, or often C j-Czz, sometimes C3-C18, such as butyl, pentyl, hexyl, and including alkyl fatty chains exemplified by, C12 or dodecyl (lauryl), saturated Cis (stearyl) or unsaturated Cis (oleyl) (iv) when the alkylamine represented by the structure A is a primary or secondary amine then at least one of R1, R2, and R3are alkyl or alkenyl or alkynyl groups, wherein Cn is Ce- 26, commonly Cs~C24, or often Cs~C22, such as alkyl fatty chains exemplified by, C12 or dodecyl (lauryl), saturated Cis (stearyl) or unsaturated Cis (oleyl). 5

[0119] In some embodiments, alkyl, which may be optionally substituted, denotes a linear or branched or cyclic hydrocarbon groupcomprising n carbon atoms.

[0120] In some embodiments the alkyl groups are long chains such as CHftCHzkCHz. CH3(CH2)IOCH2, CH3(CH2)I2CH2, CH3(CH2)I4CH2, CH3(CH2)I6CH2, CH3(CH2)I8CH2. Similarly, these long chains may be, substituted, linear, branched or unsaturated analogues 10 thereof.

[0121] 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. 15

[0122] In some embodiments, aryl, which may be optionally substituted, denotes to carbocyclic aromatic radicals having from 6 to 14 carbon atoms.

[0123] 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. 20

[0124] In some embodiments, substituted means that the group (R1, R2and / or R3) may or may not be further substituted by one or more groups such as Cnalkyl, aryl, halogen, hydroxyl, thio, amino, cyano, oxo, nitro, acyl, amido, C1-6 alkoxy, C1-6 alkenyloxy, aryloxy, acyloxy, C1-6 alkylamino, arylamino, C1-6 alkylthio, arylthio, alkylsulfonyl, arylsulfonyl, alkylsulfmyl, arylsulfmyl, Ci- 8 alkylamido, and carboxyl. 25

[0125] In some embodiments, all of, R1, R2, R3are alkyl or olefin.

[0126] In some embodiments, all of, R1, R2, R3are the same alkyl or olefin group.

[0127] In some embodiments, all of, R1, R2, R3are butyl.

[0128] In some embodiments, all of, R1, R2, R3are butenyl.

[0129] In some embodiments, each of R1, R2, R3are different alkyl or olefin (unsaturated) groups. 30 In some embodiments, an alkyl is an alkyl fatty chain.

[0130] In some embodiments, R1, R2and R3are methyl.

[0131] In some embodiments, R1, R2and R3are ethyl. In some embodiments, the R1is H and R2and R3are C 12-22 alkyl such as Cis.

[0132] In some embodiments, the R1is H and R2and R3are C12-22 alkenyl such as Cis.

[0133] In some embodiments, the selected copper shielding agent is a di-alkyl amine which such as di -oleyl amine, or a trialkyl amine such as tri-oleyl amine.

[0134] In some embodiments, the di-alkylamine is di-dodecyl amine or a trialkyl amine such as tri- 5 dodecyl amine.

[0135] In some embodiments, the di-alkylamine is di-benzyl amine or a trialkyl amine such as tribenzyl amine.

[0136] In some embodiments, copper shielding agent is hexamethylene tetra amine.

[0137] In some embodiments, copper shielding 10

[0138] In some embodiments, copper shielding agent is ethylene diamine.

[0139] In some embodiments, di-alkylamine is di-Butylamine or substituted sterically hindered by substitution with further hydrocarbon groups.

[0140] In some embodiments, trialkyl amine is tributylamine.

[0141] In some embodiments, alkylamine is Di-lauryl amine or tri-lauryl amine. 15

[0142] In some exemplary embodiments the inventive triazole compatibilizing agent (copper- shielding additive), is a tertiary and / or sterically hindered alkylamine, aryl or olefinic amine ,and illustratively exemplified by tributylamine. The addition or inclusion of copper shielding agent 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 20 compositions, where the improvement does not appear to be related to the usual activity of alkylamine in pesticidal formulations. The amount of free triazole available for fungicidal efficacy contained in the compositions is maintained both during compounding and over periods of storage up to shelf life, and the amount of complexed triazole fungicide is minimized, and thus the addition of compounds whose function might be described as de- 25 complexing agents is not needed, as the formation of these complexes has been avoided during the period when the composition is still a non- aqueous concentrate rather than reversed at the time of aqueous dilution.

[0143] 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 30 with triazoles might have a different character.

[0144] 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 copper shielding triazole compatibilizing agents (aka copper shielding agents), most notably tertiary amines such as tributylamines or other amines which do not form strong copper-compatibilizing agent complexes. The compatibilized triazole fungicide obtained are useful to prepare improved inventive oil-based compositions of (compatibilized) triazole fungicide and copper fungicide. 5

[0145] 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.

[0146] 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 than others. 10

[0147] (a) dissolve the azole fungicide (e.g., prothioconazole, Tebuconazole etc.), in immiscible solvent(s) such as aromatic hydrocarbons and / or dialkyl decanamide);

[0148] (b) Add

[0149] (i) immiscible carrier such as Methyl Soyate;

[0150] (ii) dispersant 15

[0151] (iii) surfactant and optionally antifoam agent;

[0152] (c) add, a. copper shielding agent such as Tributylamine, b. copper fungicide e.g., Copper Oxychloride, and optionally c. a thickening agent exemplified by colloidal or fumed, silicon dioxide; 20

[0153] (d) homogenize & sieve.

[0154] 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.

[0155] 25

[0156] It should be clear that the order of the steps in the above general process for preparing one embodiment of the oil-based copper and azole (triazole) fungicide composition, is not always absolutely critical although in particular instances a particular order of steps may be easier to process than others, it may be that there is an advantage in compatibilizing the triazole before adding the copper compound depending on the other ingredients. This type of process 30 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 copperbased 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.

[0157] In many embodiments the process steps are completed by a packaging step wherein the oil 5 based composition is packaged in a container or package that ensures stability of the composition over the intended shelf life.

[0158] 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 10 described herein without departing from the general teaching provided.

[0159] Non-limiting illustrative compositions might include the following components. Persons skilled at formulating agricultural Oil Dispersions formulation will immediately see options for alternative inactive ingredients.

[0160] While the astonishing advantages of this invention are most apparent in compositions where 15 the amount of copper-based compound vastly exceeds the amount of copper-shielding triazole compatibilizing agent, and relatively small amounts of the agent can compatibilize an large excess of triazole fungicide, this invention is not dependent on the relative amounts (ratio), of the azole (triazole) and copper active pesticidal ingredients but rather the inclusion of relatively very small amounts of the copper-shielding amine-type ingredient which compatibilizes the 20 triazole to being in the same composition as the copper compound so that that least about 70%, and preferably considerably more of the azole active ingredient remains free and uncomplexed over storage and until applied at the point of use such that the invention relates to the prevention of deactivating triazole-copper complex and the maintenance of the great majority of Triazole as free, no matter how much copper and / or how much triazole is present within a very wide 25 range. Because the inclusion of the copper-shielding agent will compatibilize at least a portion of the triazole thus protecting at least some of the triazole which otherwise will disadvantageously complex with at least a portion of the copper.

[0161] As long as the oil-based composition comprises an amount of copper and an amount of Triazole (azole) in an immiscible solvent or carrier, the issue of formation of deactivating triazole- 30 copper complex is a problematic issue that is solved by the inventive use of surprisingly small amounts of copper-shielding triazole compatibilizing agent as herein defined. As alluded to above, one of the most surprising aspects of the invention is that surprisingly small amounts of copper-shielding triazole compatibilizing agent can shield very large amounts of copper from complex formation with triazoles while at the same time not being themselves neutralized or deactivated by the large excess of copper typically found in such compositions.

[0162] In order to ensure that these very small amounts of the amine type copper-shielding agents are 5 able to function as triazole compatibilizing agents the copper-shielding agent is selected primarily only from those compounds which do not form strong copper-agent type complexes, leaving the copper-shielding agent free to advantageously interact with the triazole (azole).

[0163] It is this sub-group of triazole compatibilizing agents that are herein termed “copper-shielding agents” in that they are both able to prevent formation of deactivating triazole-copper 10 complexes and at the same time are not depleted from the system (composition), by forming strong, stable and / or irreversible agent-copper type complexes.

[0164] Copper-shielding triazole compatibilizing agents are capable of compatibilizing many time their weight of triazole in oily dispersions comprising a great excess of copper.

[0165] In many oil dispersion concentrate composition embodiments according to the invention, it is 15 not uncommon for a composition comprising greater than 5% w / w triazole and greater than 20% w / w copper in immiscible carrier / solvent to be compatibilized by between about 0.3 and 1.8% w / w Copper-shielding triazole compatibilizing agents by weight based on the total weight of the composition.

[0166] The copper-shielding agents that are shown to be suitable are exemplified by tertiary organic 20 amines, aromatic amines, long-chain hydrocarbon substituted amines or fatty amines with chain lengths of at least Q or commonly greater than Cx and typically up to about C26 although more commonly having alkyl or olefin substituents with chain lengths of Cx-24 such as, C12 or Cis substituted amines as detailed herein elsewhere.

[0167] In some OD concentrate embodiments, the concentration of the copper-shielding triazole 25 compatibilizing agent as herein defined in the composition is no more than 10% by weight based on the total weight of the composition.

[0168] In some OD concentrate embodiments, the concentration of the copper-shielding triazole compatibilizing agent in the composition is between 0.1% and 8% ±10% (about 8%), more typically 0.3% to 5%± 10%, and particularly noted between 0.5 - 2.5% ±10% by weight based 30 on the total weight of the composition. In some OD concentrate embodiments, the concentration of the copper-shielding triazole compatibilizing agent in the composition is between about 0.5 - 1.8% ±10% (about 1.8%), by weight based on the total weight of the composition.

[0169] In some OD concentrate embodiments, the concentration of the copper-shielding triazole compatibilizing agent in the composition is between about 0.75 - 1.4% ±10% (about 1.4%), by 5 weight based on the total weight of the composition.

[0170] In some concentrate composition embodiments of the invention the concentration of the tributylamine in the composition is between 0.5% and 1.6% ±10%. In some exemplified OD concentrate embodiments, the concentration of the tributylamine in the composition is 0.75%±10% and in some other embodiments the concentration of the tributylamine in the 10 composition is 1.2% ±10%.

[0171] In some embodiments the concentration of the copper-shielding triazole compatibilizing agent in the composition is between about 0.5 - 1.2% ±10% (about 1.2%), by weight based on the total weight of the composition. In some embodiments the copper-shielding triazole compatibilizing agent in the composition is either tertiary amine such as tributylamine or fatty 15 (long chain) amine or otherwise sterically hindered amine unable, to form copper-agent strong, stable or irreversible complexes in the composition.

[0172] The non-limiting examples of compositions we use to illustrate the invention, include an optional additional active ingredient as well as illustrative non-active formulation ingredients, for the purposes of the non-limiting illustrations, we exemplify compositions comprising more 20 than one type of surfactant and more than type of Immiscible carrier or solvent, to reflect some common formulation practices but by no means suggesting that there is significance of these non-active ingredient choices to the operation of the invention other than optimization.

[0173] However, as the invention relates only to the interaction of triazole (azole) compounds with copper compounds in a carrier and the inventive inclusion of a copper-shielding agent (triazole 25 compatibilizing), the other (non-pesticidally active), ingredients of the illustrative compositions can be referred to by their formulation functions together with exemplified examples of each. Persons skilled in these formulation art will immediately be aware of alternative ingredients that will perform the same formulation function, such alternative ingredients are no departure from this invention as the identity of these excipient non-active 30 ingredients are not necessarily critical to the working of the invention of preventing the complex formation. Clearly however, persons skilled in the formulation arts will chose these non-active compounds to optimize the characteristics of the composition (triazole compatibilizing), but both optimized and non-optimized compositions are within the scope of the invention so long as Copper-based compound, free Azole (triazole) compound and copper shielding (triazole compatibilizing), agents are contained in an oil-based composition, such as in an Oil Dispersion concentrate, or 5 diluted ready-to-spray mixes (tank-mix) prepared by diluting the OD concentrate .

[0174] Illustrated below is a platform composition detailing both the essential and optional components of a large number of OD concentrate embodiments of the invention. The content of the Copper, Triazole and copper-shielding triazole compatibilizing agent are exemplified (non-limiting), numerically as they are the central components together with the non-aqueous 10 immiscible carrier or solvent. The other ingredients are included by their function as the relative amounts in such a composition is well within the skills of any Oil Dispersion formulation practitioner and the invention is in no way dependent on the exact numerical content of these other ingredient components.

[0175] Non-Limiting Illustration of OD Copper 300 triazole 80 Oil Dispersion OD concentrate

[0176] In the platform illustrated general composition above it can be seen that the immiscible carrier / solvent, surfactant, and emulsifier can be mixtures of these types of components as is often found in Oil Dispersion compositions. In some embodiments the Copper Shielding 5 Triazole Compatibilizing Agent comprises no more than 2% w / w of the weight of the total composition, and often between about 0.3% and 1.8% w / w.

[0177] The Copper-based compound is exemplified by 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 10 oxychloride sulfate (COCS), tribasic copper sulfate such as cupric sulfate, tri -cupric hydroxide, hemihydrate, complexed or chelated copper compounds, and any combination thereof.

[0178] 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.

[0179] Illustrative examples of the additional active ingredients can include though not limited to 5 strobilurin fungicides, benzamide fungicide, morpholines, Qil fungicide, SDHI and any combination thereof. 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, 10 metyltetraprole and fluoxastrobin. SDHI may include but is not limited to penthiopyrad, boscalid, flutolanil, fluxapyroxad, inpyrfluxam , fluopyram, fluindapyr, benzovindiflupyr, bixafen and pydiflumetofen. Qil fungicide may include but is not limited to cyazofamid, amisulbrom and fenpicoxamid. Morpholines may include but is not limited to aldimorph, fenpropimorph, tridemorph, dodemorph, spiroxamine, piperalin, fenpropidin. 15

[0180] Immiscible carrier / solvent can be illustrated by hydrocarbons, Cio, aromatics (Solvesso 150), heavy aromatic naphthalene (Solvesso 200), methylated soybean oil, N,N-dimethyl decanamide.

[0181] Surfactant can be illustrated by ) ABA poly hydroxyester-PEG-poly hydroxyester copolymers (Zephrym PD2206 block copolymer), tristyrylphenol ethoxylated(Soprophor BSU), 20 polyoxyethylene (20) sorbitan monolaurate (Tween 24-lq-(ap), oxirane, monobutyl ether (Atlas G-5002L-lq-cq), alkyl end-capped polyethylene oxide-polypropylene block copolymer, Benzenesulfonic acid, Cio-i3-(linear)alkyl derivatives, calcium salt, (Rhodacal 60 / BE).

[0182] An oil dispersion concentrated composition comprising Prothioconazole 80g / L, Fluxapyroxad 50g / L, Copper Oxychloride 300 g / L and tributylamine 6 g / L in a mixture of Hydrocarbons, 25 Cio, aromatics (Solvesso 150), Methylated Soybean oil and N,N-Dimethyl Decanamide, was found to have greater than 98.5% of the Prothioconazole as free Prothioconazole after storage at 54°C for two weeks when analyzed by HPLC peak area comparison with prothioconazole reference standard. This oil dispersion concentrated composition also contained ABA poly hydroxyester-PEG-poly hydroxyester copolymers (Zephrym® PD2206 -block copolymer), 30 tristyrylphenol ethoxylated (Soprophor® BSU), Polyoxyethylene (20) sorbitan monolaurate (Tween 24-lq-(ap)), butyl polyethylene oxide-polypropylene block copolymer (Atlas G-50021- Iq-(cq)), benzenesulfonic acid, Cio-i3-(linear) alkyl derivatives, calcium salt, (Rhodacal® 60 / BE) and Distilled Tall Oil (DTO), (Altapyne M28-B), inventors do not believe these ingredients effect the ability of the tributylamine to compatibilize the prothioconazole to maintain free prothioconazole and shield the copper. Similarly, the oil dispersion concentrated composition contained fumed silica (Cab-o-Sil M5) as a thickener and Polydimethylsiloxanes 5 as an antifoam agent, inventors do not believe these ingredients are intrinsic to the effect of compatibilizing the prothioconazole to remain as free prothioconazole or the copper-shielding effect, although formulation optimization by skilled formulators by careful selection is envisaged.

[0183] The Copper Shielding (Triazole Compatibilizing) Agent has been herein defined elsewhere 10 though some illustrative examples include tertiary organic amines such as tributylamine or primary and secondary amines that may include hydrocarbon amines which may include alkyl or olefin amines wherein the hydrocarbon groups are long or fatty alkyl or olefin chains or be substituted with sterically hindered substituents that achieve the required hindrance to coppercopper shielding agent complex formation. 15

[0184] Similarly, amine type compounds substituted by one or more aromatic groups are often suitable candidates as copper shielding agents, and a simple test as outlined elsewhere in this disclosure will reveal the suitability of the candidate for a specific Oil Dispersion composition. As detailed elsewhere a simple test employing a model Oil Dispersion platform is a suitable vehicle for comparing potential candidates for selection of the optimum copper-shielding agent. It may 20 well be that the selection is based on the minimum content of the agent that is required for triazole compatibilization, although often this is not the only criterion for selection which will include many formulation quality aspects.

[0185] In some embodiments the invention provides oil-based compositions of triazole and copper fungicides and a copper shielding amine such as tributylamine optionally comprising an 25 additional pesticide (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, and preferably significantly less. In most preferred embodiments less than 5% of the triazole included when compounding the composition is measured as triazole-copper complex or nonfree triazole. The term free triazole reflects the triazole that remains fungicidally efficacious. 30

[0186] 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.

[0187] In certain embodiments the oil based composition of the invention comprises less than 15% of the triazole content as triazole-copper complex.

[0188] In several embodiments the oil based composition of the invention comprises less than 10% of 5 the triazole content as triazole-copper complex.

[0189] In several optimized embodiments the oil based composition of the invention comprises less than 5% of the triazole content as triazole-copper complex.

[0190] In some embodiments the invention provides packaged stable oil-based compositions of triazole and copper fungicides and a tertiary amine such as tributylamine, optionally 10 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 (tributylamine) acting as copper-shielding triazole compatibilizing agent.

[0191] In some embodiments the inventive oil-based composition of triazole and copper fungicides is 15 adapted for dilution with and / or dispersion in, water prior to use, wherein, the adaptation comprises including in the oil-based composition, a dispersant that is not soluble in the oilbased 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.

[0192] In some embodiments the inventive oil-based composition of triazole and copper fungicides 20 and tributylamine, is adapted for dilution with and / or dispersion in, water prior to use, wherein, the adaptation comprises including in the oil-based composition, a 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.

[0193] The present invention also provides a method for controlling pathogenic, especially, fungicidal 25 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. 30 DETAILED DESCRIPTION

[0194] Inventors have surprisingly found that oil-based (OD) compositions of triazole (azole) fungicides together with copper fungicides can be formulated without significant triazolecopper complex formation by inclusion of copper-shielding agents, including tertiary amines exemplified by tributylamine or long -chain, fatty or sterically hindered amines. This is an 5 important improvement 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. Importantly though, inventors have found that it is possible to prevent or avoid triazole-copper complex formation by inclusion of no more than about 10% by weight of the composition of the amine- type copper-shielding agents so long as the copper-shielding agent, which compatibilize 10 triazoles is carefully selected such that a minimum of strong, stable and / or irreversible agent- copper complex is formed.

[0195] In typical embodiments less than about 3% w / w, often less than about 2.5% w / w, of the copper- shielding agent is enough to entirely avoid significant copper-triazole deactivating complex formation, even when the triazole content is much greater than this. In some OD concentrate 15 embodiments of the invention no more than 2% w / w by weight based on the total weight of the composition.

[0196] While it is conceivable that when an amine-type triazole compatibilizing agent compound which does indeed form strong agent-copper complexes is in great molar excess as compared to the copper content in the composition, exemplified by situations where the entire continuous 20 phase of the dispersion is the amine-type agent, then the choice of compound for compatibilizing the triazole might conceivably be not be important.

[0197] But, as previously mentioned this is not the case when, the content of the triazole compatibilizer in the composition is no more than 10%, and particularly when the agent comprises greater than 0.1% and less than 3% w / w by weight based on the total weight of the composition, or at 25 a ratio to copper of no more than 1:2.5 or particularly when the ratio of agent to copper is less than 1:8 then the choice of the copper-shielding triazole compatibilizing agent is extremely important to avoid strong interactions of the agent with copper that might deplete the amount of amine available to compatibilize the triazole to such an excess of copper.

[0198] Thus, the inventors identify a group of copper-shielding triazole compatibilizing agent or 30 ingredient or additive, most notably tertiary amines such as tributylamine, or otherwise substituted amines that are unable to form strong, stable and / or irreversible copper- agent complexes, such as sterically hindered or amines substituted with long chain alkyl or olefin groups such as fatty amines, which when combined with triazole fungicides provide compatibilized triazole fungicide compound at very low concentrations in oily dispersion compositions while not being themselves deactivated as compatibilizers by forming strong copper-agent complexes. 5

[0199] The copper-shielding agents together with triazoles form compatibilized triazole fungicide compound which 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. In 10 compositions of the invention the amount of free triazole compared to the amount of triazole included when compounding the composition is exemplified by at least 70% and preferably, considerably in excess of 75% free triazole preserved.

[0200] Thus, in some embodiments, the composition comprises at least 70% of the amount of the azole fungicide which was used for formulating or preparing the composition as free triazole . In some 15 embodiments, the composition comprises at least 75% 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 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 20 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 25 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.

[0201] The copper shielding agent which in several embodiments are tertiary amines exemplified by 30 tributylamines, in the inventive oil -based (OD) composition at a contents of less than 10% by weight, prevents the formation of triazole-copper complex and maintains a high proportion of free triazole, available for fungicidal efficacy, mediated by being selected for being unable to form strong, stable or irreversible copper-agent complexes .

[0202] In typical embodiments the selected copper shielding agent is such that it is capable of compatibilizing at least three times the amount of triazole by weight.

[0203] In noted embodiments when carefully selected, a copper-shielding agent content of between 5 0.3% and 2% w / w weight based on the total weight of the composition is sufficient to compatibilize the great majority or even all the triazole in a composition comprising greater than 5% triazole, commonly between about 0.5% and about 1.5% is sufficient.

[0204] In an illustrative embodiment, a non-aqueous oil dispersion concentrate composition, (density about 1.2) comprising about 25% dispersed copper oxychloride (about 300g / L) and about 7% 10 dissolved prothioconazole (about 80 g / L) by weight in immiscible carrier / solvent was compatibilized by no more than about 0.5% w / w (about 6 g / L), tributyl amine. When this composition is analyzed after storage at 54°C for two weeks, greater than 98.5% of the triazole used for compounding the composition is found to remain as free prothioconazole measured by comparing the HPLC peak area against a free prothioconazole reference standard at the 15 same relative retention time (RRT). Significantly, in the above experiment, greater than 99% of the copper as oxychloride is measured in the composition after storage at 54°C for two weeks, indicating that the copper had not formed stable, irreversible or strong copper- compatibilizing agent complexes. Additionally, the composition is color stable and remains a turquoise suspension indicative of the uncomplexed copper compound. 20

[0205] Inventors foresee that particular organic amines having specified characteristics can be as useful as tertiary amines to act as copper-shielding triazole compatibilizing agents. In principal it appears that a suitable agent is one that has both a greater affinity to copper than the triazole, while simultaneously being unable to form strong complexes with the large excess of copper typically found in these oil dispersion compositions. Thus, sterically hindered amine based 25 compounds perhaps with aromatic substituents or long -chain (C8-22) fatty amines may have the characteristics of both shielding the copper from forming complexes with triazole compounds and yet not removed from the system by forming compatibilizing agent-copper complexes.

[0206] Many of the disclosed copper-shielding agents useful as triazole compatibilizing agents are required to be dissolved in (hydrophobic), non-aqueous water-immiscible solvent and / or 30 carrier and also several of the disclosed copper-shielding agents useful as triazole compatibilizing agents are long chain or fatty amines, thus, in some embodiments the copper- shielding triazole compatibilizing agents are amine type compounds which have a low Hydrophilic / Hydrophobic balance such as below HLB=9 or below HLB = 6.

[0207] In some embodiments, the copper-shielding triazole compatibilizing agents are amine type compounds with long chain hydrocarbon substituents, such as fatty alkyl or olefin chains, characterized by an HLB equal or less than 9. 5

[0208] In some embodiments, the copper-shielding triazole compatibilizing agents are organic amine type compounds with hydrocarbon substituents characterized by an HLB equal or less than 6.

[0209] Thus, for a particular Oil Dispersion composition of triazole and copper compounds a test may 10 be conducted to compare two similar compounds of different HLB values, to see which is more suitable. For example, taking ethoxylated tallow amines as candidate tertiary amines it is noticed that ethoxylated tallow amines having two moles of ethylene oxide groups per mole has a calculated HLB of 5 whereas ethoxylated tallow amines having eight moles of ethylene oxide groups per mole has a calculated HLB of 11. A useful comparative test will easily 15 determine which of these compounds is most suitable for inclusion in an oil dispersion of triazole and copper compound though it is envisaged that perhaps both are equally useful depending on the details of the composition ingredients. Conceivably this simple test will show that neither or both of these compounds is useful because of factors unconnected to the HLB value. 20

[0210] The term “triazole compatibilizing agent” does not imply that the activity or mechanism by which these agents achieve their effect is necessarily by affecting some chemical or physical change in the triazole compound itself (although it is conceivable that it might), 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 25 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 30 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.

[0211] Inventors have found that the inclusion of copper-shielding agents such as tertiary amines, such as tributylamine, or tertiary amines with different alkyl or olefin substituents, in oil-based compositions of triazole and copper fungicides, promotes multiple improvements and 5 advantages in the characteristics of compositions of triazole and copper fungicides. These aforementioned advantages might include the function of tributylamine 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. 10

[0212] It has been observed that oil dispersion compositions of triazole fungicide and copper oxychloride with copper shielding triazole compatibilizing agent are additionally stable to unwanted physical degradation such that they are for example, stable and do not appreciably change color over storage while a comparable composition absent the copper-shielding agent changes from a turquoise suspension to dark brown during storage. Such color changes may 15 perhaps be a direct result of azole-copper complexes in non-compatibilized compositions.

[0213] While inventors highlight the triazole compatibilizing activity of the tertiary amines (e.g. tributylamine, N,N,N-butyl, pentyl, hexylamine etc.), as well as the other specifically useful amines as defined elsewhere in this disclosure, 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 20 copper-shielding ingredient and no limitation is intended or implied that would limit the invention to any specific level of content other than being less than 10% by weight of the composition, or use simply based on the level of compatibilizing ability separate from other important functions and advantages obtained by their inclusion.

[0214] The invention relates to the prevention of triazole -copper complex formation rather than (or in 25 addition to), the breaking or decomplexation of a complex that had already formed. Inventors have found that the prevention of triazole -copper formation with minimal amounts of tertiary amines, exemplified by tributylamine and the other similarly useful compounds defined elsewhere in this disclosure, 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 30 compound. In all experiments performed to date, no more than 2.5% of the copper-shielding triazole compatibilizing agents were needed to maintain greater than 80 percent of free triazole in an oil dispersion even in combination with over 20% copper based compounds and often significantly more than 80% such as more than 95% or more than 98% w / w.

[0215] In experiments comparing various candidates as triazole compatibilizing agent ingredients or components, and the minimum content of each required to maintain high a proportion of the triazole as “free triazole” in the OD compositions, inventors found the optimized characteristics 5 of the most useful of these agents as detailed herein. The free azole was tested after comparing compositions having the same general composition with the tested candidate ingredient being the only variant and as measured by HPLC recovery by absorbance peak area comparison, at the RRT of the triazole used, . For illustrative purposes the triazole fungicide chosen is any of prothioconazole, tebuconazole, difenoconazole, with prothioconazole being a useful model 10 triazole.

[0216] As an example, in the samples containing 0.5 % w / w and 1.25 % w / w tributylamine of the candidates tested in the experiments, the recovery results were able to be higher than 98%.

[0217] Definitions

[0218] Unless defined otherwise, all technical and scientific terms used herein have the meaning 15 commonly understood by persons of ordinary skill in the art to which this subject matter pertains.

[0219] 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. 20

[0220] 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.

[0221] In addition, all ranges directed to the same component or property herein are inclusive of the 25 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%. 30

[0222] 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 by weight. Commonly the % water content in oil-based concentrated embodiments, is significantly lower than 5%.

[0223] 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 5 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 10 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.

[0224] 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 15 of a particular crop in this disclosure is in no way indicative of an intention to exclude.

[0225] 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. 20

[0226] 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.

[0227] It was surprisingly found that incorporating less than 10% by weight of specific organic amines such as tertiary alkyl or olefin amines exemplified by tributylamine (azole compatibilizing agent), or other organic amine type compounds which have a relatively higher affinity to copper 25 than triazoles (azoles), in an oil-based composition comprising copper-based fungicide and azole fungicide provides superior oil-based compositions exemplified by Oily Dispersion (OD) concentrate compositions, so long as the amine-type compound does not form strong stable (irreversible), complexes with copper.

[0228] The present invention provides a non-aqueous oil based compatibilized triazole fungicide, 30 comprising, (1) azole fungicidal compound (triazole),

[0229] (2) copper-shielding triazole compatibilizing agent, , and

[0230] (3) water immiscible carrier and / or solvent, wherein the copper shielding agent comprises no more than 10% by weight of the oil based compatibilized triazole fungicide, and wherein the compatibilized triazole fungicide is 5 characterized by maintaining at least 70% of the triazole as free triazole when combined with copper-based compounds.

[0231] The present invention provides an oil based composition, OD, comprising

[0232] (1) copper-based fungicide, 10

[0233] (2) azole fungicide (triazole),

[0234] (3) copper-shielding agent such as a tertiary alkylamine exemplified by tributylamine

[0235] (4) water immiscible carrier and / or solvent wherein the copper shielding agent comprises no more than 10% by weight of the oil based compatibilized triazole fungicide, and wherein the compatibilized triazole fungicide is 15 characterized by maintaining at least 70% of the triazole as free triazole in the OD composition..

[0236] The present invention provides a non-aqueous oil based fungicidal composition, comprising,

[0237] (1) compatibilized azole fungicide (triazole),

[0238] (2) copper based fungicide and 20

[0239] (3) water immiscible carrier and / or solvent, wherein the azole fungicide has been compatibilized for combination with copper fungicides by contacting the azole with copper-shielding triazole compatibilizing agent,.

[0240] The present invention provides an oil based composition, OD, comprising

[0241] (1) copper-based fungicide, 25

[0242] (2) azole fungicide,

[0243] (3) dispersant,

[0244] (4) tertiary alkylamine, such as, tributylamine (copper-shielding triazole compatibilizing agent)

[0245] (5) water immiscible carrier and / or solvent. 30 In some embodiments, the tertiary alkylamine (such as a mixed amine or such as tributylamine), is mixed with the triazole (azole), fungicide prior to combining with the copper fungicide.

[0246] In some embodiments the triazole fungicide is fully dissolved in the water immiscible carrier and / or solvent prior to combining with the tertiary alkylamine (tributylamine). 5

[0247] In some embodiments, the SC-dispersant and / or alkylamine is mixed with the copper-based fungicide prior to combining with the azole fungicide.

[0248] 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 10

[0249] 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.

[0250] In some embodiments, when preparing the oil-based compositions of the invention, the azole 15 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.

[0251] In some embodiments, the invention provides a composition comprising any one of the 20 combinations described herein and at least one agriculturally acceptable additive suitable for inclusion in oil-based pesticidal compositions.

[0252] 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 25 formulation considerations that will determine optimal additives, other than the inventive triazole compatibilizing agents and SC-dispersants.

[0253] 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.

[0254] In some embodiments, the composition comprises a solution of compatibilized azole fungicide in one or more immiscible carriers, copper-shielding triazole compatibilizing agent such as, tertiary alkylamine (e.g., tributylamine) or fatty (long chain) amine or otherwise sterically 5 hindered amine unable to form copper-agent stable, strong, or irreversible complexes, 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 10 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.

[0255] A composition according to the invention is most notably in the form of an oil-based liquid, 15 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 20 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. 25

[0256] A surprising feature of the copper triazole Oil Dispersion composition of the invention is the ability of a minimal amount of the selected copper-shielding agent is sufficient to compatibilize much larger amounts of triazole in the presence of much larger amounts of copper. The invention is focused on copper-shielding agents capable of compatibilizing amounts of triazole in the presence of much larger amounts of copper than the agent. 30

[0257] The inventive compositions are sometimes characterized by including greater than 0.1% and less than 10% w / w copper-shielding triazole compatibilizer agent and between greater than 10% and 50% copper-based compound in amounts such that the ratio between the copper- shielding agent and copper is less than 1 : 1 In some common embodiments the ratio between the copper-shielding agent and copper is much less than 1: 1 illustrated by compositions comprising about 300 g / L copper oxychloride and tributyl amine between 6 g / L and 15 g / L.

[0258] In some embodiments the ratio between the copper-shielding agent to copper of no more than 5 1:2.

[0259] In some embodiments the ratio between the copper-shielding agent to copper of no more than 1:2.5.

[0260] In some embodiments the ratio between the copper-shielding agent to copper of no more than 1:8. 10

[0261] In some embodiments the ratio between the copper-shielding agent to copper of no more than 0.5: 5.

[0262] In some embodiments the ratio between the copper-shielding agent to copper of no more than 0.5: 10.

[0263] In some embodiments the ratio between the copper-shielding agent to copper of no more than 15 0.5: 15.

[0264] In some embodiments the ratio between the copper-shielding agent to copper of no more than 0.5: 20.

[0265] In some embodiments the ratio between the copper-shielding agent to copper of no more than 0.5:25. 20

[0266] In some embodiments the ratio between the copper-shielding agent to copper of no more than 0.5: 30.

[0267] In some embodiments the ratio between the copper-shielding agent to copper of no more than

[0268] In some embodiments the ratio between the copper-shielding agent to copper of no more than 0.5: 10. 25

[0269] In some embodiments the ratio between the copper-shielding agent to copper of no more than 0.8: 20.

[0270] In some embodiments the ratio between the copper-shielding agent to copper of no more than 0.75: 20. In some embodiments the ratio between the copper-shielding agent to copper of no more than 0.75:25.

[0271] In some embodiments the ratio between the copper-shielding agent to copper of no more than 0.75: 20.

[0272] In some embodiments the ratio between the copper-shielding agent to copper of no more than 5 1.2:2.5.

[0273] In some embodiments the ratio between the copper-shielding agent to copper of no more than 1.2:8.

[0274] In some embodiments the ratio between the copper-shielding agent to copper of no more than 1.2: 5. 10

[0275] In some embodiments the ratio between the copper-shielding agent to copper of no more than 1.2: 10.

[0276] In some embodiments the ratio between the copper-shielding agent to copper of no more than 1.2: 15.

[0277] In some embodiments the ratio between the copper-shielding agent to copper of no more than 15 1.2: 20.

[0278] In some embodiments the ratio between the copper-shielding agent to copper of no more than 1.2:25.

[0279] In some embodiments the ratio between the copper-shielding agent to copper of no more than 1.2: 30. 20

[0280] In some embodiments the ratio between the copper-shielding agent to copper of no more than

[0281] In some embodiments the ratio between the copper-shielding agent to copper of no more than 1.2: 23.

[0282] In some embodiments the ratio between the copper-shielding agent to copper of no more than 1.2: 22. 25

[0283] In some embodiments the ratio between the copper-shielding agent to copper of no more than 1.2: 20. In some embodiments the ratio between the copper-shielding agent to copper of no more than 1.2:27.

[0284] In some embodiments the ratio between the copper-shielding agent to copper of no more than 1.2: 50.

[0285] In many favored embodiments the preferred triazole compatibilizer compounds are specifically 5 characterized and differentiated as being compounds that will maintain at least 75% of the triazole as free triazole in non-aqueous compositions together with copper when the copper is in both copper molar excess and weight content excess as compared to the copper shielding agent, while generally if the agent will only function when it is in excess of the copper content, it indicates that it is not a copper-shielding triazole agent within the scope of this invention. 10

[0286] As with all figures and numbers, ratios are intended to be preceded by “about” meaning, where relevant ± 10% unless the context is clearly otherwise. Where the number or figure is related to a limit, such as “not more than” or “not less than”, then the figure is understood to be within the normal understanding of rounding up or down. For example, “no more than 50” does not exclude 50.4, and not less than 31 does not exclude 30.5 etc. 15

[0287] In some embodiments the composition is an OD concentrate comprising between about 0.4% and 1.5% w / w copper shielding agents, such as about 0.5%, about 0.75%, about 0.8%, about 1%, about 1.2% or about 1.4%, wherein copper shielding agents are exemplified by tertiary amines such as, tributylamine or by fatty (long chain) amine or otherwise sterically hindered amine unable to form copper-agent strong, stable or irreversible complexes, and between about 20 1% and 15% triazole fungicide, such as, between about 3% and 10% or 4.5% and 7.5%, in an immiscible solvent or carrier comprising copper compounds in amounts in both molar and weight excess of the copper shielding agent, wherein the triazole fungicide is dissolved in the immiscible carrier or solvent and the copper-based compound is dispersed immiscible carrier or solvent. 25

[0288] In some embodiments the non aqueous compositions of the invention comprise copper shielding agent and triazole pesticides compound (fungicides), wherein the compositions comprise copper-based compounds such that the amount of copper shielding agent is less than the amount of copper-based compounds and the ratio between copper shielding agents and the 30 triazole pesticides compound is not more than 1: 1. However it should be noted that composition embodiments in which the amount of copper shielding agent and triazole pesticides compound (fungicides) are in a ratio greater than 1: 1 are within the scope of the invention as long as the amount of copper-based compound in the composition is in excess of the amount of copper shielding agent.

[0289] In some embodiments the non aqueous compositions of the invention comprise copper shielding agent and triazole pesticides compound (fungicides) in immiscible carrier or solvent, 5 wherein the compositions comprise copper-based compounds such that the amount of copper shielding agent (amine) is less than the amount of copper-based compounds and wherein the ratio between copper shielding agents and the triazole pesticide compound is 0.4-1.5 : 1-30

[0290] In some embodiments the non aqueous compositions of the invention comprise copper shielding agent and triazole pesticides compound (fungicides) in immiscible carrier or solvent, 10 wherein the compositions comprise copper-based compounds such that the amount of copper shielding agent (amine) is less than the amount of copper-based compounds and wherein the ratio between copper shielding agents and the triazole pesticide compound is 0.5-1.3 : 3-13.

[0291] In some embodiments the non aqueous compositions of the invention comprise copper shielding agent and triazole pesticides compound (fungicides) in immiscible carrier or solvent, 15 wherein the compositions comprise copper-based compounds such that the amount of copper shielding agent (amine) is less than the amount of copper-based compounds and wherein the ratio between copper shielding agents and the triazole pesticide compound is 0.5-1.2: 4.5-7.5.

[0292] In some embodiments the non aqueous compositions of the invention comprise copper shielding agent and triazole pesticides compound (fungicides) in immiscible carrier or solvent, 20 wherein the compositions comprise copper-based compounds such that the amount of copper shielding agent (amine) is less than the amount of copper-based compounds and wherein the ratio between copper shielding agents and the triazole pesticide compound is 0.5-1.2:4.5-7.5. such as, about 0.75:4.5:7.5%, in an immiscible solvent or carrier. Wherein the triazole fungicide is dissolved in the immiscible carrier or solvent and the copper-based compound is 25 dispersed immiscible carrier or solvent.

[0293] 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 30 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).

[0294] 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 5 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. 10 In some embodiments, the concentration of the metallic copper in the formulation comprising the copper-based fungicide is 180 g / L ±10%.

[0295] 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 15 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 20 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. 25

[0296] 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 30 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.

[0297] 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%.

[0298] In some embodiments, the concentration of the copper-based fungicide in the composition is 5 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 10 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.

[0299] 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 15 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 20 phytotoxicity.

[0300] In some embodiments, the concentration of 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 dispersants in the composition is between 0.01% to 10% ±10% by weight based on the total weight of the composition. In some embodiments, 25 concentration of the dispersant in the composition is between 0.1% to 8% ±10% by weight based on the total weight of the composition.

[0301] 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. 30 In some OD concentrate embodiments, the concentration of the tributylamine in the composition is between 0. 1% and 8% ±10%, more typically 0.3%to 5%± 10%, and particularly noted between 0.4 - 1.7% ±10% by weight based on the total weight of the composition. In some concentrate composition embodiments of the invention the concentration of the tributylamine in the composition is between 0.5% and 1.6% ±10%.In some exemplified OD 5 concentrate embodiments the concentration of the tributylamine in the composition is 0. 5%±10% - 0.75%±10% (about 0.5% - about 0.75%) and in others the concentration of the tributylamine in the composition is 1.2% ±10% - 1.5% ±10% (about 1.2% - about 1.5%).

[0302] Inventors note that while a range of concentrations of the tributylamine component in a particular OD composition of a copper-based fungicide and triazole fungicide is useful across 10 the whole range, often formulation considerations seemingly unconnected with the inventive compatibilizing function will determine the optimal tributylamine concentration for that particular OD concentrate.

[0303] 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 15 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 tributylamine concentrations that are equally useful in compatibilizing the azole (triazole) fungicide provides the scope for a formulator to adjust the tributylamine content to provide both the azole compatibilization required for the OD and tank mix obtained therefrom, as well 20 as the optimal pH of the tank mix obtained by diluting / dispersing the OD concentrate in water.

[0304] 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.

[0305] The methodology used in the experimental section as herein disclosed above or later in this 25 disclosure 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.

[0306] In essence a very simple protocol for assessing the acceptability of a formulated composition as is exemplified later herein. 30 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. 5

[0307] 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 a more acceptable triazole compatibilizing agent / ingredient / additive .

[0308] The percent active content of azole fungicide of the triazole fungicide as free triazole is usefully 10 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..

[0309] To establish the optimal triazole compatibilizing agent compound or the optimal content, prepare samples with the only difference being test component / ingredient variation.

[0310] The analyses may be performed after storage 12 hours at room temperature. The analysis is 15 performed after the composition is stored for a period not less than two weeks at 54°C to select even more optimal copper-shielding triazole compatibilizing agent.

[0311] In some embodiments, the triazole compatibilizing agent candidate is alkylamine, olefin amine, or aromatic amine so long as the agent has a higher affinity for copper than the triazole 20 compound but is unable itself, to form strong stable (irreversible) complexes with copper.

[0312] In some embodiments, the alkylamine is represented by the structure A;

[0313] (A) wherein: 25

[0314] R1is hydrogen, alkyl, aryl, alkenyl, alkynyl or heterocyclic; R2is hydrogen, alkyl, aryl, alkenyl, alkynyl or heterocyclic; and R3is hydrogen, alkyl, aryl, alkenyl, alkynyl or heterocyclic; and at least one of R1, R2, and R3is alkyl, aryl , alkenyl, alkynyl or heterocyclic. when all of R1, R2, and R3are alkyl or alkenyl or alkynyl groups, then Cn is Ci- 26, commonly C1-C24, or often C1--C22, sometimes C3---C18, such as butyl, pentyl, hexyl, and including alkyl fatty chains exemplified by, C12 or dodecyl (lauryl), saturated Cis (stearyl) or unsaturated Cis (oleyl) when the alkylamine represented by the structure A is a primary or secondary amine then at 5 least one of R1, R2, and R3are aromatic or alkyl or alkenyl or alkynyl groups, wherein Cn is Ce- 26, commonly C8-C24, or often Cs -C22, such as alkyl fatty chains exemplified by, C12 or dodecyl (lauryl), saturated Cis (stearyl) or unsaturated Cis (oleyl). when one or two of R1, R2, and R3is hydrogen, the other(s) should be, aromatic or long or fatty hydrocarbon chains, (or quite hydrophobic) if agent-copper complexes are to be avoided. 10

[0315] In some embodiments, alkyl, alkenyl or alkynyl, which may be optionally substituted, denotes a linear or branched or cyclic hydrocarbon group comprising n carbon atoms.

[0316] 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.

[0317] In some embodiments, alkynyl which may be optionally substituted, denotes a linear or 15 branched, hydrocarbon group comprising n carbon atoms and at least one triple bond.

[0318] In some embodiments, aryl, which may be optionally substituted, denotes to carbocyclic aromatic radicals having from 6 to 14 carbon atoms.

[0319] 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 20

[0320] 1 to 4 are from the group consisting of oxygen, nitrogen and sulfur.

[0321] In some embodiments, substituted means that the group (R1, R2and / or R3) may or may not be further substituted by one or more groups such as Cnalkyl, aryl, halogen, hydroxyl,

[0322] In some typical embodiments, all three of, R1, R2, R3are the same.

[0323] In some embodiments, each of R1, R2, R3are different though commonly encountered agents 25 often have a maximum of one hydrogen substitution, and typically none of R1, R2, or R3are hydrogen in the most optimum agents found to date.

[0324] In some embodiments, an alkyl is cyclic and sterically hindered.

[0325] In some embodiments, an alkyl is an alkyl fatty chain and preferably the agent is at least a secondary amine. 30

[0326] In some embodiments, R1, R2and R3are butyl.

[0327] In some embodiments, R1, R2and R3are hexyl or pentyl. In some embodiments, at least one of R1R2and R3is C12 - C22 alkyl alkenyl or alkynyl.

[0328] In some embodiments, at least one of R1and R2and R3is Cis alkyl, alkenyl or alkynyl.

[0329] In some embodiments, the selected copper shielding triazole compatibilizing agent is an oleyl substituted amine.

[0330] In some embodiments, the copper shielding triazole compatibilizing agent is a dodecyl 5 substituted amine such as a di -dodecyl substituted amine.

[0331] In some embodiments, the alkylamine is a benzyl substituted amine.

[0332] In some embodiments, the copper shielding triazole compatibilizing agent is a butyl substituted amine.

[0333] In some embodiments, alkylamine is tributylamine as herein exemplified. 10

[0334] In some embodiments, triazole compatibilizing agent comprises tertiary fatty alkylamine In some embodiments, alkylamine comprises a Butyl substituted amine.

[0335] In some embodiments, alkylamine comprises di-oleyl, di-dodecyl, di-lauryl, or di-stearyl amine, sometimes further substituted with another hydrocarbon.

[0336] In some embodiments, alkylamine comprises tributylamine. 15

[0337] In some embodiments, alkylamine comprises a tallow amine often being relatively hydrophobic in nature.

[0338] In some noted 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 a typical solubility of less than about 25mg / L in 20 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 generally between 1% to 10% ±10% by weight based on the total weight of the composition. In some embodiments, the 25 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 30 of the composition.

[0339] While the compositions of the invention are completely or essentially free of water (less than 5% by weight), as mentioned previously, some of the inventive compatibilizer 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 5% by weight of water. In the great majority of embodiments, the composition comprises no more 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, 5 the composition comprises no more than 1% by weight of water.

[0340] 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.

[0341] In typical embodiments, the azole fungicide is dissolved in the water-immiscible carrier and / or 10 solvent and the copper-based fungicide is suspended therein.

[0342] In common embodiments, the azole (triazole), fungicide is dissolved in the water-immiscible (non-aqueous), carrier and / or solvent, compatibilized by the copper-shielding triazole compatibilizing agent, and the copper-based fungicide is suspended therein often accompanied by milling or homogenization if necessary suspending agents or thickeners are added, as per 15 general OD formulating practice.

[0343] In some embodiments, the additional fungicide is selected from the group of strobilurin fungicides, benzamide fungicide, morpholines, Qil fungicide, SDHI and any combination thereof.

[0344] 20 In the following embodiments “essentially non-aqueous” indicates a water content below about 5% and typically much lower.

[0345] In an embodiment, the composition comprises an essentially non-aqueous combination of:

[0346] (1) 10-50% w / w copper-based fungicide,

[0347] (2) 1-20% w / w prothioconazole, 25

[0348] (3) picoxystrobin

[0349] (4) water immiscible carrier and / or solvent, and

[0350] (5) 0.3 -1.5% tributylamine or other copper shielding agent as detailed herein.

[0351] In some embodiments the composition is an OD concentrate.

[0352] 30 In an embodiment, the composition comprises an essentially non-aqueous combination of:

[0353] (1) 15-40% w / w copper-based fungicide, (2) 2-15% prothioconazole,

[0354] (3) azoxy strobin

[0355] (4) water immiscible carrier and / or solvent, and

[0356] (5) 0.4-1.8% tributylamine.

[0357] 5

[0358] In some embodiments the composition is an OD concentrate.

[0359] In an embodiment, the composition comprises an essentially non-aqueous combination of:

[0360] (1) copper-based fungicide,

[0361] (2) prothioconazole, 10

[0362] (3) fluxapyroxad

[0363] (4) water immiscible carrier and / or solvent, and

[0364] (5) copper shielding tertiary amine such as tributylamine.

[0365] In some embodiments the composition is an OD concentrate.

[0366] 15

[0367] In an embodiment, the composition comprises an essentially non-aqueous combination of:

[0368] (1) copper-based fungicide,

[0369] (2) tebuconazole,

[0370] (3) fluxapyroxad

[0371] (4) water immiscible carrier and / or solvent, and 20

[0372] (5) copper shielding tertiary amine-type agent such as tributylamine or fatty, or long chain amine or otherwise sterically hindered amine unable to form copper-agent stable, strong, or irreversible complexes.

[0373] In some embodiments the composition is an OD concentrate.

[0374] 25

[0375] In an embodiment, the composition comprises an essentially non-aqueous combination of:

[0376] (1) copper-based fungicide,

[0377] (2) Tebuconazole,

[0378] (3) picoxy strobin

[0379] (4) water immiscible carrier and / or solvent, and 30

[0380] (5) between 0.1% and 10% w / w copper shielding tertiary amine-type agent such as tributylamine or fatty, or long chain amine or otherwise sterically hindered amine unable to form copper-agent stable, strong or irreversible complexes

[0381] In some embodiments the composition is an OD concentrate, intended to be diluted in aqueous media immediately prior to fungicidal application.

[0382] In an embodiment, the composition comprises an essentially non-aqueous combination of:

[0383] (1) copper-based fungicide,

[0384] (2) prothioconazole, 5

[0385] (3) picoxystrobin,

[0386] (4) at least one water immiscible carrier and / or solvent,

[0387] (5) AMPS-ethylacrylate copolymer,

[0388] (6) lignosulfonate, and

[0389] (7) between 0. 1% and 10% w / w copper shielding tertiary amine agent such as tributylamine 10 or fatty (long chain) amine or otherwise sterically hindered amine unable to form copper- agent stable or irreversible complexes

[0390] In some embodiments the composition is an OD concentrate..

[0391] In an embodiment, the composition comprises an essentially non-aqueous combination of: 15

[0392] (1) copper-based fungicide,

[0393] (2) prothioconazole,

[0394] (3) azoxy strobin

[0395] (4) at least one water immiscible carrier and / or solvent,

[0396] (5) AMPS-ethylacrylate copolymer, 20

[0397] (6) lignosulfonate, and

[0398] (7) between 0. 1% and 10% w / w copper shielding tertiary amine-type agent such as tributylamine or fatty (long chain) amine or otherwise sterically hindered amine unable to form copper agent stable or irreversible complexes.

[0399] In some embodiments the composition is an OD concentrate.. 25

[0400] In an embodiment, the composition comprises an essentially non-aqueous combination of:

[0401] (1) copper-based fungicide,

[0402] (2) prothioconazole,

[0403] (3) fluxapyroxad 30

[0404] (4) at least one water immiscible carrier and / or solvent,

[0405] (5) AMPS-ethylacrylate copolymer,

[0406] (6) lignosulfonate, and

[0407] (7) between 0. 1% and 10% w / w copper shielding tertiary amine-type agent such as tributylamine or fatty (long chain) amine or otherwise sterically hindered amine unable to form copper-agent stable, strong or irreversible complexes

[0408] In some embodiments the composition is an OD concentrate..

[0409] In an embodiment, the composition comprises an essentially non-aqueous combination of: 5

[0410] (1) copper-based fungicide,

[0411] (2) tebuconazole,

[0412] (3) fluxapyroxad

[0413] (4) at least one water immiscible carrier and / or solvent,

[0414] (5) AMPS-ethyl acrylate copolymer, 10

[0415] (6) lignosulfonate, and

[0416] (7) between 0. 1% and 10% w / w copper shielding tertiary amine-type agent such as tributylamine or fatty (long chain) amine or otherwise sterically hindered amine unable to form copper-agent stable, strong or irreversible complexes

[0417] In some embodiments the composition is an OD concentrate.. 15

[0418] In an embodiment, the composition comprises an essentially non-aqueous combination of:

[0419] (1) copper-based fungicide,

[0420] (2) Tebuconazole,

[0421] (3) picoxystrobin 20

[0422] (4) at least one water immiscible carrier and / or solvent,

[0423] (5) AMPS-ethyl acrylate copolymer,

[0424] (6) lignosulfonate, and

[0425] (7) between 0. 1% and 10% w / w copper shielding tertiary amine-type agent such as tributylamine or fatty (long chain) amine or otherwise sterically hindered amine unable to 25 form copper-agent stable, strong or irreversible complexes.

[0426] In some embodiments the composition is an OD concentrate additionally comprising distilled tall oil (DTO) CAS number 8002-26-4- (Altapyne® M-28B).

[0427] In some embodiments the compositions of the invention comprise between 0. 1% and 10% w / w 30 copper shielding tertiary amine agent such as tributylamine or fatty or long chain amine or otherwise sterically hindered amine unable to form strong copper-agent stable, strong or irreversible complexes. In some embodiments the composition is an OD concentrate comprising between about 0.4% and 1.5% w / w copper shielding tertiary amine-type agent such as about 0.5%, about 0.75%, about 0.8%, about 1%, about 1.2% or about 1.4%, tributylamine or fatty (long chain) amine or otherwise sterically hindered amine unable to form copper-agent stable, strong or irreversible complexes, between 12% and 30% copper-based compound such as about 25% 5 copper oxychloride or other copper fungicidal compound, and between about 1% and 8% triazole fungicide, such as, between about 4.5% and 7.5%, in an immiscible solvent or carrier. Wherein the triazole fungicide is dissolved in the immiscible carrier or solvent and the copperbased compound is dispersed immiscible carrier or solvent.

[0428] 10

[0429] In some embodiments the composition is a tank mix or spray mix prepared from an OD concentrate according to the invention, diluted in water in a concentration of between 1 part OD concentrate to 100 parts water or aqueous medium to 1 part OD concentrate to 500 parts water or aqueous medium. In some embodiments the tank mix or spray mix comprises additional components such as adjuvants, surface acting agents, emulsifiers etc. or dispersants 15 and / or other tank mix or spray mix additives.

[0430] 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 20 triazole fungicide has been compatibilized with the copper shielding tertiary amine-type agent such as tributylamine or fatty (long chain) amine or otherwise sterically hindered amine unable to form copper-agent stable, strong or irreversible complexes.

[0431] In the above exemplified embodiments, the copper-based fungicide is suspended in the at least 25 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.

[0432] 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 30 formulated. That being said, in each of the above embodiments the water immiscible carrier and / or solvent can usefully be selected from any one of, 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 polyalkyl-substituted 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 5 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 Q - Cis carboxylic acids), dimethylamide of fatty acid, N,N- dimethyl alkylamide (N,N-dimethyl 10 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.

[0433] 15 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 20 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.

[0434] 25 Oil-based compositions comprising all the inventive components that have been “sabotaged” or compromised by the inclusion of known, or predictably 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”.

[0435] Inventors consider this disclosure as being directed to skilled formulators who would make 30 reasonable efforts to prepare useful compositions, a composition that ignored the basic principles of the art of formulation are not preferred embodiments, though the composition may still be encompassed by the invention in certain circumstances for example where a “damaging” ingredient is included and then removed or safened by reversing its unwanted effect to regain the free azole, perhaps in an attempt to circumvent these teachings.

[0436] In a particular embodiment, the water immiscible earner may include but is not limited to aromatic hydrocarbons, fatty acid amides, alkyl ester of vegetable oils and vegetable oils.

[0437] In some embodiments, water immiscible carrier is exemplified by acetophenone. 5

[0438] In some embodiments, water immiscible carrier is exemplified by fatty acid amides.

[0439] In some embodiments, water immiscible carrier is exemplified by N,N-Dimethyldecanamide.

[0440] In some embodiments, water immiscible carrier is exemplified by methyl soyate.

[0441] In some embodiments, water immiscible carrier is exemplified by aromatic hydrocarbons.

[0442] In some embodiments, water immiscible carrier is exemplified by vegetable oil. 10

[0443] In an embodiment, the oil-based composition comprises an essentially non-aqueous combination of:

[0444] (1) copper-based fungicide,

[0445] (2) prothioconazole, 15

[0446] (3) picoxystrobin,

[0447] (4) aromatic hydrocarbons CAS 64742-94-5,

[0448] (5) methyl soyate CAS 67784-80-9,

[0449] (6) dimethyl decanamide CAS 14433-76-2

[0450] (7) AMPS-ethylacrylate copolymer, 20

[0451] (8) lignosulfonate, and

[0452] (9) copper shielding tertiary alkyl or olefin amine-type agent such as tributylamine, mixed trialkyl amine, or fatty amine, or long chain amine or otherwise sterically hindered amine unable to form copper-agent stable, strong or irreversible complexes.

[0453] 25

[0454] In each case, throughout this disclosure alkyl groups of the organic amines can be replaced by substituted alkyl groups or by unsaturated substituted or unsubstituted hydrocarbon groups without departing from the invention.

[0455] In an embodiment, the composition comprises an essentially non-aqueous combination of: 30

[0456] (1) copper-based fungicide,

[0457] (2) prothioconazole,

[0458] (3) azoxy strobin

[0459] (4) aromatic hydrocarbons CAS 64742-94-5, (5) methyl soyate CAS 67784-80-9,

[0460] (6) dimethyl decanamide CAS 14433-76-2

[0461] (7) AMPS-ethylacrylate copolymer (SC-Dispersant),

[0462] (8) lignosulfonate (SC-Dispersant), and

[0463] (9) copper shielding tertiary amine-type agent such as tributylamine or fatty (long chain) 5 amine or otherwise sterically hindered amine unable to form copper-agent stable, strong or irreversible complexes.

[0464] In an embodiment, the composition comprises an essentially non-aqueous combination of:

[0465] (1) copper-based fungicide, 10

[0466] (2) prothioconazole,

[0467] (3) fluxapyroxad

[0468] (4) aromatic hydrocarbons CAS 64742-94-5,

[0469] (5) methyl soyate CAS 67784-80-9,

[0470] (6) dimethyl decanamide CAS 14433-76-2 15

[0471] (7) AMPS-ethylacrylate copolymer ,

[0472] (8) lignosulfonate, and

[0473] (9) copper shielding tertiary amine-type agent such as tributylamine or fatty (long chain) amine or otherwise sterically hindered amine unable to form copper-agent stable or irreversible complexes. 20

[0474] In an embodiment, the composition comprises an essentially non-aqueous combination of:

[0475] (1) copper-based fungicide,

[0476] (2) tebuconazole,

[0477] (3) fluxapyroxad 25

[0478] (4) aromatic hydrocarbons CAS 64742-94-5,

[0479] (5) methyl soyate CAS 67784-80-9,

[0480] (6) dimethyl decanamide CAS 14433-76-2

[0481] (7) AMPS-ethylacrylate copolymer,

[0482] (8) lignosulfonate, and 30

[0483] (9) copper shielding tertiary amine-type agent such as tributylamine or fatty (long chain) amine or otherwise sterically hindered amine unable to form copper-agent stable, strong or irreversible complexes. In an embodiment, the composition comprises an essentially non-aqueous combination of:

[0484] (1) copper-based fungicide,

[0485] (2) tebuconazole,

[0486] (3) picoxystrobin,

[0487] (4) aromatic hydrocarbons CAS 64742-94-5, 5

[0488] (5) methyl soyate CAS 67784-80-9,

[0489] (6) dimethyl decanamide CAS 14433-76-2,

[0490] (7) AMPS-ethylacrylate copolymer,

[0491] (8) lignosulfonate, and

[0492] (9) copper shielding tertiary amine-type agent such as tributylamine or fatty (long chain) 10 amine or otherwise sterically hindered amine unable to form copper-agent stable, strong or irreversible complexes.

[0493] In several embodiments the oil-based composition comprises an essentially non-aqueous combination of suspended copper-based fungicide, dissolved triazole fungicide, and 0.5% - 15

[0494] 1.2% copper shielding agent in a non-aqueous solvent or carrier, such as a water immiscible solvent or carrier.

[0495] In an embodiment, the oil-based composition comprises an essentially non-aqueous combination of 20

[0496] (1) copper-based fungicide, suspended in a solution of compatibilized prothioconazole and picoxystrobin, in aromatic hydrocarbons, methyl soyate dimethyl decanamide,

[0497] (2) AMPS-ethyl acrylate copolymer and lignosulfonate dispersants, and

[0498] (3) copper shielding tertiary amine-type agent such as tributylamine or fatty (long chain) amine or otherwise sterically hindered amine unable to form copper-agent stable, strong or 25 irreversible complexes, wherein the prothioconazole has been compatibilized by the copper shielding tertiary amine-type agent such as tributylamine or fatty (long chain) amine or otherwise sterically hindered amine unable to form copper-agent stable, strong or irreversible complexes.

[0499] 30 In an embodiment, the oil-based composition comprises an essentially non-aqueous combination of

[0500] (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 (Dispersants), and

[0501] (3) copper shielding tertiary amine-type agent such as tributylamine or fatty (long chain) amine or otherwise sterically hindered amine unable to form copper-agent stable, strong or irreversible complexes, wherein the prothioconazole has been compatibilized by the copper shielding agent. 5

[0502] In an embodiment, the oil-based composition comprises an essentially non-aqueous combination of

[0503] (1) copper-based fungicide, suspended in a solution of compatibilized prothioconazole and fluxapyroxad, in aromatic hydrocarbons, methyl soyate dimethyl decanamide, 10

[0504] (2) AMPS-ethyl acrylate copolymer and lignosulfonate (Dispersants), and

[0505] (3) copper shielding tertiary amine-type agent such as tributylamine or fatty (long chain) amine or otherwise sterically hindered amine unable to form copper-agent stable, strong or irreversible complexes, wherein the prothioconazole has been compatibilized by the copper shielding agent. 15

[0506] In an embodiment, the oil-based composition comprises an essentially non-aqueous combination of

[0507] (1) copper-based fungicide, suspended in a solution of compatibilized tebuconazole and fluxapyroxad, in aromatic hydrocarbons, methyl soyate dimethyl decanamide, 20

[0508] (2) AMPS-ethyl acrylate copolymer and lignosulfonate (Dispersants), and

[0509] (3) copper shielding tertiary amine-type agent such as tributylamine or fatty (long chain) amine or otherwise sterically hindered amine unable to form copper-agent stable, strong or irreversible complexes, wherein the tebuconazole has been compatibilized by the copper shielding agent. 25

[0510] In an embodiment, the oil-based composition comprises an essentially non-aqueous combination of

[0511] (1) copper-based fungicide, suspended in a solution of compatibilized tebuconazole and picoxystrobin, in aromatic hydrocarbons, methyl soyate dimethyl decanamide, 30

[0512] (2) AMPS-ethyl acrylate copolymer and lignosulfonate (Dispersants), and

[0513] (3) copper shielding tertiary amine-type agent such as tributylamine or fatty (long chain) amine or otherwise sterically hindered amine unable to form copper-agent stable, strong or irreversible complexes, wherein the tebuconazole has been compatibilized by the copper shielding agent.

[0514] In an embodiment, the oil-based composition comprises an essentially non-aqueous combination of:

[0515] (1) copper-based fungicide, 5

[0516] (2) prothioconazole,

[0517] (3) picoxystrobin,

[0518] (4) aromatic hydrocarbons CAS 64742-94-5,

[0519] (5) methyl soyate CAS 67784-80-9,

[0520] (6) dimethyl decanamide CAS 14433 -76-2, and 10

[0521] (7) about 0.5 - about 1.2% w / w copper shielding tertiary amine-type agent such as tributylamine or fatty (long chain) amine or otherwise sterically hindered amine unable to form copper-agent stable, strong or irreversible complexes.

[0522] In an embodiment, the oil-based composition comprises an essentially non-aqueous 15 combination of:

[0523] (1) copper-based fungicide,

[0524] (2) prothioconazole,

[0525] (3) azoxy strobin,

[0526] (4) aromatic hydrocarbons CAS 64742-94-5, 20

[0527] (5) methyl soyate CAS 67784-80-9,

[0528] (6) dimethyl decanamide CAS 14433-76-2, and

[0529] (7) about 0.5 - about 1.2% w / w copper shielding tertiary amine-type agent such as tributylamine or fatty (long chain) amine or otherwise sterically hindered amine unable to form copper-agent stable, strong or irreversible complexes. 25

[0530] In an embodiment, the oil-based composition comprises an essentially non-aqueous combination of:

[0531] (1) copper-based fungicide,

[0532] (2) prothioconazole, 30

[0533] (3) fluxapyroxad

[0534] (4) aromatic hydrocarbons CAS 64742-94-5,

[0535] (5) methyl soyate CAS 67784-80-9,

[0536] (6) dimethyl decanamide CAS 14433-76-2, and (7) about 0.5 - about 1.2% w / w copper shielding tertiary amine-type agent such as tributylamine or fatty (long chain) amine or otherwise sterically hindered amine unable to form copper-agent stable, strong or irreversible complexes.

[0537] In an embodiment, the oil-based composition comprises an essentially non-aqueous 5 combination of:

[0538] (1) copper-based fungicide,

[0539] (2) tebuconazole,

[0540] (3) fluxapyroxad

[0541] (4) aromatic hydrocarbons CAS 64742-94-5, 10

[0542] (5) methyl soyate CAS 67784-80-9,

[0543] (6) dimethyl decanamide CAS 14433-76-2, and

[0544] (7) about 0.5% - about 1.2% w / w copper shielding tertiary amine-type agent such as tributylamine or fatty (long chain) amine or otherwise sterically hindered amine unable to form copper-agent stable, strong or irreversible complexes. 15

[0545] In an embodiment, the oil-based composition comprises an essentially non-aqueous combination of:

[0546] (1) copper-based fungicide,

[0547] (2) tebuconazole, 20

[0548] (3) picoxystrobin,

[0549] (4) aromatic hydrocarbons cas 64742-94-5,

[0550] (5) methyl soyate cas 67784-80-9,

[0551] (6) dimethyl decanamide cas 14433-76-2, and

[0552] (7) about 0.5 - about 1.2% w / w copper shielding tertiary amine-type agent such as 25 tributylamine or fatty (long chain) amine or otherwise sterically hindered amine unable to form copper-agent stable, strong or irreversible complexes (triazole compatibilizing agent). in an embodiment, the oil-based composition comprises an essentially non-aqueous combination of: 30

[0553] 1) copper oxychloride

[0554] 2) picoxystrobin

[0555] 3) prothioconazole

[0556] 4) polydimethylsiloxanes ) oxirane, monobutyl ether (Atlas g-50021-1 q-(cq)) ) fumed silica (cab-o-sil® m5) ) co-polymer of 2-acrylamido-2-methylpropane sulfonic acid (amps) monomers and ethyl acrylate monomers (AMPS-EA) ) N,N-dimethyl decanamide, (Hallcomid M-10) 5) lignosulfonic acid, sodium salt, sulfomethylated (Reax 88a) 0) benzenesulfonic acid, cio-i3-(linear)alkyl derivatives, calcium salt, (Rhodacal 60 / BE) 1) hydrocarbons, cio, aromatics (Solvesso 150) 2) tri styrylphenol ethoxylated (Soprophor BSU) 3) about 0.5 - about 1.2% w / w copper shielding agent which is selected from, tertiary amine 10 such as tributylamine, fatty (long chain) amine, or otherwise sterically hindered amine unable to form copper-agent stable, strong or irreversible complexes, 4) polyoxyethylene (20) sorbitan monolaurate (Tween 24-LQ-(ap)) 5) methylated soybean oil

[0557] 15

[0558] In an embodiment, the oil-based composition comprises an essentially non-aqueous combination of:

[0559] In an embodiment, the oil-based composition comprises an essentially non-aqueous combination of:

[0560] In an embodiment, the oil-based composition comprises an essentially non-aqueous combination of:

[0561] The term “essentially non-aqueous” in the composition and / or combination embodiments 5 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%.

[0562] In an embodiment, the amount of the one or more water immiscible carrier or solvent may be 10 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.

[0563] In some embodiments, the composition comprises - excipients in addition to the above detailed 5 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.

[0564] In some embodiments, the excipients which may be referred to as adjuvants, additives or 10 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 15 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) 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 25 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, poly oxyethyl ene / polypropylene oxide, ethoxylated tristyrylphenol, ethoxylated tristyrylphenol sulphate, ethoxylated 30 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 5 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.

[0565] In some embodiments, the composition comprises one or commonly two or more surface active materials including emulsifiers etc.

[0566] In some embodiments, wetting agent is alkoxylated alcohol and a di-block EO / PO block 10 copolymer exemplified by Atlox® 4894.

[0567] In some embodiments, the dispersant is an anionic polymeric surfactant exemplified by Atlox® Metasperse 500L.

[0568] In some embodiments, the excipient is an anionic dispersant exemplified by Geropon® T-77.

[0569] In some embodiments, the composition comprises at least one rheology modifier. In some 15 embodiments, the agriculturally acceptable additive is a rheology modifier.

[0570] In some embodiments, the rheology modifier is a thickener. In some embodiments, the composition comprises at least one thickener.

[0571] A thickening agent, when present, is preferably selected from agar, alginic acid, alginate, carrageenan, gellan gum, xanthan gum, succinoglycan gum, guar gum, acetylated distarch 20 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.

[0572] In some embodiments, the thickener is xanthan gum.

[0573] In some embodiments, the rheology modifier is Agrhopol 23, Rhodopol® 23 (sold by Solvay). 25 In some embodiments, the rheology modifier is xanthan gum.

[0574] In some embodiments, the antifoaming agent is SAG 1572.

[0575] 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.

[0576] 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 . 5

[0577] 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.

[0578] Various agrochemicals may be used as additional bioactive ingredient. Exemplary among such agrochemicals without limitation are crop protection agents, for example pesticides, safeners, 10 plant growth regulators, repellents, bio-stimulants and preservatives such as bacteriostats or bactericides.

[0579] In some embodiments, the composition comprises at least one additional bioactive ingredient, commonly, an additional insecticide, fungicide and / or herbicide.

[0580] Additional agrochemicals that may be used with the combination and composition of the 15 present invention are described below.

[0581] The present invention inter aha provides typical non-aqueous compositions comprising combinations of ingredients containing at least one member of each of,

[0582] (i) Copper Al component;

[0583] (ii) Azole (triazole) Al component

[0584] (iii) non-aqueous carrier or solvent, and

[0585] (iv) copper shielding agent which are tertiary amine such as tributylamine or fatty (long chain) amine or otherwise sterically hindered amine unable to form copper-agent stable, strong or irreversible complexes.

[0586] The present invention inter aha provides typical non-aqueous compositions comprising combinations of ingredients containing at least one member of each of,

[0587] (i) copper Al component;

[0588] (ii) azole (triazole) Al component

[0589] (iii) non-aqueous carrier or solvent,

[0590] (iv) dispersant, (v) about 0.2% - about 1.7% w / w, such as 0.5% - 1.2%, copper shielding tertiary amine-type agent such as tributylamine or fatty (long chain) amine or otherwise sterically hindered amine unable to form copper-agent stable, strong or irreversible complexes

[0591] Typical, essentially non-aqueous (<5% water) compositions of the invention may for example contain in addition to the copper shielding agent, representative ingredients chosen from these classes, exemplified by,

[0592] (1) Copper oxychloride tech (Copper Al component)

[0593] (2) Prothioconazole, difeoconazole or Tebuconazole (Azole Al component)

[0594] (3) Acetophenone (non-aqueous carrier / solvent)

[0595] (4) Dimethyl Decanamide (non-aqueous carrier / solvent)

[0596] (5) Fatty acid alkyl esters, Methyl Soyate etc (non-aqueous carrier / solvent)

[0597] (6) Aromatic hydrocarbons (non-aqueous carrier / solvent)

[0598] (7) Lignosulfonate salt e.g., Ca or Na salt (dispersant)

[0599] (8) Co-polymer of 2-Acrylamido-2 -methylpropane sulfonic acid (AMPS) monomers and ethyl acrylate monomers (dispersant)

[0600] (9) copolymers of styrene and methacrylic acid monomers (dispersant).

[0601] 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, picoxystrobin, azoxystrobin, or fluxapyroxad (optional additional ai component)

[0602] Acetic Acid (Optional acidifying additive)

[0603] Agnique BP 420 (Optional additive)

[0604] Agsolex 8 (Optional additive)

[0605] Propylene glycol (Optional antifreeze additive)

[0606] Proxel GXL (Optional preservative additive)

[0607] SAG 1572 (Optional antifoaming agent) sodium acetate (Optional buffer additive)

[0608] Soprophor TS / 16 (Optional surfactant additive)

[0609] Synergen SOC (Optional additive) smectite clay, silicon Dioxide (Optional thickener additive) Polydimethylsiloxane(Optional antifoam additive)

[0610] Persons skilled in formulating agricultural oil based compositions will include those formulation excipients that most suit the specific composition being formulated as is usual so long as the non active ingredient does not adversely affect the prevention of copper-triazole complexes. 5

[0611] Method and Uses

[0612] 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, illustrated by tributylamine and any combination 10 thereof to the composition. A preference is noted for the addition of both, at least one dispersant and tributylamine.

[0613] 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 15 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 20 advantages might be realized comparing a composition produced using one order of addition than another.

[0614] Process

[0615] 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 25 carrier and / or solvent. Below is presented an example of the process comprising the following steps using some typical ingredients simply for illustrative purposes:

[0616] (a) In a tank with agitation, add

[0617] (i) Aromatic hydrocarbons,

[0618] (ii) Dimethyl Decanamide, 30 (iii) Prothioconazole and

[0619] (iv) Picoxystrobin,

[0620] (b) agitate, optionally with heating until complete Al solubilization.

[0621] (c) add,

[0622] (v) Polyethylene-Polypropylene Glycol butyl ether Block polymer, 5

[0623] (vi) Tristyrylphenol ethoxylate,

[0624] (vii) Tween 20

[0625] (viii) Antifoam,

[0626] (ix) Dodecylbenzene sulfonic acid calcium salt

[0627] (x) AMPS-Ethylacrylate block co-polymer 10

[0628] (xi) Methyl Soyate

[0629] (xii) Sodium lignosulfonate and if needed, cool down to below 35°C

[0630] (d) add

[0631] (xiii) Tributylamine 15

[0632] (xiv) Copper Oxychloride and / or Chelated Copper

[0633] (xv) Fumed Silicon Dioxide and agitate at high speed exemplified by greater than 1000 rpm to homogenize,

[0634] (xi) sieve to remove excessively large solids through a 100 mesh screen.

[0635] 20

[0636] 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.

[0637] In some embodiments, the resultant suspended copper-based fungicide particles size 25 distribution is characterized by a D90 of 10 microns or less and a D50 of 5 microns or less.

[0638] In some embodiments, the ingredients are incorporated in a different order of addition, without any departure from the invention.

[0639] 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 30 fungicide in a water immiscible carrier and SC-dispersant insoluble in the carrier and tributylamine. 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.

[0640] In some embodiments, the water immiscible carrier is fatty acid amide exemplified by N,N- dimethyldecanamide. 5

[0641] 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.

[0642] 10

[0643] Azole fungicide

[0644] 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; 15 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. 20

[0645] In some embodiments, the azole fungicide is tebuconazole.

[0646] In some embodiments, the azole fungicide is prothioconazole.

[0647] In some embodiments, the azole fungicide is cyproconazole.

[0648] In some embodiments, the azole fungicide is difenoconazole.

[0649] 25

[0650] Additional fungicide

[0651] In some embodiments, the additional fungicide is selected from the group of strobilurin fungicides, benzamide fungicide, morpholines, Qil fungicide, SDHI and any combination thereof

[0652] In some embodiments, strobilurin fungicide may include but is not limited to azoxystrobin, 30 coumoxystrobin, enoxastrobin, flufenoxystrobin, picoxystrobin, pyraoxystrobin, mandestrobin, pyraclostrobin, pyrametostrobin, triclopyricarb, kresoxim-methyl, trifloxystrobin, dimoxystrobin, fenaminstrobin, metominostrobin, orysastrobin, metyltetraprole and fluoxastrobin.

[0653] In some embodiments, the strobilurin fungicide is selected from group of picoxystrobin, trifloxystrobin, azoxystrobin, pyraclostrobin, metominostrobin, metyltetraprole, mandestrobin 5 and a combination thereof.

[0654] In some embodiments, the strobilurin fungicide is picoxystrobin.

[0655] In some embodiments, the strobilurin fungicide is azoxystrobin.

[0656] In some embodiments, the SDHI may include but is not limited to penthiopyrad, boscalid, flutolanil, fluxapyroxad, inpyrfluxam , fluopyram, fluindapyr, benzodiflupyr, bixafen and 10 pydiflumetofen.

[0657] In some embodiments, the SDHI fungicide is selected from group of bixafen; fluxapyroxad, fluindapyr; inpyrfluxam, benzodiflupyr and pydiflumetofen.

[0658] In some embodiments, the SDHI fungicide is fluxapyroxad.

[0659] In some embodiments, Qil fungicide may include but is not limited to cyazofamid, amisulbrom 15 and fenpicoxamid.

[0660] In some embodiments, Qil is fenpicoxamid.

[0661] In some embodiments, morpholines may include but is not limited to aldimorph, fenpropimorph, tridemorph, dodemorph, spiroxamine, piperalin, fenpropidin.

[0662] Copper-based fungicide 20

[0663] 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, 25 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.

[0664] 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, 30 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.

[0665] 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 5 chromate, copper sulfate pentahydrate, Bordeaux mixture, cuprous oxide, copper oxychloride, and any combination thereof.

[0666] In some embodiments, the copper-based fungicide is bordeaux mixture.

[0667] In some embodiments, the copper-based fungicide is copper hydroxide.

[0668] In some embodiments, the copper-based fungicide is copper oxychloride. 10

[0669] In some embodiments, the copper-based fungicide is selected from the group of copper sulfate pentahydrate, Bordeaux mixture and any combination thereof.

[0670] 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.

[0671] As used herein, the term "metallic copper" typically refers to Cu2+cation as was previously 15 described.

[0672] Methods of Use

[0673] 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 20 the unwanted insects so as to thereby control the pathogen disease.

[0674] Controlling refer to preventing curative and persistence.

[0675] 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, 25 propagation material thereof, or an area infested with the unwanted insect so as to thereby control the plant disease caused by pathogen.

[0676] In some embodiments, the locus of the plant is the vicinity of the plant.

[0677] In some embodiments, the area infested with the pathogen.

[0678] In some embodiments the present invention provides a method for controlling pathogen 30 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 tributylamine.

[0679] In some embodiments the present invention provides a method for controlling pathogen infection comprising applying a OD composition (typically after dilution / dispersion in water), 5 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 tributylamine.

[0680] In some embodiments the present invention provides a method for controlling pathogen 10 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 tributylamine. 15

[0681] 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). 20

[0682] 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, 25

[0683] 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.

[0684] 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 30 contacting the plant, or part of the plant, with any one or any combination and / or composition described herein.

[0685] 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. 5

[0686] 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.

[0687] In some embodiments, the method of treating the plant, or the part of a plant against a pathogen 10 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.

[0688] 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 15 material thereof, which method comprises contacting the plants, or propagation material thereof, with any one of any combination and / or composition described herein.

[0689] 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. 20

[0690] 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.

[0691] In some embodiments, the method of treating the plant, or the part of a plant against a pathogen 25 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.

[0692] Rates of application may refer to application rates of the additional fungicide (when included in the composition) exemplified by anilide / carboxamide fungicides, exemplified by 5 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 10 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%.

[0693] 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 15 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.

[0694] In some embodiments, the combination and / or composition, is applied at an amount , of 0.018 20 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. 25

[0695] 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 30 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 5 previously, being understood to include ±10% (i.e., about), of that value.

[0696] 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)

[0697] In some embodiments, the combination and / or composition, is applied at an amount of about 10 0.0075 g / ha, 0.075 g / ha, 0.75 g / ha, 7.5 g / ha or 75 g / ha of copper metal.

[0698] 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. 15 In some embodiments, the combination and / or composition, is applied at an amount of about 0.0095 g / ha of copper metal.

[0699] 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 20 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.

[0700] In some embodiments, the combination and / or composition, is applied at an amount of about 750 g / ha of copper metal.

[0701] A composition and / or combination according to the invention is suitable for the control of pests 25 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, 30 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.

[0702] To control agricultural pests, the invention provides a use of a composition comprising a 5 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.

[0703] Said compositions are used, for example, to control soybean rust, powdery mildew and downy 10 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 15 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.

[0704] 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 20 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.

[0705] 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 25 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.

[0706] A plant of part thereof may be coated with a diluted ready-for-application composition 30 comprising a copper-based fungicide and azole (e.g., triazole) and tertiary alkylamine (tributylamine), 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. 5 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 10 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 15 be used in the process, method and use embodiments described herein and vice versa.

[0707] 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.

[0708] The invention is illustrated by the following examples without limiting it thereby. 20

[0709] Copper Oxychloride 300 / Fluxapiroxad50 / Prothioconazole 80 OD

[0710] Density about 1.2

[0711] Exemplified Non-Limiting Illustration of a Method of Preparation

[0712] In a tank with agitation, add Solvesso 150, Dimethyl Decanamide, Prothioconazole (triazole), 5 and Fluxapyroxad (additional a.i.), heat at e.g., 70°C, keeping under agitation (e.g., 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, Distilled Tall Oil (DTO) - (Altapyne M28-B), 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. 5

[0713] Stability studies:

[0714] A series of tests were performed with the objective to confirm that the inclusion of the exemplified copper shielding triazole compatibilizing agent, tributylamine is able to prevent the exemplified triazole, prothioconazole complexation with the copper by comparing the inventive composition with an equivalent composition absent the copper shielding triazole 10 compatibilizing agent. As can clearly be seen in the above non-limiting illustrative example, when the non aqueous oil dispersion composition comprises the Copper Shielding Triazole Compatibilizing Agent, tributyl amine (Inventive), greater than 99% of the Prothioconazole remains free after two weeks storage at 54°C. In addition, it can be seen that the compatibilized inventive Oil 5 Dispersion Concentrate remains a Flowable turquoise suspension.

[0715] In contrast when the comparative composition is absent the Copper Shielding Triazole Compatibilizer (Comparative), the composition changes to a dark brown color and the Free Prothioconazole content is reduced to 62% after two weeks stored at 54°C. Even when comparing the compositions after only two weeks at room temperature, it is apparent that the 10 inventive OD composition maintains a greater Free Prothioconazole content.

[0716] While the pesticidal efficacy advantages of this invention has been linked to the numerical % content of Free triazole available for maintaining fungicidal activity in non-aqueous oil-based compositions of triazole and Copper-based compounds, clearly the physical quality of such compositions is an important aspect of any commercial product and as can be seen, 15 compositions in which there have been significant loss of free triazole through formation of azole-copper complex will also suffer from a qualitative degradation. In the above example the uncompatibilized oil-based composition changes from a Turquoise color to dark brown after two weeks stored at 54°C. This type of degradation of the appearance of the composition would be unacceptable even if efficacy was not so clearly affected. 20

Claims

CLAIMS:1) A non-aqueous composition comprising, a) an amount of azole pesticide, b) an amount of copper-based compound, c) an amount of a copper-shielding agent, and 5 d) non-aqueous water-immiscible solvent and / or carrier, wherein copper-shielding agent is an amine-type compound characterized in being incapable of forming stable, strong and / or irreversible copper-compatibilizing agent complexes with the copper-based compound in the composition, and wherein the amount of copper-based compound exceeds the amount of the copper-shielding agent. 102) The non-aqueous composition as claimed in claim 1, wherein the copper-shielding agent is an organic amine represented by the structure A;wherein: 15R1is hydrogen, Cn alkyl, aryl, Cn alkenyl, Cn alkynyl or heterocyclic; R2is hydrogen, Cn alkyl, aryl, Cn alkenyl, Cn alkynyl or heterocyclic; and R3is hydrogen, Cn alkyl, aryl, Cn alkenyl, Cn alkynyl or heterocyclic, and at least one of R1, R2, and R3is alkyl, aryl , alkenyl, alkynyl or heterocyclic, wherein, when all of R1, R2, and R3are alkyl, alkenyl or alkynyl groups, then Cn is Ci- 26, such as C3-C18, when one or more of R1, R2, and R3are hydrogen then at least one of 20 R1, R2, and R3are aromatic, or alkyl or alkenyl or alkynyl groups, wherein Cnis Ce- 26, wherein the alkyl, alkenyl or alkynyl groups are substituted, unsubstituted linear, branched or cyclic characterized by the inability of the organic amine type agent compound to form strong, stable irreversible complexes with copper.3) The non-aqueous composition as claimed in claim 1, wherein the copper-shielding agent is 25 an organic amine selected from the group of tertiary amines, long chain C&- C26 amines, or C8-C22 fatty amines.4) The non-aqueous composition as claimed in claim 1, wherein the copper-shielding agent is tributyl amine. 305) The non-aqueous composition as claimed in claim 1, wherein the amount of copper- shielding agent in the composition is between 0.1% and 8% ±10% (about 8%), by weight based on the total weight of the composition and the ratio of the amount of copper-shielding agent to the amount of copper-based compound does not exceed 1:2.

5. 56) The non-aqueous composition as claimed in claim 1, wherein the amount of copper- shielding agent in the composition is between greater than 0.1% and less than less than 3% w / w by weight based on the total weight of the composition and the ratio of the amount of copper-shielding agent to the amount of copper-based compound does not exceed 1:

8. 107) The non-aqueous composition as claimed in claim 1, wherein the amount of copper- shielding agent in the composition is between greater than 0.1% and less than less than 3% w / w by weight based on the total weight of the composition and the ratio of the amount of copper-shielding agent to the amount of copper-based compound is about 6-15:

300. 158) The non-aqueous composition as claimed in claim 2, wherein the copper-shielding agent is a tertiary organic amine represented by the structure A;wherein: 20R1, R2, and R3are each independently selected from substituted or unsubstituted Cn alkyl, aryl, Cn alkenyl, Cn alkynyl or heterocyclic group, wherein Cn is Ci- 26, such as C3- is, and wherein each of the alkyl, alkenyl or alkynyl groups are linear, branched or cyclic.9) The non-aqueous composition as claimed in claim 2, wherein the copper-shielding agent is a tertiary organic amine represented by the structure A; 25wherein all of R1, R2, and R3are the same group selected from substituted or unsubstituted Cn alkyl, aryl, Cn alkenyl, Cn alkynyl or heterocyclic group, wherein Cn is Ci-26, and wherein each of the alkyl, alkenyl or alkynyl groups are linear, branched or cyclic.10) A non-aqueous oil-based composition comprising, a) an amount of azole which is triazole pesticide, 5 b) an amount of copper-based compound, c) an amount of a copper-shielding agent, and d) non-aqueous water-immiscible solvent and / or carrier, wherein the amount of triazole pesticide comprises no less than 70% as free triazole uncomplexed with copper-based compound and wherein copper-shielding agent is amine-type 10 compound characterized in being incapable of forming stable, strong and / or irreversible copper-agent complexes with the copper-based compound in the composition, and wherein the amount of copper-based compound exceeds the amount of the copper-shielding agent.11) The non-aqueous oil-based composition claimed in claim 10 wherein the amount of triazole 15 pesticide comprises no less than 80% as free triazole uncomplexed with copper-based compound after storage at 54°C for two weeks.12) The non-aqueous oil-based composition claimed in any one of claims 1 - 11, wherein the azole is triazole fungicide selected from one or more of prothioconazole, cyproconazole, 20 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 25 (triazole), triadimefon, triadimenol, triticonazole, uniconazole and uniconazole -P, their salts, esters, isomers and derivatives thereof.13) The non-aqueous oil-based composition claimed in any one of claims 1 - 12, wherein the copper-based fungicidal compound is selected from one or more selected from the group 30 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.14) The non-aqueous oil-based composition claimed in any one of claims 1 - 13, wherein the non-aqueous solvent and / or carrier comprises one or more water immiscible carriers or 5 solvents selected from the group of aromatic hydrocarbons such as, toluene, o-, m-, p- xylene, ethylbenzene, isopropylbenzene, tert-butylbenzene, naphthalenes, mono- or polyalkyl-substituted naphthalenes), paraffins such as, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, hepta-decane, octa-decane, nona-decane, eicosane, heneicosane, docosane, tricosane, tetracosane, pentacosane, and 10 branched chain isomers thereof, petroleum, ketones such as, acetophenone, cyclohexanone, vegetable oil such as, 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 esters of vegetable oils, such as, rapeseed oil methyl ester rapeseed oil ethyl ester, methyl soyate, 15 epoxidized vegetable oil, rapeseed oil propyl esters, rapeseed oil butyl esters, tall oil fatty acids esters and the like, diesel, mineral oil, fatty acid amides such as, ( C1-C3 amines, alkylamines or alkanolamines with G, - C ix 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 20 fatty acids, alkyl esters of fatty acids such as, C1-C4 monohydric alcohol esters of C8 to C22 fatty acids such as methyl oleate, ethyl oleate), modified vegetable oils and combinations thereof.2515) A non-aqueous oil dispersion composition comprising, a) an amount of azole pesticide such as triazole fungicide, b) an amount of copper-based fungicidal compound, c) an amount of a copper-shielding agent, d) and an amount of additional pesticidal active compound 30 e) non-aqueous water-immiscible solvent and / or carrier, wherein the amount of azole pesticide, the amount of a copper-shielding agent and the amount of additional pesticidal active compound are dissolved in the non-aqueous water- immiscible solvent and / or carrier and the copper-based fungicidal compound is dispersedas solid particles in the non-aqueous water-immiscible solvent and / or carrier, wherein the non-aqueous oil-based dispersion comprises greater than 80% of the amount of azole pesticide as free triazole fungicide and less than 20% of the triazole compound as triazole complexed with the copper-based fungicidal compound when measured by comparing the peak area at the same retention time of the azole pesticide reference standard compound 5 and wherein the amount of copper-based fungicidal compound exceeds the amount of the copper-shielding agent.16) The non-aqueous oil-based composition claimed in claim 15, wherein the amount of additional pesticidal active compound is selected from the group of strobilurin fungicide, 10 benzamide fungicide, morpholines, Qil fungicide, SDHI and any combination thereof and copper-shielding agent is an amine-type compound characterized in being incapable of forming stable, strong and / or irreversible copper-copper-shielding agent complexes with the copper-based compound in the composition, and wherein the amount of copper-based compound exceeds the amount of the copper-shielding agent. 1517) The non-aqueous oil-based composition claimed in either claims 15-16, wherein the additional pesticidal active compound is selected from the group of azoxystrobin, coumoxystrobin, enoxastrobin, flufenoxystrobin, picoxystrobin, pyraoxystrobin, mandestrobin, pyraclostrobin, pyrametostrobin, triclopyricarb, kresoxim-methyl, 20 trifloxystrobin, dimoxystrobin, fenaminstrobin, metominostrobin, orysastrobin, metyltetraprole and fluoxastrobin, penthiopyrad, boscalid, flutolanil, fluxapyroxad, inpyrfluxam , fluopyram, fluindapyr, benzovindiflupyr, bixafen and pydiflumetofen cyazofamid, amisulbrom, fenpicoxamid, aldimorph, fenpropimorph, tridemorph, dodemorph, spiroxamine, piperalin, fenpropidin and combinations thereof. 2518) An oil dispersion concentrated composition comprising, a) Prothioconazole, b) Fluxapyroxad, c) Copper Oxychloride, and 30 d) Tributylamine, e) non-aqueous water-immiscible solvent and / or carrier wherein the non-aqueous water-immiscible solvent and / or carriercomprises one or more of hydrocarbons, Cio, aromatics, Methylated Soybean oil and N,N- Dimethyl Decanamide.19) The oil dispersion concentrated composition as claimed in claim 18, further comprising one or more further ingredients selected from, ABA poly hydroxyester-PEG-poly 5 hydroxyester copolymers (Zephrym® PD2206 -block copolymer), tristyrylphenol ethoxylated (Soprophor® BSU), Polyoxyethylene (20) sorbitan monolaurate (Tween 24- Iq-(ap)), butyl polyethylene oxide-polypropylene block copolymer (Atlas G-50021-lq-(cq)), benzenesulfonic acid, Cio-B-(linear) alkyl derivatives, calcium salt, (Rhodacal® 60 / BE) and Distilled Tall Oil (DTO), (Altapyne M28-B). 1020. A non-aqueous oil dispersion composition comprising, about 80 g / L triazole pesticide compound, about 300 g / L copper oxychloride,5-20 g / L copper-shielding amine-type agent, and 15 a non-aqueous water-immiscible solvent and / or carrier wherein the composition comprises no more than about 20% by weight as triazole complexed with the copper oxychloride compound.

21. A non-aqueous oil dispersion composition comprising, 20 about 80 g / L prothioconazole, about 300 g / L copper oxychloride,5-20 g / L tertiary organic amine such as tributyl amine, and a non-aqueous water-immiscible solvent and / or carrier wherein the amount of triazole pesticide compound comprises no more than about 20% by 25 weight as triazole complexed with the copper oxychloride compound.

22. A non-aqueous oil dispersion composition comprising, about 80 g / L prothioconazole, about 300 g / L copper oxychloride, 30 about 6-15 g / L tributyl amine,About 50 g / L Eluxapyroxad, non-aqueous water-immiscible solvent and / or carrier, andformulation ingredients selected from surfactants, emulsifiers dispersants, thickeners, and antifoam agents, wherein the amount of triazole pesticide compound comprises no more than about 15% by weight as triazole complexed with the copper oxychloride compound, wherein the numerical values modified by the term about, include ±10% from the indicated value.

523. A non-aqueous oil dispersion composition comprising, about 80 g / L prothioconazole pesticide compound, about 300 g / L copper oxychloride, about 6-15 g / L tributyl amine,About 50 g / L Fluxapyroxad, 10 non-aqueous water-immiscible solvent and / or carrier, Tristyrylphenol ethoxylated (Soprophor® BSU), Polyoxyethylene (20) sorbitan monolaurate (Tween 24-LQ-(ap)), Hydrocarbons, Cio, aromatics (Solvesso® 150),Butyl polyethylene oxide-polypropylene block copolymer (Atlas G-50021-LQ-(CQ)), 15Benzenesulfonic acid, Cio-B-(linear) alkyl derivatives, calcium salt, (Rhodacal® 60 / BE), Methylated Soybean oil, Lignosulfonic acid, sodium salt, sulfomethylated (Reax 88A), Polydimethylsiloxanes (Antifoam),Fumed silica (Cab-o-Sil M5), 20N,N-Dimethyl Decanamide, (Hallcomid M-10), and Distilled Tall Oil (DTO) - (Altapyne M28-B).

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