RU2829578C1 - Oil liquid fungicidal composition - Google Patents

Abstract

FIELD: agriculture.

SUBSTANCE: invention relates to agriculture, in particular to means of protection against phytopathogenic fungi. Fungicidal liquid oil dispersion composition containing: (i) a dithiocarbamate fungicide mancozeb, suspended in a solution of fungicides in an agrochemically acceptable non-aqueous liquid carrier, and (ii) a zinc oxide stabilizer as an ingredient for improving the stability of said composition, wherein said fungicide solution contains a triazole fungicide tebuconazole or prothioconazole and a pyrazole-carboxamide fungicide fluxapiroxade, dissolved in said non-aqueous liquid carrier, is adapted for compatibility with glyphosate formulations without increasing the viscosity of said liquid oil composition. Agrochemically acceptable non-aqueous liquid carrier additionally contains 2-ethylhexanol.

EFFECT: disclosed fungicidal liquid oil dispersion composition is stable during storage in a sealed container, the viscosity of the composition is maintained in range of 500–2500 cP, composition retention is 2% or less when performing wet sieve analysis in accordance with CIPAC MT 185 and using a sieve with mesh size of 75 microns after storage for 2 weeks at 54 °C, and the density of composition is 1–1,5 g/cm³ when analysing density in accordance with CIPAC MT 3.3.2 at temperature of 20 °C after storage for 6 months at room temperature.

10 cl, 3 dwg, 7 tbl, 3 ex

Description

This application claims priority to U.S. Provisional Patent Application No. 62/895,602, filed September 4, 2019, the entire contents of which are incorporated herein by reference.

This application references various publications. The contents of these documents are incorporated herein by reference in their entirety to more fully describe the state of the art in the field to which this invention pertains.

FIELD OF INVENTION

The present invention provides oily liquid fungicidal compositions comprising: (i) at least one dithiocarbamate fungicide, (ii) at least one triazole fungicide, (iii) at least one pyrazole-carboxamide fungicide and (iv) at least one agrochemically acceptable non-aqueous liquid carrier, wherein the dithiocarbamate fungicide is suspended in said liquid carrier and the triazole fungicide and the pyrazole-carboxamide fungicide are dissolved in said liquid carrier. The present invention also provides methods of using and methods of preparing the compositions described herein.

LEVEL OF TECHNOLOGY

It is well known that dithiocarbamates have good fungicidal activity. However, these active ingredients have the disadvantage of being relatively unstable. This is due to the low stability of the C-S bonds and the thiocarbamate functional group, in particular at low pH values and in the presence of nucleophilic agents.

To improve the stability of these active ingredients, they can be formulated as solid formulations. Known solid powder formulations are, for example, Manzate® 75 WG (a DuPont product), Polyram® DF (a Nufarm product) and Vondozeb 75 WG (a Agrosimex product). However, there are also known disadvantages associated with solid formulations such as water-dispersible granules. Some of these may include poor dispersion in water, difficulty in adjusting dosages, compatibility with other components of the tank mix and the high cost of producing such formulations.

In many cases, liquid products are now preferred over the above solid formulations. The advantage of liquid products is that even at very low volumes they exhibit good miscibility with oil additives for tank mixes in water/oil formulations or oil formulations (see EP0435760 and EP0697171).

Agrochemical oil dispersions (OD) are stable suspensions of agrochemical active ingredients, such as pesticides and crop protection chemicals, in non-aqueous liquids which may contain other dissolved active ingredients. Oil dispersions are particularly suitable for the preparation of formulations based on oil-insoluble solid active ingredients.

Oil dispersion formulations are a concentrate that is diluted with water before use to form an aqueous composition used to protect agricultural crops. To ensure dispersion in water, such formulations contain emulsifiers, dispersants, and additional formulation components such as thickeners, defoamers, and solid carriers. Oil dispersions are often selected when the active ingredient is sensitive to water, or when it is necessary for the oil to act as an auxiliary substance to improve the biological characteristics of the pesticide. Oil dispersions are usually water-free. This is necessary either to prevent the decomposition of the active substances or to prevent phase separation of the formulation.

Oil dispersion formulations offer a number of advantages to farmers. They allow active ingredients that are usually unstable in water to be prepared in a solid suspended form. They can be combined with oil-based excipients to increase the effectiveness of this type of formulation. In addition, suspension of active ingredients in a non-aqueous liquid carrier can provide formulations with higher levels of active ingredients. This is because the active ingredients have a solubility limit in terms of the amount that can be added to the formulation.

However, oil dispersion formulations are difficult to prepare. Oil dispersion formulations often undergo phase separation during storage. Thus, storage even at ambient temperature results in aggregation, lumping or pronounced sedimentation of the suspended phase. Depending on the density of the active ingredient and the non-aqueous liquid carrier used, separation of particles of the active ingredient from the non-aqueous liquid carrier may also occur. In some cases, the effects may be irreversible.

The need for new agrochemical compositions with high performance characteristics is constantly increasing, while the number of chemicals approved for use in agrochemical compositions by regulatory authorities is decreasing due to stricter standards regarding the toxicological and environmental characteristics of these materials. Therefore, there is a need in the art for a fungicide composition that allows for a reduction in the applied amounts of individual active ingredients while maintaining increased efficiency of these active ingredients. In addition, the combination of a multisite fungicide (such as a dithiocarbamate fungicide) with two systemic fungicides (such as a triazole fungicide and a pyrazole carboxamide fungicide) in a stable formulation provides a solution that allows for a reduction in disease resistance, a reduction in the applied amounts of active ingredients, an increase in yield, and a reduction in costs.

In view of the above aspects, there is a need in the art for a stable liquid oil formulation comprising a combination of a multisite fungicide (such as a dithiocarbamate fungicide) with two systemic fungicides.

BRIEF DESCRIPTION OF THE INVENTION

The present invention provides a fungicidal liquid oil composition comprising:

(i) at least one dithiocarbamate fungicide,

(ii) at least one triazole fungicide,

(iii) at least one pyrazole carboxamide fungicide, and

(iv) at least one agrochemically acceptable non-aqueous liquid carrier, wherein the dithiocarbamate fungicide is suspended in said liquid carrier and the triazole fungicide and the pyrazole carboxamide fungicide are dissolved in said liquid carrier.

The present invention also provides a combination comprising:

(i) an amount of at least one dithiocarbamate fungicide,

(ii) an amount of at least one triazole fungicide, and

(iii) an amount of at least one pyrazole carboxamide fungicide,

Moreover, the specified combination is more effective for treating a plant or locus from a fungal infection than when using each fungicide in the same amount separately.

The present invention also provides a combination comprising:

(i) an amount of at least one dithiocarbamate fungicide,

(ii) an amount of at least one triazole fungicide, and

(iii) an amount of at least one pyrazole carboxamide fungicide,

wherein the specified amount of dithiocarbamate fungicide, the specified amount of triazole fungicide and the specified amount of pyrazole-carboxamide fungicide when applied together are more effective in treating a plant or locus from a fungal infection than when each fungicide is applied in the same amount separately.

The present invention also provides a combination comprising:

(i) an amount of at least one dithiocarbamate fungicide,

(ii) an amount of at least one triazole fungicide, and

(iii) an amount of at least one pyrazole carboxamide fungicide,

wherein the said amount of dithiocarbamate fungicide is less than the fungicidally effective amount of the compound of formula I when using the compound of formula I alone,

wherein the specified amount of triazole fungicide is less than the fungicidally effective amount of the triazole fungicide when the triazole fungicide is used alone, and/or

wherein the specified amount of pyrazole-carboxamide fungicide is less than the fungicidally effective amount of pyrazole-carboxamide fungicide when using the pyrazole-carboxamide fungicide separately.

The present invention also provides a mixture comprising any of the combinations disclosed herein.

The present invention also provides a fungicidal composition comprising any of the combinations or mixtures disclosed herein.

The present invention also provides a method of treating a plant or locus for a fungal infection, comprising applying an effective amount of any of the combinations, mixtures or compositions disclosed herein to the plant or locus, thereby treating the plant or locus for the fungal infection.

The present invention also provides the use of any of the combinations, mixtures or compositions disclosed herein for treating a plant or locus for a fungal infection.

The present invention also provides any of the combinations, mixtures and compositions described herein for use in treating a plant or locus for a fungal infection.

The present invention also provides a package comprising any of the combinations, mixtures or compositions disclosed herein.

The present invention also provides a method for producing any of the combinations, mixtures or compositions disclosed herein from the individual components.

DESCRIPTION OF GRAPHIC MATERIALS

Fig. 1 shows the efficacy of the premixed formulations according to Examples 1 and 2 compared to tank mixes of the same agents and a three-component premixed formulation of tebuconazole, picoxystrobin and mancozeb (commercial standard) for the control of Phakopsora pachyrhizi infecting soybean plants of the BONUS variety (test conducted in Uberlandia (UJ)/Brazil).

Fig. 2 shows the efficacy of the premixed formulations according to Examples 1 and 2 compared to tank mixes of the same agents and a three-component premixed formulation of tebuconazole, picoxystrobin and mancozeb (commercial standard) for the control of Phakopsora pachyrhizi infecting soybean plants of the M 5917 IPRO variety (test conducted in Ponta Grossa (PR)/Brazil).

Fig. 3 shows the efficacy of the premixed formulations according to Examples 1 and 2 compared to tank mixes of the same agents and a three-component premixed formulation of tebuconazole, picoxystrobin and mancozeb (commercial standard) for the control of Phakopsora pachyrhizi infecting soybean plants of the BONUS variety (test conducted in Rio Verde (GO)/Brazil).

DETAILED DESCRIPTION OF THE INVENTION

Definitions

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

As used in this application, the term "stable" with respect to a composition means that the composition is physically stable and chemically stable. As used in this application, the term "chemically stable" means that after at least 2 weeks of storage in a sealed package at a temperature of 54°C, no significant degradation of the active components was observed. As used in this application, the term "physically stable" means that after at least 2 weeks of storage in a sealed package at a temperature of 54°C, no significant phase separation and/or precipitation was observed.

Stability is assessed according to the test protocol established by the Collaborative International Pesticides Analytical Council Ltd. (CIPAC), namely: accelerated storage method (CIPAC MT 46.3); density (CIPAC MT 3.3.2) and wet sieving method (CIPAC MT 185). The CIPAC test protocols are industry standard for assessing stability before and after storage. Other stability parameters, such as flowability and concentrations of active ingredients before and after storage, can be assessed using tests commonly used in the agrochemical industry. Stability can be assessed under normal storage conditions, i.e. after two years of storage at room temperature. Stability can also be assessed under accelerated storage conditions, i.e. after 2 weeks of storage at 54°C, or after 8 weeks at 40°C, or after 12 weeks at 35°C, or after 3 months at room temperature, or after 2 weeks at 0°C.

As used in this application, the term "combination" means a set of agrochemicals for either joint or simultaneous use.

As used in this application, the term "combined" in the context of the application of agrochemicals means that the agrochemicals are applied in a mixture, such as a tank mix. In the case of combined application, the combination may be a mixture or separate containers, each containing an agrochemical, which are combined before application.

As used in this application, the term "simultaneous" in the context of application of agrochemicals means that an individual agrochemical is applied separately from another agrochemical or premix at the same time or at times close enough to each other to provide an activity that is additive, or more than additive, or synergistic with respect to the activity of either agrochemical applied alone at the same rate.

As used in this application, the term "mixture" refers, without limitation, to a combination in any physical form, such as a mixture, solution, suspension, dispersion, emulsion, alloy, etc.

As used herein, the term "tank-mix" means that one or more components of a combination, mixture, or composition of the present invention are mixed in a spray tank during or prior to spray application.

As used herein, the term "composition" includes at least one of the combinations or mixtures of the present invention with an agriculturally acceptable carrier. The composition may be a formulation, including a commercial formulation.

As used herein, the term "effective" with respect to an amount of an active ingredient, combination, mixture, or composition refers to an amount of the active ingredient, combination, mixture, or composition that provides an agriculturally beneficial level of control of a fungus, pathogen, and/or disease when applied to a plant, plant propagation material, soil, or locus.

As used in this application, the term "fungicidally effective amount" refers to the amount of the active ingredient that is commercially recommended for use to control fungi. The commercially recommended amount for each active ingredient, which is often referred to as the application amount of a commercial formulation, can be found on the label provided with the commercial formulation. The commercially recommended application amounts of a commercial formulation may vary depending on factors such as the plant species and fungus being controlled.

As used in this application, the term "effective" in relation to a method of treating a plant or locus from a fungal infection means that the method provides an agriculturally beneficial level of treatment without significantly affecting the normal growth and development of the plant.

As used in this application, the term "treating a plant or locus against a fungal infection" includes, but is not limited to, protecting a plant or locus from a fungal infection and/or controlling a fungal infection of a plant or locus.

As used in this application, the term "protecting a plant or locus from a fungal infection" includes, but is not limited to, protecting a plant or locus from infection by a fungus, protecting a plant or locus from a fungal disease, and/or preventing a fungal infection in a plant or locus.

As used in this application, the term "controlling a fungal infection of a plant or locus" includes, but is not limited to, controlling a fungal disease infecting a plant or locus, controlling a plant or soil disease caused by a phytopathogenic fungus, controlling infection of a plant or locus by a fungus, reducing a fungal infection of a plant or locus, and/or treating a plant or soil disease caused by phytopathogenic fungi.

As used in this application, the term "more effective in protecting a plant or locus from fungal infection" includes, but is not limited to, increasing the duration of protection from fungal infection after application and prolonging the period of protection from fungal infection.

As used in this application, the term "more effective in controlling a fungal disease" includes, but is not limited to, increasing the effectiveness of controlling a fungal disease and reducing the time required to achieve a given level of control of a fungal disease.

As used in this application, the term "agriculturally acceptable carrier" means carriers that are known and used in the art for preparing compositions for agricultural or horticultural use.

As used in this application, the term "adjuvant" broadly means any substance that is not itself an active ingredient but enhances or is intended to enhance the effectiveness of a fungicide with which it is used. Adjuvants may be considered to include spreading agents, penetration enhancing agents, compatibility enhancing agents, and drift reducing agents.

As used in this application, the term "agriculturally acceptable inert additives" means any substance that is not itself an active ingredient but is added to the composition, such as mucilages, surfactants, synergists, buffers, acidifiers, antioxidants, antifoams and thickeners.

As used in this application, the term "plant" includes reference to the entire plant, a plant organ (e.g. leaves, stems, branches, roots, trunks, twigs, shoots, fruits, etc.), plant cells, and plant propagation material.

As used in this application, the term "plant" includes reference to agricultural crops, including field crops (soybeans, corn, wheat, rice, etc.), vegetable crops (potatoes, cabbage, etc.) and fruits (peach, etc.).

As used in this application, the term "propagation material" shall be understood to mean all generative parts of the plant, such as seeds and spores, seedlings, and vegetative structures, such as bulbs, corms, tubers, rhizomes, rhizomes, shoots, stolons and buds.

As used in this application, the term "locus" includes not only areas where fungal infection has already occurred, but also areas where fungal infection has not yet occurred, as well as cultivated lands. The locus includes, but is not limited to, soil and other plant growth media.

As used in this application, the term "ha" refers to hectare.

As used herein, the term "excipient" refers to any chemical substance that does not have significant pesticidal activity, such as a surfactant(s), solvent(s), or excipient(s). One or more excipients may be added to any combination, mixture, or composition disclosed herein.

As used in this application, the indefinite article (a or an) includes the singular and the plural unless otherwise specifically stated. Therefore, the terms "a", "an" or "at least one" may be used interchangeably in this application.

In this application, the term "comprising" is used to describe various embodiments; however, one skilled in the art will appreciate that in some specific instances, an embodiment of the present invention may be described using the phrase "consisting essentially of" or "consisting of."

The term "about" as used herein specifically includes ±10% of the stated range values. Furthermore, the limits of all ranges relating to the same component or property as used herein include all end values, may be independently combined, and include all intermediate values and ranges.

It is obvious that where a range of parameters is given, all integers within that range and their tenths are also included within the scope of the invention, as if the said integers and their tenths were expressly given herein. For example, "0.1-80 wt.%" includes 0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, etc. up to 80 wt.%.

All publications, patents and patent applications mentioned in this specification are herein incorporated by reference in their entirety to the same extent as if each individual publication, patent or patent application was specifically and individually indicated to be incorporated by reference.

The following examples illustrate the implementation of the present invention in some embodiments, but should not be considered as limiting the scope of the present invention. Other embodiments, obvious to those skilled in the art after reading the description and examples given herein, which are within the scope of the appended claims, are part of the present invention. The present description, including examples, is intended only to illustrate, but not to limit the scope and essence of the present invention.

Aspects and embodiments of the present invention will now be described.

Oily liquid fungicidal compositions

Dithiocarbamate fungicides are usually prepared as dry formulations. Triazole fungicides are usually prepared as emulsifiable concentrates or suspension concentrates, and it is known that emulsifiable concentrates are more effective. Fluxapyroxad, which is a pyrazole carboxamide, is usually prepared as emulsifiable concentrates or suspension concentrates. There is a need in the art for a stable liquid oil composition containing a dithiocarbamate fungicide, a triazole fungicide and a pyrazole carboxamide fungicide, as proposed in the present invention.

Being stable even after long-term storage, the composition according to the present invention also enhances the fungicidal activity of the active ingredients contained therein, so that the use of said composition for treating a plant or locus from a fungal infection is more effective compared to the use of the same amount of each fungicide in the form of a tank mixture or separately. The composition according to the present invention is also more effective for treating a plant or locus from a fungal infection than known three-component compositions, including a composition containing a dithiocarbamate fungicide, a triazole fungicide and a strobilurin fungicide, described in the publication of international application WO 2017/203527 A1.

The present invention provides a fungicidal liquid oil composition comprising:

(i) at least one dithiocarbamate fungicide,

(ii) at least one triazole fungicide,

(iii) at least one pyrazole carboxamide fungicide, and

(iv) at least one agrochemically acceptable non-aqueous liquid carrier, wherein the dithiocarbamate fungicide is suspended in said liquid carrier and the triazole fungicide and the pyrazole carboxamide fungicide are dissolved in said liquid carrier.

The present invention provides a stable fungicidal liquid oil composition comprising:

(i) at least one dithiocarbamate fungicide,

(ii) at least one triazole fungicide,

(iii) at least one pyrazole carboxamide fungicide, and

(iv) at least one agrochemically acceptable non-aqueous liquid carrier,

wherein the dithiocarbamate fungicide is suspended in said liquid carrier, and the triazole fungicide and pyrazole-carboxamide fungicide are dissolved in said liquid carrier.

In some embodiments, the dithiocarbamate fungicide is selected from the group consisting of mancozeb, maneb, metiram, propineb, thiram, zinc thiazole, zineb, and ziram.

In some embodiments, the dithiocarbamate fungicide is mancozeb.

In some embodiments, the triazole fungicide is selected from the group consisting of azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, and prothioconazole.

In some embodiments, the triazole fungicide is prothioconazole.

In some embodiments, the triazole fungicide is tebuconazole.

In some embodiments, the pyrazole carboxamide fungicide is selected from the group consisting of benzovindiflupyr, bixafen, fluxapyroxad, furametpyr, isopyrazam, penflufen, penthiopyrad, and sedaxan.

In some embodiments, the pyrazole carboxamide fungicide is fluxapyroxad.

For chemical classes of fungicides, as well as specific compounds within each class, see The Pesticide Manual Eighteenth Edition (British Crop Protection Council, Hampshire, UK, 2018) and The e-Pesticide Manual, Version 5.2 (British Crop Protection Council, Hampshire, UK, 2008-2011), the contents of each of which are incorporated herein by reference in their entirety.

In a preferred embodiment, the present invention relates to a fungicidal liquid oil composition comprising: a) mancozeb, b) tebuconazole, c) fluxapyroxad and d) a non-aqueous liquid carrier, wherein mancozeb is suspended in said non-aqueous liquid carrier and tebuconazole and fluxapyroxad are dissolved in said non-aqueous liquid carrier.

In another preferred embodiment, the present invention relates to a fungicidal liquid oil composition comprising: a) mancozeb, b) prothioconazole, c) fluxapyroxad and d) a non-aqueous liquid carrier, wherein mancozeb is suspended in said non-aqueous liquid carrier and prothioconazole and fluxapyroxad are dissolved in said non-aqueous liquid carrier.

In some embodiments, the amount of dithiocarbamate fungicide is about 0.1-80 wt. % based on the total weight of the composition. In some embodiments, the amount of dithiocarbamate fungicide is about 10-60 wt. % based on the total weight of the composition. In some embodiments, the amount of dithiocarbamate fungicide is about 20-50 wt. % based on the total weight of the composition. In some embodiments, the amount of dithiocarbamate fungicide is about 30-40 wt. % based on the total weight of the composition. In some embodiments, the amount of dithiocarbamate fungicide is about 35 wt. % based on the total weight of the composition.

In some embodiments, the amount of dithiocarbamate fungicide in the composition is about 300-600 g/L. In some embodiments, the amount of dithiocarbamate fungicide in the composition is about 400-500 g/L. In some embodiments, the amount of dithiocarbamate fungicide in the composition is about 418-462 g/L. In some embodiments, the amount of dithiocarbamate fungicide in the composition is about 440 g/L.

In some embodiments, the amount of the triazole fungicide and the pyrazole carboxamide fungicide together is about 0.1-20 wt. % based on the total weight of the composition. In some embodiments, the amount of the triazole fungicide and the pyrazole carboxamide fungicide together is about 1-10 wt. % based on the total weight of the composition. In some embodiments, the amount of the triazole fungicide and the pyrazole carboxamide fungicide together is about 4-7 wt. % based on the total weight of the composition. In some embodiments, the amount of the triazole fungicide and the pyrazole carboxamide fungicide together is about 5-6 wt. % based on the total weight of the composition. In some embodiments, the amount of the triazole fungicide and the pyrazole carboxamide fungicide together is about 5.5 wt. % based on the total weight of the composition. In some embodiments, the amount of the triazole fungicide and the pyrazole-carboxamide fungicide together is 5.38 wt. % based on the total weight of the composition. In some embodiments, the amount of the triazole fungicide and the pyrazole-carboxamide fungicide together is about 3-6 wt. % based on the total weight of the composition. In some embodiments, the amount of the triazole fungicide and the pyrazole-carboxamide fungicide together is about 4-5 wt. % based on the total weight of the composition. In some embodiments, the amount of the triazole fungicide and the pyrazole-carboxamide fungicide together is about 4.5 wt. % based on the total weight of the composition. In some embodiments, the amount of the triazole fungicide and the pyrazole-carboxamide fungicide together is 4.25 wt. % based on the total weight of the composition.

In some embodiments, the amount of triazole fungicide is about 0.1-15 wt. % based on the total weight of the composition. In some embodiments, the amount of triazole fungicide is about 1-10 wt. % based on the total weight of the composition. In some embodiments, the amount of triazole fungicide is about 2-5 wt. % based on the total weight of the composition. In some embodiments, the amount of triazole fungicide is about 3-4 wt. % based on the total weight of the composition. In some embodiments, the amount of triazole fungicide is about 3.5 wt. % based on the total weight of the composition. In some embodiments, the amount of triazole fungicide is 3.57 wt. % based on the total weight of the composition. In some embodiments, the amount of triazole fungicide is about 1-4 wt. % based on the total weight of the composition. In some embodiments, the amount of triazole fungicide is about 2-3 wt. % based on the total weight of the composition. In some embodiments, the amount of triazole fungicide is about 2.5 wt. % based on the total weight of the composition. In some embodiments, the amount of triazole fungicide is 2.48 wt. % based on the total weight of the composition.

In some embodiments, the amount of the triazole fungicide in the composition is about 20-60 g/L. In some embodiments, the amount of the triazole fungicide in the composition is about 40-50 g/L. In some embodiments, the amount of the triazole fungicide in the composition is 40.05-48.95 g/L. In some embodiments, the amount of the triazole fungicide in the composition is about 44.5 g/L. In some embodiments, the amount of the triazole fungicide in the composition is about 25-35 g/L. In some embodiments, the amount of the triazole fungicide in the composition is about 28.35-34.65 g/L. In some embodiments, the amount of the triazole fungicide in the composition is about 31.5 g/L.

In some embodiments, the amount of pyrazole-carboxamide fungicide is about 0.1-10 wt. % based on the total weight of the composition. In some embodiments, the amount of pyrazole-carboxamide fungicide is about 0.1-5 wt. % based on the total weight of the composition. In some embodiments, the amount of pyrazole-carboxamide fungicide is about 1-2 wt. % based on the total weight of the composition. In some embodiments, the amount of pyrazole-carboxamide fungicide is about 1.7 wt. % based on the total weight of the composition. In some embodiments, the amount of pyrazole-carboxamide fungicide is about 1.8 wt. % based on the total weight of the composition. In some embodiments, the amount of pyrazole-carboxamide fungicide is about 1.77 wt. % based on the total weight of the composition. In some embodiments, the amount of pyrazole-carboxamide fungicide is about 1.81 wt. % based on the total weight of the composition.

In some embodiments, the amount of pyrazole-carboxamide fungicide in the composition is about 15-30 g/L. In some embodiments, the amount of pyrazole-carboxamide fungicide in the composition is about 19.13-25.88 g/L. In some embodiments, the amount of pyrazole-carboxamide fungicide in the composition is about 22.5 g/L.

In some embodiments, the composition comprises at least one non-aqueous liquid carrier. The non-aqueous liquid carrier may include, but is not limited to, 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, heptadecane, octadecane, nonadecane, eicosane, heneicosane, docosane, tricosane, tetracosane, pentacosane and their branched chain isomers), petroleum, alcohols (e.g. 2-ethylhexanol), ketones (e.g. acetophenone, cyclohexanone), vegetable oil (e.g. olive oil, kapok oil, castor oil, papaya oil, camellia oil, palm oil, sesame oil, corn oil, rice bran oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil, linseed oil, tung oil, sunflower oil, safflower oil, tall oil), alkyl esters of vegetable oils (e.g. methyl ester of rapeseed oil or ethyl ester of rapeseed oil, propyl esters of rapeseed oil, butyl esters of rapeseed oil, methyl ester of soybean oil, fatty acid esters of tall oil, etc.), diesel fuel, mineral oil, alkyl amides (e.g. N,N-dimethyldecanamide), fatty acid amides (e.g. C ₁ -C ₃ amines, alkyl amines or alkanolamines of C ₆ -C ₁₈ carboxylic acids), fatty acids, tall oil fatty acids, alkyl esters of fatty acids (e.g. esters formed by C ₁ -C ₄ monohydric alcohols and C ₈ -C ₂₂ fatty acids, such as methyl oleate, ethyl oleate), modified vegetable oils and their combinations.

In some embodiments, the non-aqueous liquid carrier is selected from the group consisting of aromatic hydrocarbons, alkyl amides, alkyl esters of vegetable oils, alcohols, and any combination thereof.

In some embodiments, the total amount of non-aqueous liquid carrier in the composition is about 0.1-80 weight % based on the total weight of the composition. In some embodiments, the total amount of non-aqueous liquid carrier in the composition is about 1-60 weight % based on the total weight of the composition. In some embodiments, the total amount of non-aqueous liquid carrier in the composition is about 10-50 weight % based on the total weight of the composition. In some embodiments, the total amount of non-aqueous liquid carrier in the composition is about 20-50 weight % based on the total weight of the composition. In some embodiments, the total amount of non-aqueous liquid carrier in the composition is about 35-45 weight % based on the total weight of the composition. In some embodiments, the total amount of non-aqueous liquid carrier in the composition is about 35-40 weight % based on the total weight of the composition. In some embodiments, the total amount of non-aqueous liquid carrier in the composition is 38.21-39 weight % based on the total weight of the composition. In some embodiments, the total amount of non-aqueous liquid carrier in the composition is about 39 wt. % based on the total weight of the composition. In some embodiments, the total amount of non-aqueous liquid carrier in the composition is about 35-36 wt. % based on the total weight of the composition. In some embodiments, the total amount of non-aqueous liquid carrier in the composition is about 35 wt. % based on the total weight of the composition. In some embodiments, the total amount of non-aqueous liquid carrier in the composition is 34.65-35.45 wt. % based on the total weight of the composition. In some embodiments, the total amount of non-aqueous liquid carrier in the composition is 35.45 wt. % based on the total weight of the composition.

In some embodiments, the non-aqueous liquid carrier comprises at least one aromatic hydrocarbon. In some embodiments, the non-aqueous liquid carrier is an aromatic hydrocarbon. In some embodiments, the aromatic hydrocarbon is naphthalene. In some embodiments, the aromatic hydrocarbon is aromatic heavy solvent naphtha 200. In some embodiments, the aromatic hydrocarbon is Solvesso™ 200 (available from Exxon Mobil). In some embodiments, the aromatic hydrocarbon is aromatic solvent naphtha 150. In some embodiments, the aromatic hydrocarbon is Solvesso™ 150 (available from Exxon Mobil). In some embodiments, the aromatic hydrocarbon is aromatic solvent naphtha 100. In some embodiments, the aromatic hydrocarbon is Solvesso™ 100 (available from Exxon Mobil). In some embodiments, the aromatic hydrocarbon has a CAS number of 64742-94-5. The aromatic hydrocarbon has the CAS number 64742-95-6.

In some embodiments, the amount of aromatic hydrocarbon in the composition is about 0.1-60 wt. % based on the total weight of the composition. In some embodiments, the amount of aromatic hydrocarbon in the composition is about 0.1-30 wt. % based on the total weight of the composition. In some embodiments, the amount of aromatic hydrocarbon in the composition is about 1-20 wt. % based on the total weight of the composition. In some embodiments, the amount of aromatic hydrocarbon in the composition is about 10-15 wt. % based on the total weight of the composition. In some embodiments, the amount of aromatic hydrocarbon in the composition is about 11-12 wt. % based on the total weight of the composition. In some embodiments, the amount of aromatic hydrocarbon in the composition is about 11 wt. % based on the total weight of the composition. In some embodiments, the amount of aromatic hydrocarbon in the composition is 11.24 wt. % based on the total weight of the composition. In some embodiments, the amount of aromatic hydrocarbon in the composition is about 12 wt. % based on the total weight of the composition. In some embodiments, the amount of aromatic hydrocarbon in the composition is 11.81 wt.% based on the total weight of the composition.

In some embodiments, the non-aqueous liquid carrier comprises at least one alkylamide. In some embodiments, the non-aqueous liquid carrier is an alkylamide. In some embodiments, the non-aqueous carrier is decanamide optionally substituted with at least one alkyl. In some embodiments, the non-aqueous carrier is decanamide optionally substituted with two alkyls. In some embodiments, the alkylamide is N,N-dimethyldecanamide. N,N-dimethyldecanamide has a CAS number of 14433-76-2. In some embodiments, N,N-dimethyldecanamide is Hallomid® M-10 (available from Stepan). In some embodiments, the non-aqueous carrier is octanamide optionally substituted with at least one alkyl. In some embodiments, the non-aqueous carrier is octanamide optionally substituted with two alkyls. In some embodiments, the non-aqueous carrier is N,N-dimethyloctanamide. In some embodiments, the non-aqueous carrier is a mixture of N,N-dimethyloctanamide and N,N-dimethyldecanamide.

The use of an alkylamide, preferably octanamide and/or decanamide, as a non-aqueous carrier stabilizes the pyrazole carboxamide fungicide solution because the amide group of the non-aqueous carrier strongly interacts with the pyrazole carboxamide fungicide (e.g. fluxapyroxad) and prevents crystal growth in the composition.

In some embodiments, the amount of alkylamide in the composition is about 0.1-30 weight % based on the total weight of the composition. In some embodiments, the amount of alkylamide in the composition is about 0.1-20 weight % based on the total weight of the composition. In some embodiments, the amount of alkylamide in the composition is about 0.1-10 weight % based on the total weight of the composition. In some embodiments, the amount of alkylamide in the composition is about 1-5 weight % based on the total weight of the composition. In some embodiments, the amount of alkylamide in the composition is about 2-3 weight % based on the total weight of the composition. In some embodiments, the amount of alkylamide in the composition is about 3-4 weight % based on the total weight of the composition. In some embodiments, the amount of alkylamide in the composition is 2.81 weight % based on the total weight of the composition. In some embodiments, the amount of alkylamide in the composition is 3.15 weight % based on the total weight of the composition.

In some embodiments, the non-aqueous liquid carrier comprises at least one vegetable oil alkyl ester. In some embodiments, the non-aqueous liquid carrier is a vegetable oil alkyl ester. In some embodiments, the vegetable oil alkyl ester is a soybean oil alkyl ester. In some embodiments, the vegetable oil alkyl ester is a soybean oil methyl ester. In some embodiments, the soybean oil methyl ester has a CAS number of 67784-62-9. In some embodiments, the soybean oil methyl ester is methylated soybean oil (available from Cargill).

In some embodiments, the amount of vegetable oil alkyl ester in the composition is about 0.1-50 wt. % based on the total weight of the composition. In some embodiments, the amount of vegetable oil alkyl ester in the composition is about 1-40 wt. % based on the total weight of the composition. In some embodiments, the amount of vegetable oil alkyl ester in the composition is about 1-30 wt. % based on the total weight of the composition. In some embodiments, the amount of vegetable oil alkyl ester in the composition is about 5-30 wt. % based on the total weight of the composition. In some embodiments, the amount of vegetable oil alkyl ester in the composition is about 10-20 wt. % based on the total weight of the composition. In some embodiments, the amount of vegetable oil alkyl ester in the composition is about 10-15 wt. % based on the total weight of the composition. In some embodiments, the amount of vegetable oil alkyl ester in the composition is about 20-30 wt. % based on the total weight of the composition. In some embodiments, the amount of vegetable oil alkyl ester in the composition is about 20-25 wt. % based on the total weight of the composition. In some embodiments, the amount of vegetable oil alkyl ester in the composition is about 13-14 wt. % based on the total weight of the composition. In some embodiments, the amount of vegetable oil alkyl ester in the composition is about 13 wt. % based on the total weight of the composition. In some embodiments, the amount of vegetable oil alkyl ester in the composition is 12.57-13.37 wt. % based on the total weight of the composition. In some embodiments, the amount of vegetable oil alkyl ester in the composition is 13.37 wt. % based on the total weight of the composition. In some embodiments, the amount of vegetable oil alkyl ester in the composition is about 24-25 wt. % based on the total weight of the composition. In some embodiments, the amount of vegetable oil alkyl ester in the composition is 23.5-24.04 wt. % based on the total weight of the composition. In some embodiments, the amount of vegetable oil alkyl ester in the composition is about 24 wt. % based on the total weight of the composition. In some embodiments, the amount of vegetable oil alkyl ester in the composition is 24.04 wt. % based on the total weight of the composition.

In some embodiments, the non-aqueous carrier comprises at least one alcohol. In some embodiments, the non-aqueous liquid carrier is an alcohol. In some embodiments, the alcohol is 2-ethylhexanol. 2-ethylhexanol has a CAS number of 104-76-7. In some embodiments, 2-ethylhexanol is available from Elekeiroz. It has been noted that in compositions containing tebuconazole, especially with a high concentration of tebuconazole, a viscous layer may form at the bottom of the package. 2-ethylhexanol has good polarity and low viscosity. The use of 2-ethylhexanol in the composition prevents the formation of this viscous layer.

In some embodiments, the amount of alcohol in the composition is about 0.1-30 wt. % based on the total weight of the composition. In some embodiments, the amount of alcohol in the composition is about 1-20 wt. % based on the total weight of the composition. In some embodiments, the amount of alcohol in the composition is about 1-10 wt. % based on the total weight of the composition. In some embodiments, the amount of alcohol in the composition is about 5-10 wt. % based on the total weight of the composition. In some embodiments, the amount of alcohol in the composition is about 8-9 wt. % based on the total weight of the composition. In some embodiments, the amount of alcohol in the composition is 8.03 wt. % based on the total weight of the composition.

In some embodiments, the composition comprises at least two non-aqueous liquid carriers. In some embodiments, the composition comprises at least three non-aqueous liquid carriers. In some embodiments, the composition comprises three non-aqueous liquid carriers. In some embodiments, the composition comprises four non-aqueous liquid carriers.

In some embodiments, the non-aqueous liquid carrier is a combination of an aromatic hydrocarbon, an alkyl amide, and an alkyl ester of a vegetable oil.

In some embodiments, the non-aqueous liquid carrier is a combination of aromatic heavy solvent naphtha 200, N,N-dimethyldecanamide, and soybean oil methyl ester.

In some embodiments, the non-aqueous liquid carrier is a combination of an aromatic hydrocarbon, an alkyl amide, an alkyl ester of a vegetable oil, and an alcohol.

In some embodiments, the non-aqueous liquid carrier is a combination of aromatic heavy solvent naphtha 200, N,N-dimethyldecanamide, methyl soybean oil, and 2-ethylhexanol.

In some embodiments, the non-aqueous liquid carrier is a combination of an aromatic hydrocarbon and an alkylamide. The combination of an aromatic hydrocarbon, such as Solvesso™, and an alkylamide, such as decanamide, as a non-aqueous liquid carrier provides solubility of the pyrazole carboxamide fungicide and the triazole fungicide.

In some embodiments, the non-aqueous liquid carrier is a combination of an aromatic hydrocarbon, an alkylamide, and an alcohol. In some embodiments, the non-aqueous liquid carrier is a combination of (i) solvent naphtha, (ii) N,N-dimethyloctanamide, N,N-dimethyldecanamide, or a mixture thereof, and (iii) 2-ethylhexanol.

In some embodiments, the composition comprises at least one excipient. In some embodiments, the excipient is in a liquid carrier.

The excipient may include, but is not limited to, vegetable oils, alkyl esters of vegetable oils such as, for example, soybean methyl ester, soybean ethyl ester, rapeseed oil methyl ester or rapeseed oil ethyl ester, alkoxylated sorbitan esters such as, for example, sorbitan monolaurate alkoxylates such as, for example, polyoxyethylene (16) sorbitan monolaurate (Tween™ 24), polyoxyethylene (20) sorbitan monolaurate (Tween™ 20; Alkamuls® PSML-20), polyoxyethylene (4) sorbitan monolaurate (Tween™ 21), polyoxyethylene (8) sorbitan monolaurate (Tween™ 22), polyoxyethylene (12) sorbitan monolaurate (Tween™ 23), sorbitan monolaurate (Alkamuls® S/20, Glycomul® LK, Glycomul® LC, Span® 20), polyoxyethylene (20) sorbitan monostearate alkoxylates, such as, for example, polyoxyethylene (20) sorbitan monostearate (Tween™ 60), polyoxyethylene (4) sorbitan monostearate (Tween™ 61), sorbitan monostearate (Alkamuls® S/90, Glycomul® S, Span® 60), sorbitan monooleate alkoxylates, such as, for example, polyoxyethylene (20) sorbitan monooleate (Tween™ 80, Emulgin® SMO 20, T-Maz® 80, Agnique® SMO 20U), polyoxyethylene (5) sorbitan monooleate (Tween™ 81), sorbitan monooleate (Alkamuls® S/80, Span® 80), and combinations thereof.

In some embodiments, the excipient is tall oil fatty acids (TOFA) and/or soy methyl ester and/or sorbitan monolaurate alkoxylates such as polyoxyethylene (16) sorbitan monolaurate. In some embodiments, the excipient is sorbitan monolaurate alkoxylate. In some embodiments, the excipient is polyoxyethylene (16) sorbitan monolaurate. In some embodiments, the excipient is Tween™ 24 (available from Croda).

In some embodiments, the amount of excipient in the composition is about 0.1-80 wt. % based on the total weight of the composition. In some embodiments, the amount of excipient in the composition is about 1-20 wt. % based on the total weight of the composition. In some embodiments, the amount of excipient in the composition is about 10-15 wt. % based on the total weight of the composition. In some embodiments, the amount of excipient in the composition is about 11-12 wt. % based on the total weight of the composition. In some embodiments, the amount of excipient in the composition is about 12-13 wt. % based on the total weight of the composition. In some embodiments, the amount of excipient in the composition is about 12 wt. % based on the total weight of the composition. In some embodiments, the amount of excipient in the composition is 11.81 wt. % based on the total weight of the composition. In some embodiments, the amount of excipient in the composition is 12.05 wt. % based on the total weight of the composition.

In some embodiments, the fungicidal liquid oil composition further comprises at least one surfactant. The surfactant may include, but is not limited to, alkyl sulfonates, alkyl benzene sulfonates, alkyl aryl sulfonates, alkyl phenol alkoxylates, tristyryl phenol ethoxylates, natural or synthetic fatty ethoxylated alcohols, natural or synthetic fatty acid alkoxylates, natural or synthetic fatty alcohol alkoxylates, alkoxylated alcohols (such as n-butyl alcohol polyglycol ether), block copolymers (such as ethylene oxide-propylene oxide block copolymers and ethylene oxide-butylene oxide block copolymers), or combinations thereof.

In some embodiments, the surfactant is selected from the group consisting of tristyrylphenol ethoxylates, alkylbenzenesulfonates and their salts, ethylene oxide-propylene oxide block copolymers, and any combination thereof.

In some embodiments, the composition comprises at least two surfactants. In some embodiments, the composition comprises at least three surfactants. In some embodiments, the composition comprises three surfactants.

In some embodiments, the total amount of surfactants in the composition is about 0.1-40 weight % based on the total weight of the composition. In some embodiments, the total amount in the composition is about 1-40 weight % based on the total weight of the composition. In some embodiments, the total amount in the composition is about 1-25 weight % based on the total weight of the composition. In some embodiments, the total amount in the composition is about 1-15 weight % based on the total weight of the composition. In some embodiments, the total amount in the composition is about 5-15 weight % based on the total weight of the composition. In some embodiments, the total amount in the composition is about 7-10 weight % based on the total weight of the composition. In some embodiments, the total amount in the composition is about 8-9 weight % based on the total weight of the composition. In some embodiments, the total amount in the composition is about 9-12 weight % based on the total weight of the composition. In some embodiments, the total amount in the composition is about 10-11 weight % based on the total weight of the composition. In some embodiments, the total amount in the composition is about 8.5 wt. % based on the total weight of the composition. In some embodiments, the total amount in the composition is about 10 wt. % based on the total weight of the composition. In some embodiments, the total amount in the composition is 8.69 wt. % based on the total weight of the composition. In some embodiments, the total amount in the composition is 10.13 wt. % based on the total weight of the composition.

In some embodiments, the composition comprises tristyrylphenol ethoxylate. In some embodiments, the tristyrylphenol ethoxylate is tristyrylphenol ethoxylated 16 EO. Tristyrylphenol ethoxylated 16 EO has a CAS number of 99734-09-05. In some embodiments, the tristyrylphenol ethoxylate is Surfom® CE 1299 (manufactured by Oxiteno).

In some embodiments, the amount of tristyrylphenol ethoxylate in the composition is about 0.1-20 wt. % based on the total weight of the composition. In some embodiments, the amount of tristyrylphenol ethoxylate in the composition is about 0.5-10 wt. % based on the total weight of the composition. In some embodiments, the amount of tristyrylphenol ethoxylate in the composition is about 0.5-5 wt. % based on the total weight of the composition. In some embodiments, the amount of tristyrylphenol ethoxylate in the composition is about 1-2 wt. % based on the total weight of the composition. In some embodiments, the amount of tristyrylphenol ethoxylate in the composition is 1.69 wt. % based on the total weight of the composition. In some embodiments, the amount of tristyrylphenol ethoxylate in the composition is 1.65 wt. % based on the total weight of the composition.

In some embodiments, the composition comprises an alkyl benzene sulfonate or a salt thereof. In some embodiments, the alkyl benzene sulfonate is docetyl benzene sulfonate. In some embodiments, the alkyl benzene sulfonate salt is a calcium salt of alkyl benzene sulfonate. In some embodiments, the alkyl benzene sulfonate salt is a calcium salt of docetyl benzene sulfonate. The calcium salt of docetyl benzene sulfonate has a CAS number of 26264-06-2. In some embodiments, the calcium salt of docetyl benzene sulfonate is Rhodacal® 60/BE (available from Solvay).

In some embodiments, the amount of alkyl benzene sulfonate or salt thereof in the composition is about 0.1-30 wt. %, based on the total weight of the composition. In some embodiments, the amount of alkyl benzene sulfonate or salt thereof in the composition is about 1-20 wt. %, based on the total weight of the composition. In some embodiments, the amount of alkyl benzene sulfonate or salt thereof in the composition is about 1-10 wt. %, based on the total weight of the composition. In some embodiments, the amount of alkyl benzene sulfonate or salt thereof in the composition is about 5-8 wt. %, based on the total weight of the composition. In some embodiments, the amount of alkyl benzene sulfonate or salt thereof in the composition is about 6-7 wt. %, based on the total weight of the composition. In some embodiments, the amount of alkyl benzene sulfonate or salt thereof in the composition is about 6.83 wt. %, based on the total weight of the composition. In some embodiments, the amount of alkyl benzene sulfonate or salt thereof in the composition is 6.69 wt. % based on the total weight of the composition.

In some embodiments, the composition comprises an ethylene oxide-propylene oxide block copolymer. In some embodiments, the ethylene oxide-propylene oxide block copolymer has a CAS number of 9038-95-3. In some embodiments, the ethylene oxide-propylene oxide block copolymer is Atlas™ 5002 L LQ (CQ) (available from Croda). In some embodiments, the ethylene oxide-propylene oxide block copolymer has a CAS number of 9003-11-6. In some embodiments, the ethylene oxide-propylene oxide block copolymer is Symperonic PE/F 68FL (available from Croda).

In some embodiments, the amount of ethylene oxide-propylene oxide block copolymer in the composition is about 0.1-15 weight % based on the total weight of the composition. In some embodiments, the amount of ethylene oxide-propylene oxide block copolymer in the composition is about 0.1-10 weight % based on the total weight of the composition. In some embodiments, the amount of ethylene oxide-propylene oxide block copolymer in the composition is about 0.1-5 weight % based on the total weight of the composition. In some embodiments, the amount of ethylene oxide-propylene oxide block copolymer in the composition is about 0.1-2 weight % based on the total weight of the composition. In some embodiments, the amount of ethylene oxide-propylene oxide block copolymer in the composition is about 0.1-1 weight % based on the total weight of the composition. In some embodiments, the amount of ethylene oxide-propylene oxide block copolymer in the composition is about 1-2 weight % based on the total weight of the composition. In some embodiments, the amount of ethylene oxide-propylene oxide block copolymer in the composition is about 0.1-0.5 wt. % based on the total weight of the composition. In some embodiments, the amount of ethylene oxide-propylene oxide block copolymer in the composition is about 1.5-2 wt. % based on the total weight of the composition. In some embodiments, the amount of ethylene oxide-propylene oxide block copolymer in the composition is about 0.3-0.4 wt. % based on the total weight of the composition. In some embodiments, the amount of ethylene oxide-propylene oxide block copolymer in the composition is about 0.35 wt. % based on the total weight of the composition. In some embodiments, the amount of ethylene oxide-propylene oxide block copolymer in the composition is 1.61 wt. % based on the total weight of the composition.

In some embodiments, the composition comprises tristyrylphenol ethoxylate, alkyl benzene sulfonate or a salt thereof, and an ethylene oxide-propylene oxide block copolymer.

In some embodiments, the composition comprises tristyrylphenol ethoxylated 16 EO, calcium salt of docecylbenzenesulfonate, and an ethylene oxide-propylene oxide block copolymer.

Other ingredients such as adhesives, neutralizers, thickeners, binders, sequestrants, biocides, stabilizers, suspension additives, buffering preservatives, antioxidants, antifoams or antifreezes may also be added to the present compositions to increase the stability, density and viscosity of the described compositions.

In some embodiments, the composition comprises an antifoaming agent. In some embodiments, the antifoaming agent is polydimethylsiloxane. In some embodiments, the polydimethylsiloxane has a CAS number of 63148-62-9. In some embodiments, the polydimethylsiloxane is Silcolapse® 500 (available from Elkem).

In some embodiments, the amount of defoamer in the composition is about 0.01-10 wt. % based on the total weight of the composition. In some embodiments, the amount of defoamer in the composition is about 0.01-5 wt. % based on the total weight of the composition. In some embodiments, the amount of defoamer in the composition is about 0.01-1 wt. % based on the total weight of the composition. In some embodiments, the amount of defoamer in the composition is about 0.01-0.1 wt. % based on the total weight of the composition. In some embodiments, the amount of defoamer in the composition is about 0.01-0.05 wt. % based on the total weight of the composition. In some embodiments, the amount of defoamer in the composition is about 0.04 wt. % based on the total weight of the composition.

In some embodiments, the composition comprises a suspension additive. In some embodiments, the suspension additive is silica, fumed silica, silicic anhydride, silicon dioxide, and/or amorphous silicon dioxide. In some embodiments, the suspension additive is fumed silica. In some embodiments, the suspension additive has a CAS number of 112945-52-5. In some embodiments, the suspension additive is CARB-O-SIL® M5 (available from Cabot Corporation). The addition of the suspension additive, preferably silica, reduces the caking of the composition.

In some embodiments, the amount of suspension additive in the composition is about 0.01-20 wt. % based on the total weight of the composition. In some embodiments, the amount of suspension additive in the composition is about 0.1-20 wt. % based on the total weight of the composition. In some embodiments, the amount of suspension additive in the composition is about 0.1-10 wt. % based on the total weight of the composition. In some embodiments, the amount of suspension additive in the composition is about 0.1-5 wt. % based on the total weight of the composition. In some embodiments, the amount of suspension additive in the composition is about 0.1-1 wt. % based on the total weight of the composition. In some embodiments, the amount of suspension additive in the composition is about 0.8 wt. % based on the total weight of the composition.

In some embodiments, the composition does not contain a suspension additive. In some embodiments, the composition does not contain fumed silica.

In some embodiments, the composition comprises a stabilizer. In some embodiments, the stabilizer is zinc oxide (CAS number 1314-13-2). In some embodiments, the stabilizer is available from Produquimica. Preferably, the compositions described herein are compatible with most commercial glyphosate formulations. It has been found that amphoteric surfactants (such as zinc oxide) or zwitterionic surfactants can aid in this compatibility. Additionally, the use of zinc oxide in the composition has the added benefit of increasing compatibility with glyphosate formulations without increasing the viscosity of the composition. In some embodiments, the viscosity of the composition is 500-2500 cP (speed 6, spindle 2). In some embodiments, the viscosity of the composition is 500-2000 cP (speed 6, spindle 2). In some embodiments, the viscosity of the composition is 800-1500 cP (speed 6, spindle 2).

In some embodiments, the amount of stabilizer in the composition is about 0.1-10 wt. % based on the total weight of the composition. In some embodiments, the amount of stabilizer in the composition is about 0.1-5 wt. % based on the total weight of the composition. In some embodiments, the amount of stabilizer in the composition is about 1-2 wt. % based on the total weight of the composition. In some embodiments, the amount of stabilizer in the composition is about 1.5 wt. % based on the total weight of the composition. In some embodiments, the amount of stabilizer in the composition is about 1.57 wt. % based on the total weight of the composition. In some embodiments, the amount of stabilizer in the composition is about 1.6 wt. % based on the total weight of the composition. In some embodiments, the amount of stabilizer in the composition is 1.61 wt. % based on the total weight of the composition.

In some embodiments, the composition has a pH of 5-9. In some embodiments, the composition has a pH of 5.5-8.5.

In some embodiments, the density of the composition at 20°C is about 1-1.5 g/ ^cm3 . In some embodiments, the density of the composition at 20°C is 1.245 g/ ^cm3 . In some embodiments, the density of the composition at 20°C is 1.27 g/ ^cm3 .

The present invention also provides a fungicidal liquid oil composition comprising:

(i) 33-36 wt. % mancozeb,

(ii) 2-3 wt. % prothioconazole,

(iii) 1-2 wt. % fluxapyroxade,

(iv) 2.5-3.5 wt.% N,N-dimethyldecanamide,

(v) 1-2 wt.% tristyrylphenol ethoxylated 16 EO,

(vi) 0.1-1 wt.% of ethylene oxide-propylene oxide block copolymer,

(vii) 10-13 wt. % ethoxylated sorbitan monolaurate,

(viii) 6-7 wt.% calcium salt of dodecylbenzenesulfonate,

(ix) 0.01-0.1 wt.% polydimethylsiloxane,

(x) 22-26 wt.% soybean oil methyl ester,

(xi) 10-13 wt.% aromatic heavy solvent naphtha 200, and

(xii) 1-2 wt.% zinc oxide.

The present invention also provides a fungicidal liquid oil composition comprising:

(i) 33-36 wt. % mancozeb,

(ii) 2-3 wt. % prothioconazole,

(iii) 1-2 wt. % fluxapyroxade,

(iv) 2.5-3.5 wt.% N,N-dimethyldecanamide,

(v) 1-2 wt.% tristyrylphenol ethoxylated 16 EO,

(vi) 0.1-1 wt.% of ethylene oxide-propylene oxide block copolymer,

(vii) 10-13 wt. % ethoxylated sorbitan monolaurate,

(viii) 6-7 wt.% calcium salt of dodecylbenzenesulfonate,

(ix) 0.01-0.1 wt.% polydimethylsiloxane,

(x) 22-26 wt.% soybean oil methyl ester,

(xi) 10-13 wt.% aromatic heavy solvent naphtha 200,

(xii) 1-2 wt.% zinc oxide and

(xiii) 0-1 wt.% silica.

The present invention also provides a fungicidal liquid oil composition comprising:

(i) 33-36 wt. % mancozeb,

(ii) 3-4 wt. % tebuconazole,

(iii) 1-2 wt. % fluxapyroxade,

(iv) 2-3 wt.% N,N-dimethyldecanamide,

(v) 11-13 wt. % ethoxylated sorbitan monolaurate,

(vi) 1-2 wt.% tristyrylphenol ethoxylated 16 EO,

(vii) 6-7 wt.% calcium salt of dodecylbenzenesulfonate,

(viii) 0.01-0.1 wt.% polydimethylsiloxane,

(ix) 11-15 wt.% soybean oil methyl ester,

(x) 10-13 wt.% aromatic heavy solvent naphtha 200,

(xi) 1-2 wt. % ethylene oxide-propylene oxide block copolymer,

(xii) 7.5-8.5 wt. % 1-ethylhexanol and

(xiii) 1-2 wt.% zinc oxide.

The present invention also provides a fungicidal liquid oil composition comprising:

(i) 33-36 wt. % mancozeb,

(ii) 3-4 wt. % tebuconazole,

(iii) 1-2 wt. % fluxapyroxade,

(iv) 2-3 wt.% N,N-dimethyldecanamide,

(v) 11-13 wt. % ethoxylated sorbitan monolaurate,

(vi) 1-2 wt.% tristyrylphenol ethoxylated 16 EO,

(vii) 6-7 wt.% calcium salt of dodecylbenzenesulfonate,

(viii) 0.01-0.1 wt.% polydimethylsiloxane,

(ix) 11-15 wt.% soybean oil methyl ester,

(x) 10-13 wt.% aromatic heavy solvent naphtha 200,

(xi) 1-2 wt. % ethylene oxide-propylene oxide block copolymer,

(xii) 7.5-8.5 wt. % 1-ethylhexanol,

(xiii) 1-2 wt.% zinc oxide and

(xiv) 0-1 wt.% silica.

The present invention also provides a fungicidal liquid oil composition comprising:

(i) 34.64 wt. % mancozeb,

(ii) 2.48 wt. % prothioconazole,

(iii) 1.77 wt. % fluxapyroxade,

(iv) 3.15 wt.% N,N-dimethyldecanamide,

(v) 1.65 wt.% tristyrylphenol ethoxylated 16 EO,

(vi) 0.35 wt.% of ethylene oxide-propylene oxide block copolymer,

(vii) 11.81 wt. % ethoxylated sorbitan monolaurate,

(viii) 6.69 wt.% calcium dodecylbenzenesulfonate,

(ix) 0.04 wt.% polydimethylsiloxane,

(x) 24.04 wt.% soybean oil methyl ester,

(xi) 11.81 wt.% aromatic heavy solvent naphtha 200, and

(xii) 1.57 wt.% zinc oxide.

The present invention also provides a fungicidal liquid oil composition comprising:

(i) 34.64 wt. % mancozeb,

(ii) 2.48 wt. % prothioconazole,

(iii) 1.77 wt. % fluxapyroxade,

(iv) 3.15 wt.% N,N-dimethyldecanamide,

(v) 1.65 wt.% tristyrylphenol ethoxylated 16 EO,

(vi) 0.35 wt.% of ethylene oxide-propylene oxide block copolymer,

(vii) 11.81 wt. % ethoxylated sorbitan monolaurate,

(viii) 6.69 wt.% calcium dodecylbenzenesulfonate,

(ix) 0.04 wt.% polydimethylsiloxane,

(x) 23.25-24.04 wt.% soybean oil methyl ester,

(xi) 11.81 wt.% aromatic heavy solvent naphtha 200,

(xii) 1.57 wt.% zinc oxide and

(xiii) 0-0.79 wt.% silica.

The present invention also provides a fungicidal liquid oil composition comprising:

(i) 35.34 wt. % mancozeb,

(ii) 3.57 wt. % tebuconazole,

(iii) 1.81 wt. % fluxapyroxade,

(iv) 2.81 wt.% N,N-dimethyldecanamide,

(v) 12.05 wt. % ethoxylated sorbitan monolaurate,

(vi) 1.69 wt.% tristyrylphenol ethoxylated 16 EO,

(vii) 6.83 wt.% calcium dodecylbenzenesulfonate,

(viii) 0.04 wt.% polydimethylsiloxane,

(ix) 13.37 wt.% soybean oil methyl ester,

(x) 11.24 wt.% aromatic heavy solvent naphtha 200,

(xi) 1.61 wt. % ethylene oxide-propylene oxide block copolymer,

(xii) 8.03 wt. % 1-ethylhexanol and

(xiii) 1.61 wt.% zinc oxide.

The present invention also provides a fungicidal liquid oil composition comprising:

(i) 35.34 wt. % mancozeb,

(ii) 3.57 wt. % tebuconazole,

(iii) 1.81 wt. % fluxapyroxade,

(iv) 2.81 wt.% N,N-dimethyldecanamide,

(v) 12.05 wt. % ethoxylated sorbitan monolaurate,

(vi) 1.69 wt.% tristyrylphenol ethoxylated 16 EO,

(vii) 6.83 wt.% calcium dodecylbenzenesulfonate,

(viii) 0.04 wt.% polydimethylsiloxane,

(ix) 12.57-13.37 wt.% soybean oil methyl ester,

(x) 11.24 wt.% aromatic heavy solvent naphtha 200,

(xi) 1.61 wt. % ethylene oxide-propylene oxide block copolymer,

(xii) 8.03 wt. % 1-ethylhexanol,

(xiii) 1.61 wt.% zinc oxide and

(xiv) 0-0.8 wt.% silica.

In some embodiments, the composition is chemically stable.

In some embodiments, the degradation of the dithiocarbamate fungicide in the composition is less than 35% after 2 weeks of storage at room temperature. In some embodiments, the degradation of the dithiocarbamate fungicide in the composition is less than 35% after 2 weeks of storage at 54°C. In some embodiments, the degradation of the dithiocarbamate fungicide in the composition is less than 35% after 8 weeks of storage at room temperature. In some embodiments, the degradation of the dithiocarbamate fungicide in the composition is less than 35% after 8 weeks of storage at 40°C. In some embodiments, the degradation of the dithiocarbamate fungicide in the composition is less than 35% after 1 week of storage at 0°C. In some embodiments, the degradation of the dithiocarbamate fungicide in the composition is less than 35% after 1 week of storage at -10°C.

In some embodiments, the degradation of the dithiocarbamate fungicide in the composition is less than 30%, less than 25%, less than 20%, less than 15%, less than 10%, less than 8%, less than 6%, less than 5%, less than 2.5%, or less than 1% after 2 weeks of storage at room temperature. In some embodiments, the degradation of the dithiocarbamate fungicide in the composition is less than 30%, less than 25%, less than 20%, less than 15%, less than 10%, less than 8%, less than 6%, less than 5%, less than 2.5%, or less than 1% after 2 weeks of storage at 54°C. In some embodiments, the degradation of the dithiocarbamate fungicide in the composition is less than 30%, less than 25%, less than 20%, less than 15%, less than 10%, less than 8%, less than 6%, less than 5%, less than 2.5%, or less than 1% after 8 weeks of storage at room temperature. In some embodiments, the degradation of the dithiocarbamate fungicide in the composition is less than 30%, less than 25%, less than 20%, less than 15%, less than 10%, less than 8%, less than 6%, less than 5%, less than 2.5%, or less than 1% after 8 weeks of storage at 40°C. In some embodiments, the degradation of the dithiocarbamate fungicide in the composition is less than 30%, less than 25%, less than 20%, less than 15%, less than 10%, less than 8%, less than 6%, less than 5%, less than 2.5%, or less than 1% after 1 week of storage at 0°C. In some embodiments, the degradation of the dithiocarbamate fungicide in the composition is less than 30%, less than 25%, less than 20%, less than 15%, less than 10%, less than 8%, less than 6%, less than 5%, less than 2.5%, or less than 1% after 1 week of storage at -10°C.

In some embodiments, the degradation of the triazole fungicide in the composition is less than 20% after 2 weeks of storage at room temperature. In some embodiments, the degradation of the triazole fungicide in the composition is less than 20% after 2 weeks of storage at 54°C. In some embodiments, the degradation of the triazole fungicide in the composition is less than 10% after 8 weeks of storage at room temperature. In some embodiments, the degradation of the triazole fungicide in the composition is less than 20% after 8 weeks of storage at 40°C. In some embodiments, the degradation of the triazole fungicide in the composition is less than 20% after 1 week of storage at 0°C. In some embodiments, the degradation of the triazole fungicide in the composition is less than 20% after 1 week of storage at -10°C.

In some embodiments, the degradation of the triazole fungicide in the composition is less than 20%, less than 17%, less than 15%, less than 11%, less than 10%, less than 7.5%, less than 5%, less than 4%, less than 3%, less than 2%, or less than 1% after 2 weeks of storage at room temperature. In some embodiments, the degradation of the triazole fungicide in the composition is less than 20%, less than 17%, less than 15%, less than 11%, less than 10%, less than 7.5%, less than 5%, less than 4%, less than 3%, less than 2%, or less than 1% after 2 weeks of storage at 54°C. In some embodiments, the degradation of the triazole fungicide in the composition is less than 20%, less than 17%, less than 15%, less than 11%, less than 10%, less than 7.5%, less than 5%, less than 4%, less than 3%, less than 2%, or less than 1% after 8 weeks of storage at room temperature. In some embodiments, the degradation of the triazole fungicide in the composition is less than 20%, less than 17%, less than 15%, less than 11%, less than 10%, less than 7.5%, less than 5%, less than 4%, less than 3%, less than 2%, or less than 1% after 8 weeks of storage at 40°C. In some embodiments, the degradation of the triazole fungicide in the composition is less than 20%, less than 17%, less than 15%, less than 11%, less than 10%, less than 7.5%, less than 5%, less than 4%, less than 3%, less than 2%, or less than 1% after 1 week of storage at 0°C. In some embodiments, the degradation of the triazole fungicide in the composition is less than 20%, less than 17%, less than 15%, less than 11%, less than 10%, less than 7.5%, less than 5%, less than 4%, less than 3%, less than 2%, or less than 1% after 1 week of storage at -10°C.

In some embodiments, the degradation of the pyrazole-carboxamide fungicide in the composition is less than 15% after 2 weeks of storage at room temperature. In some embodiments, the degradation of the pyrazole-carboxamide fungicide in the composition is less than 15% after 2 weeks of storage at 54°C. In some embodiments, the degradation of the pyrazole-carboxamide fungicide in the composition is less than 15% after 8 weeks of storage at room temperature. In some embodiments, the degradation of the pyrazole-carboxamide fungicide in the composition is less than 15% after 8 weeks of storage at 40°C. In some embodiments, the degradation of the pyrazole-carboxamide fungicide in the composition is less than 15% after 1 week of storage at 0°C. In some embodiments, the degradation of the pyrazole-carboxamide fungicide in the composition is less than 15% after 1 week of storage at -10°C.

In some embodiments, the degradation of the pyrazole-carboxamide fungicide in the composition is less than 12.5%, less than 10%, less than 7.5%, less than 5%, less than 4%, less than 3%, less than 2%, or less than 1% after 2 weeks of storage at room temperature. In some embodiments, the degradation of the pyrazole-carboxamide fungicide in the composition is less than 12.5%, less than 10%, less than 7.5%, less than 5%, less than 4%, less than 3%, less than 2%, or less than 1% after 2 weeks of storage at 54°C. In some embodiments, the degradation of the pyrazole-carboxamide fungicide in the composition is less than 12.5%, less than 10%, less than 7.5%, less than 5%, less than 4%, less than 3%, less than 2%, or less than 1% after 8 weeks of storage at room temperature. In some embodiments, the degradation of the pyrazole-carboxamide fungicide in the composition is less than 12.5%, less than 10%, less than 7.5%, less than 5%, less than 4%, less than 3%, less than 2%, or less than 1% after 8 weeks of storage at 40°C. In some embodiments, the degradation of the pyrazole-carboxamide fungicide in the composition is less than 12.5%, less than 10%, less than 7.5%, less than 5%, less than 4%, less than 3%, less than 2%, or less than 1% after 1 week of storage at 0°C. In some embodiments, the degradation of the pyrazole-carboxamide fungicide in the composition is less than 12.5%, less than 10%, less than 7.5%, less than 5%, less than 4%, less than 3%, less than 2%, or less than 1% after 1 week of storage at -10°C.

In some embodiments, the composition is physically stable.

In some embodiments, the phase separation in the composition after 2 weeks of storage at room temperature is less than 30%, less than 25%, less than 20%, less than 15%, less than 10%, less than 7.5%, less than 5%, less than 2.5%, or less than 1%. In some embodiments, the phase separation in the composition after 2 weeks of storage at 54°C is less than 30%, less than 25%, less than 20%, less than 15%, less than 10%, less than 7.5%, less than 5%, less than 2.5%, or less than 1%. In some embodiments, the phase separation in the composition after 8 weeks of storage at room temperature is less than 30%, less than 25%, less than 20%, less than 15%, less than 10%, less than 7.5%, less than 5%, less than 2.5%, or less than 1%. In some embodiments, the phase separation in the composition after 8 weeks of storage at 40°C is less than 30%, less than 25%, less than 20%, less than 15%, less than 10%, less than 7.5%, less than 5%, less than 2.5%, or less than 1%. In some embodiments, the phase separation in the composition after 1 week of storage at 0°C is less than 30%, less than 25%, less than 20%, less than 15%, less than 10%, less than 7.5%, less than 5%, less than 2.5%, or less than 1%. In some embodiments, the phase separation in the composition after 1 week of storage at -10°C is less than 30%, less than 25%, less than 20%, less than 15%, less than 10%, less than 7.5%, less than 5%, less than 2.5%, or less than 1%.

In some embodiments, the phase separation in the composition after 2 weeks of storage at room temperature is 4%. In some embodiments, the phase separation in the composition after 2 weeks of storage at room temperature is 2%. In some embodiments, the phase separation in the composition after 2 weeks of storage at 54°C is 4%. In some embodiments, the phase separation in the composition after 8 weeks of storage at room temperature is 25%. In some embodiments, the phase separation in the composition after 8 weeks of storage at room temperature is 4%. In some embodiments, the phase separation in the composition after 8 weeks of storage at 40°C is 8%. In some embodiments, the phase separation in the composition after 8 weeks of storage at 40°C is 4%. In some embodiments, there is no phase separation in the composition after 1 week of storage at 0°C. In some embodiments, there is no phase separation in the composition after 1 week of storage at -10°C. In some embodiments, the phase separation in the composition after 1 week of storage at -10°C is 2%.

In some embodiments, after 2 weeks of storage at room temperature, there is less than 2 ml, less than 1 ml, or less than 0.5 ml of sediment per 250 ml of the composition. In some embodiments, after 2 weeks of storage at 54°C, there is less than 2 ml, less than 1 ml, or less than 0.5 ml of sediment per 250 ml of the composition. In some embodiments, after 8 weeks of storage at room temperature, there is less than 2 ml, less than 1 ml, or less than 0.5 ml of sediment per 250 ml of the composition. In some embodiments, after 8 weeks of storage at 40°C, there is less than 2 ml, less than 1 ml, or less than 0.5 ml of sediment per 250 ml of the composition.

In some embodiments, after 2 weeks of storage at room temperature, there is 0.3 ml of sediment per 250 ml of the composition. In some embodiments, after 2 weeks of storage at room temperature, there is 0.15 ml of sediment per 250 ml of the composition. In some embodiments, after 2 weeks of storage at 54°C, there is 0.3 ml of sediment per 250 ml of the composition. In some embodiments, after 2 weeks of storage at 54°C, there is 0.15 ml of sediment per 250 ml of the composition. In some embodiments, after 8 weeks of storage at room temperature, there is 0.3 ml of sediment per 250 ml of the composition. In some embodiments, after 8 weeks of storage at room temperature, there is 0.15 ml of sediment per 250 ml of the composition. In some embodiments, after 8 weeks of storage at 40°C, there is 0.3 ml of sediment per 250 ml of the composition. In some embodiments, after 8 weeks of storage at 40°C, there is 0.2 ml of sediment per 250 ml of the composition.

In some embodiments, the composition is stored in a sealed container.

In some embodiments, the composition is more effective in treating a plant or locus from a fungal infection compared to using the same amount of each fungicide in a form other than the compositions described herein.

In some embodiments, the composition is more effective in treating a plant or locus from a fungal infection compared to using the same amount of each fungicide in the form of a tank mix.

In some embodiments, the composition is more effective in treating a plant or locus from a fungal infection compared to using the same amount of each fungicide separately.

The compositions described herein can be used in combination with one or more other pesticides to control a broader range of unwanted pests. When used in combination with other pesticides, the composition described herein can be formulated with the other pesticide(s), tank-mixed with the other pesticide(s), or applied sequentially with the other pesticide(s). Additionally, the composition described herein can optionally be combined or mixed with other pesticide compositions. The pesticide mixture can be used to control pests in or out of the crop environment.

Combinations and mixtures

The present invention also provides a combination comprising:

(i) an amount of at least one dithiocarbamate fungicide,

(ii) an amount of at least one triazole fungicide, and

(iii) an amount of at least one pyrazole carboxamide fungicide.

The present invention also provides a combination comprising:

(i) an amount of at least one dithiocarbamate fungicide,

(ii) an amount of at least one triazole fungicide, and

(iii) an amount of at least one pyrazole carboxamide fungicide,

Moreover, the specified combination is more effective for treating a plant or locus from a fungal infection than when using each fungicide in the same amount separately.

The present invention also provides a combination comprising:

(i) an amount of at least one dithiocarbamate fungicide,

(ii) an amount of at least one triazole fungicide, and

(iii) an amount of at least one pyrazole carboxamide fungicide,

wherein the specified amount of dithiocarbamate fungicide, the specified amount of triazole fungicide and the specified amount of pyrazole-carboxamide fungicide when applied together are more effective in treating a plant or locus from a fungal infection than when each fungicide is applied in the same amount separately.

The present invention also provides a combination comprising:

(i) an amount of at least one dithiocarbamate fungicide,

(ii) an amount of at least one triazole fungicide, and

(iii) an amount of at least one pyrazole carboxamide fungicide,

wherein the specified amount of dithiocarbamate fungicide is less than the fungicidally effective amount of dithiocarbamate fungicide when using the dithiocarbamate fungicide alone,

wherein the specified amount of triazole fungicide is less than the fungicidally effective amount of the triazole fungicide when the triazole fungicide is used alone, and/or

wherein the specified amount of pyrazole-carboxamide fungicide is less than the fungicidally effective amount of pyrazole-carboxamide fungicide when using the pyrazole-carboxamide fungicide separately.

In some embodiments, said combination comprises at least one agrochemically acceptable non-aqueous liquid carrier.

In some embodiments, the combination is a mixture.

In some embodiments, the combination is synergistic.

In some embodiments, said mixture is synergistic.

The combination or mixture may further comprise one or more of the components described above herein in the context of the fungicidal liquid oil composition.

The present invention also provides a fungicidal composition comprising any of the combinations or mixtures disclosed herein.

In some embodiments, said fungicidal composition is a fungicidal liquid oil composition.

In some embodiments, said fungicidal composition is a fungicidal liquid oil composition.

In some embodiments, the combination is diluted with water. In some embodiments, the mixture is diluted with water. In some embodiments, the fungicidal composition is diluted with water.

Methods of application

The present invention also provides a method of treating a plant or locus for a fungal infection, comprising applying an effective amount of any of the combinations, mixtures or compositions described herein to the plant or locus, thereby treating the plant or locus for the fungal infection.

The present invention also provides a method for treating a plant or locus from a fungal infection, comprising applying to the plant or locus:

(i) an amount of at least one dithiocarbamate fungicide,

(ii) an amount of at least one triazole fungicide, and

(iii) an amount of at least one pyrazole carboxamide fungicide,

thereby ensuring the treatment of the plant or locus from fungal infection.

The present invention also provides a method for treating a plant or locus from a fungal infection, comprising applying to the plant or locus:

(i) an amount of at least one dithiocarbamate fungicide,

(ii) an amount of at least one triazole fungicide, and

(iii) an amount of at least one pyrazole carboxamide fungicide

thereby ensuring the treatment of a plant or locus from a fungal infection, wherein the specified amount of a dithiocarbamate fungicide, the specified amount of a triazole fungicide and the specified amount of a pyrazole-carboxamide fungicide when used together are more effective in treating a plant or locus from a fungal infection than when each fungicide is used separately in the same amount.

The present invention also provides a method for treating a plant or locus from a fungal infection, comprising applying to the plant or locus:

(i) an amount of at least one dithiocarbamate fungicide,

(ii) an amount of at least one triazole fungicide, and

(iii) an amount of at least one pyrazole carboxamide fungicide

thereby ensuring the treatment of a plant or locus against a fungal infection, wherein the applied amount of dithiocarbamate fungicide is less than the fungicidally effective amount of the dithiocarbamate fungicide when using the dithiocarbamate fungicide alone,

wherein the applied amount of the triazole fungicide is less than the fungicidally effective amount of the triazole fungicide when the triazole fungicide is used alone, and/or

wherein the applied amount of pyrazole-carboxamide fungicide is less than the fungicidally effective amount of pyrazole-carboxamide fungicide when using the pyrazole-carboxamide fungicide alone.

In some embodiments, the method is effective in controlling a fungal infection of a plant or locus.

In some embodiments, controlling a fungal infection includes controlling a fungal disease that infects a plant or a locus. In some embodiments, controlling a fungal infection includes controlling a plant or soil disease caused by phytopathogenic fungi. In some embodiments, controlling a fungal infection includes controlling a fungal infestation of a plant or a locus. In some embodiments, controlling a fungal infection includes reducing a fungal infection in a plant or a locus. In some embodiments, controlling a fungal infection includes treating a plant or soil disease caused by phytopathogenic fungi.

In some embodiments, the method is effective in protecting a plant or locus from a fungal infection.

In some embodiments, protecting a plant or locus from a fungal infection includes protecting the plant or locus from infection by a fungus. In some embodiments, protecting a plant or locus from a fungal infection includes protecting the plant or locus from a fungal disease. In some embodiments, protecting a plant or locus from a fungal infection includes preventing a fungal infection in a plant or locus.

In some embodiments, the method comprises applying an effective amount of any of the combinations, mixtures, or compositions disclosed herein to a plant propagation material. In some embodiments, the method comprises applying an effective amount of any of the combinations, mixtures, or compositions disclosed herein to a seed and/or plant seedling.

In some embodiments, the method includes using any of the combinations, mixtures, or compositions disclosed herein as a protectant. In some embodiments, the method includes therapeutic use of any of the combinations, mixtures, or compositions disclosed herein.

In some embodiments, the fungal infestation is controlled by preventing the fungal infestation of the plant, seed, or seedling. In some embodiments, the fungal infestation is controlled by treating the fungal infestation of the plant, seed, or seedling.

In some embodiments, fungicides are applied together.

In some embodiments, fungicides are applied simultaneously.

In some embodiments, fungicides are applied sequentially.

In some embodiments, fungicides are applied separately.

In some embodiments, fungicides are applied together.

In some embodiments, the fungicides are applied together as a tank mix.

In some embodiments, the fungicides are applied in the form of any of the combinations, mixtures, or compositions disclosed herein.

In some embodiments, an amount of a dithiocarbamate fungicide, an amount of a triazole fungicide, and an amount of a pyrazole carboxamide fungicide when applied together in the form of any of the compositions described herein is more effective in treating a plant or locus from a fungal infection than when each fungicide is applied in the same amount in a form other than the compositions described herein.

In some embodiments, an amount of a dithiocarbamate fungicide, an amount of a triazole fungicide, and an amount of a pyrazole carboxamide fungicide when applied together in the form of any of the compositions described herein is more effective in treating a plant or locus from a fungal infection than when each fungicide is applied in the same amount in the form of a tank mix.

In some embodiments, an amount of a dithiocarbamate fungicide, an amount of a triazole fungicide, and an amount of a pyrazole carboxamide fungicide when used together in the form of any of the compositions described herein is more effective in treating a plant or locus from a fungal infection than when each fungicide is used in the same amount separately.

In some embodiments, fungicides are applied to a part of a plant, an area near a plant, soil in contact with a plant, soil near a plant, any surface near a plant, any surface in contact with a plant, a seed, and/or equipment used in agriculture. In some embodiments, fungicides are applied to a locus of a plant, a locus near a plant, a locus of a fungus, or a locus near a fungus. In some embodiments, fungicides are applied to the soil in which the plant is grown. In some embodiments, fungicides are applied to the soil in which the plant is to grow.

In some embodiments, fungicides are applied at the time of planting.

In some embodiments, fungicides are applied 1-60 days after planting.

In some embodiments, fungicides are applied 1-9 months after planting.

In some embodiments, fungicides are applied once during the growing season.

In some embodiments, fungicides are applied at least once during the growing season.

In some embodiments, fungicides are applied two or more times during the growing season.

In some embodiments, fungicides are applied three times during the growing season.

In some embodiments, the interval between applications is 15 days.

In some embodiments, fungicides are applied by soil application. In some embodiments, fungicides are applied by foliar application.

The combinations, mixtures and compositions described herein are suitable for the control of unwanted pests such as phytopathogenic fungi.

Effective application amounts of the fungicide composition cannot be specified for a general case, since they vary depending on various conditions, such as the type of pesticide, the target pest, weather conditions, the nature of the soil, and the type of agricultural crop. In some embodiments, the fungicide composition is applied in an amount of from about 1 to about 5 L/ha. In some embodiments, the fungicide composition is applied in an amount of from about 2 to about 3 L/ha. In some embodiments, the fungicide composition is applied in an amount of about 2 L/ha. In some embodiments, the fungicide composition is applied in an amount of about 3 L/ha. In some embodiments, the fungicide composition is applied in an amount of about 2.25 L/ha. In some embodiments, the fungicide composition is applied in an amount of about 2.5 L/ha. In some embodiments, the fungicide composition is applied in an amount of about 2.75 L/ha.

In some embodiments, the pyrazole carboxamide fungicide is applied in an amount of about 10 g a.i./ha to about 100 g a.i./ha. In some embodiments, the pyrazole carboxamide fungicide is applied in an amount of about 30 g a.i./ha to about 80 g a.i./ha. In some embodiments, the pyrazole carboxamide fungicide is applied in an amount of about 50 g a.i./ha to about 65 g a.i./ha. In some embodiments, the pyrazole carboxamide fungicide is applied in an amount of about 51 g a.i./ha. In some embodiments, the pyrazole carboxamide fungicide is applied in an amount of about 56 g a.i./ha. In some embodiments, the pyrazole carboxamide fungicide is applied in an amount of about 62 g a.i./ha.

In some embodiments, the triazole fungicide is applied in an amount of from about 10 g a.i./ha to about 200 g a.i./ha. In some embodiments, the triazole fungicide is applied in an amount of from about 70 g a.i./ha to about 130 g a.i./ha. In some embodiments, the triazole fungicide is applied in an amount of from about 50 g a.i./ha to about 150 g a.i./ha. In some embodiments, the triazole fungicide is applied in an amount of from about 70 g a.i./ha to about 90 g a.i./ha. In some embodiments, the triazole fungicide is applied in an amount of from about 100 g a.i./ha to about 130 g a.i./ha. In some embodiments, the triazole fungicide is applied in an amount of about 71 g a.i./ha. In some embodiments, the triazole fungicide is applied at about 79 g a.i./ha. In some embodiments, the triazole fungicide is applied at about 87 g a.i./ha. In some embodiments, the triazole fungicide is applied at about 101 g a.i./ha. In some embodiments, the triazole fungicide is applied at about 111 g a.i./ha. In some embodiments, the triazole fungicide is applied at about 122 g a.i./ha.

In some embodiments, the dithiocarbamate fungicide is applied in an amount of from about 100 g a.i./ha to about 2000 g a.i./ha. In some embodiments, the dithiocarbamate fungicide is applied in an amount of from about 500 g a.i./ha to about 1500 g a.i./ha. In some embodiments, the dithiocarbamate fungicide is applied in an amount of from about 900 g a.i./ha to about 1200 g a.i./ha. In some embodiments, the dithiocarbamate fungicide is applied in an amount of about 990 g a.i./ha. In some embodiments, the dithiocarbamate fungicide is applied in an amount of about 1100 g a.i./ha. In some embodiments, the dithiocarbamate fungicide is applied in an amount of about 1210 g a.i./ha.

In some embodiments, the dithiocarbamate fungicide is mancozeb.

In some embodiments, the triazole fungicide is prothioconazole. In some embodiments, the triazole fungicide is tebuconazole.

In some embodiments, the pyrazole carboxamide fungicide is fluxapyroxad.

The application methods include adding the fungicide composition to a carrier such as water and using the resulting solution containing the fungicide composition for spraying to control phytopathogenic fungi in a plant or plant propagation material in or outside the agricultural environment. By diluting the fungicide composition with water, a suspension emulsion can be obtained.

In some embodiments, the combination is diluted with water before application. In some embodiments, the mixture is diluted with water before application. In some embodiments, the composition is diluted with water before application.

In some embodiments, the fungicidal composition can be diluted with a carrier, such as water, in an amount of from about 1 to 100 L of fungicidal composition per 1000 L of water. In some embodiments, the composition can be diluted with a carrier, such as water, in an amount of from about 1 to 30 L of fungicidal composition per 1000 L of water. In some embodiments, the composition can be diluted with a carrier, such as water, in an amount of from about 5 to 15 L of fungicidal composition per 1000 L of water.

The methods of the present invention can be applied to any agricultural crops, including but not limited to soybeans, grains, wheat, corn, papaya, melon, cocoa and coffee. In some embodiments, the plant is a soybean plant. In some embodiments, the soybean plant is a BONUS variety plant. In some embodiments, the soybean plant is a M 5917 IPRO variety plant.

In some embodiments, the phytopathogenic fungi are fungi of one or more classes, including, but not limited to, soybean rust (Phakopsora pachyrhizi), target spot (Corynespora cassiicola), late-season diseases (Septoria glycines and Cercospora kikuchii), northern leaf spot (Exserohilum turcicum), yellow spot of wheat (Dreshslera tritici-repentis), phaeosphaeria leaf spot (Phaeosphaeria maydis), anthracnose (Colletotrichum gloeosporioides), black head blight, corn smut (Ustilago maydis), loose smut of corn (Sphacelotheca reiliana), false smut (Ustilaginoidea virens), and wheat stem smut. (Usrocystis agropyri), loose smut of wheat/barley (Ustilago nuda), loose smut of barley (Ustilago segetum var. hordei), and loose smut of oats (Ustilago avenae). In some embodiments, the phytopathogenic fungi are soybean rust (Phakopsora pachyrhizi).

The combinations, mixtures and compositions described herein can be mixed with water and/or fertilizers and applied to the target locus by any means, such as aircraft sprayers, knapsack sprayers, cattle dipping vats, agricultural equipment used for ground spraying (e.g., boom sprayers, hand sprayers) and the like. The target locus can be soil, plants and the like.

The combinations, mixtures and compositions described herein can be applied to soybeans from the vegetative growth stage V2 (second trifoliate - two sets of expanded trifoliate leaves) to the reproductive growth stage R8 (full maturity - 95% of pods have reached their full maturity colour).

The combinations, mixtures and compositions may include additional crop protection agents, such as insecticides, herbicides, fungicides, bactericides, nematicides, molluscicides, growth regulators, biological agents, fertilizers or mixtures thereof. When used in combination with additional crop protection agents, the composition may be formulated together with these additional agents, prepared as a tank mixture together with the said additional agents or applied sequentially with the said additional agents.

The present invention also provides the use of any of the combinations, mixtures or compositions described herein for treating a plant or locus for a fungal infection.

The present invention also provides any of the combinations, mixtures and compositions described herein for use in treating a plant or locus for a fungal infection.

The present invention also provides a package comprising any of the combinations, mixtures or compositions disclosed herein.

Methods of obtaining

The present invention also provides a method for producing any of the combinations, mixtures or compositions disclosed herein from the individual components.

The present invention also provides a method for producing any of the fungicidal liquid oil compositions described herein, comprising the steps of:

(i) dissolving at least one triazole fungicide and at least one pyrazole carboxamide fungicide in at least one non-aqueous liquid carrier to form a solution;

(ii) adding to the solution obtained in step (i) at least one auxiliary substance, surfactant, antifoam and/or stabilizer to obtain a mixture; and

(iii) adding to the mixture obtained in step (ii) at least one dithiocarbamate fungicide, thereby obtaining a fungicidal liquid oil composition.

In some embodiments, step (i) is carried out with stirring. In some embodiments, step (i) is carried out with stirring at a speed of 300-400 rpm.

In some embodiments, step (i) comprises heating the triazole fungicide, the pyrazole carboxamide fungicide, and the non-aqueous liquid carrier to form a solution. In some embodiments, step (i) comprises heating the triazole fungicide, the pyrazole carboxamide fungicide, and the non-aqueous liquid carrier at 70°C to form a solution.

In some embodiments, step (ii) is carried out with stirring.

In some embodiments, step (ii) is carried out without heating the mixture.

In some embodiments, the method comprises cooling the mixture obtained in step (ii) to a temperature of <35°C before performing step (iii).

In some embodiments, step (iii) is carried out with stirring. In some embodiments, step (iii) is carried out with stirring at a speed of 1000 to 1500 rpm.

In some embodiments, the method further comprises the step of adjusting the viscosity of the composition by adding silica.

In some embodiments, the method further comprises filtering the fungicidal liquid oil composition obtained in step (iii) prior to packaging.

In some embodiments, the fungicidal liquid oil composition obtained in step (iii) is a homogeneous solution.

It is intended that each of the embodiments disclosed herein is applicable to each of the other embodiments disclosed. Thus, the scope of the present invention includes all combinations of the various elements described herein. Furthermore, elements provided in the embodiments of the composition can be used in the embodiments of the combination, mixture (including synergistic mixture), packaging, method and use described herein, and vice versa.

The present invention is illustrated and described in more detail with reference to the following non-limiting examples. The following examples illustrate the implementation of the present invention in some of its embodiments, but should not be considered as limiting the scope of the present invention. Other embodiments will be obvious to a person skilled in the art after reading the description of the invention and the examples. It is intended that the description of the invention, including the examples, is considered only as illustrative, without limiting the scope and spirit of the present invention.

Experimental examples

Example 1: Composition MD mancozeb 440+tebuconazole 44.5+fluxapyroxad 22.5

The composition according to Table 1 was obtained in accordance with the following procedure:

Solvesso™ 200, Hallcomid® M-10, 2-ethylhexanol, fluxapyroxad and tebuconazole were added to the container with stirring (300-400 rpm) and heated at 70°C until the active ingredients were completely solubilized. The heat was then turned off and Atlas Symperonic™ PE/F 68FL, Tween™ 24, defoamer, Rhodacal® 60/BE, tristyrylphenol 16 EO, methyl soyate and zinc oxide were added with stirring. The container contents were cooled until the temperature reached <35°C. The stirring speed was increased to 1000-1500 rpm using a Coles stirrer and mancozeb was added. The viscosity was adjusted with silica. The contents of the container were cooled to room temperature and filtered (100 mesh sieve) followed by packaging.

Example 2: Composition MD mancozeb 440+prothioconazole 31.5+fluxapyroxad 22.5

The composition according to Table 5 was obtained in accordance with the following procedure:

Solvesso™ 200, decanamide, fluxapyroxad, and prothioconazole were added to the container with stirring and heated at 70°C until the active ingredients were completely solubilized. The heat was then turned off and Atlas™ G-5002L-LQ-(CQ), tristyrylphenol 16 EO, Tween™ 24, defoamer, Rhodacal® 60/BE, methyl soyate, and zinc oxide were added with stirring. The container contents were cooled until the temperature reached <35°C. The stirring speed was increased to 1000-1500 rpm using a Coles stirrer and mancozeb was added. The viscosity was adjusted with silica. The container contents were cooled to room temperature and filtered (100 mesh) before packaging.

Example 3: Effectiveness Study

The objective of this experiment was to evaluate the efficacy of the premixed formulations of Examples 1 and 2 compared to tank mixes of the same agents and the three-component premixed formulation of tebuconazole, picoxystrobin and mancozeb described in International Application Publication WO 2017/203527 A1.

The premixed compositions and tank mixes used are summarized in Table 7 below.

Each premix or tank mix was sprayed at the indicated rate three times at 15 day intervals starting from the onset of flowering onto soybean plants infested with Phakopsora pachyrhizi.

Fig. 1 shows the results of the above-mentioned study conducted in Uberlandia (U)/Brazil using soybean variety BONUS. Fig. 2 shows the results of the above-mentioned study conducted in Ponta Grossa (PR)/Brazil using soybean variety M 5917 IPRO. Fig. 3 shows the results of the above-mentioned study conducted in Rio Verde (GO)/Brazil using soybean variety BONUS.

Figures 1-3 show that the premixed formulation of fluxapyroxad, prothioconazole and mancozeb (Table 4) was more effective in controlling Phakopsora pachyrhizi than tank mixes of the same three active ingredients when applied at the same rate.

Figures 1 and 3 show that the premixed formulation of fluxapyroxad, tebuconazole and mancozeb (Table 1) was more effective in controlling Phakopsora pachyrhizi than tank mixes of the same three active ingredients when applied at the same rate.

Figures 1-3 show that the premixed formulation of fluxapyroxad, prothioconazole and mancozeb (Table 4) was more effective in controlling Phakopsora pachyrhizi than the premixed formulation of tebuconazole, picoxystrobin and mancozeb (commercial standard).

Figures 1-3 show that the premixed formulation of fluxapyroxad, tebuconazole and mancozeb (Table 1) was more effective in controlling Phakopsora pachyrhizi than the premixed formulation of tebuconazole, picoxystrobin and mancozeb (commercial standard).

Claims (28)

1. Fungicidal liquid oil dispersion composition containing the following ingredients: (i) the dithiocarbamate fungicide mancozeb suspended in a solution of fungicides in an agrochemically acceptable non-aqueous liquid carrier, and (ii) a stabilizer zinc oxide as an ingredient for improving the stability of said composition, wherein said fungicide solution comprises a triazole fungicide tebuconazole or prothioconazole and a pyrazole-carboxamide fungicide fluxapyroxad, dissolved in said non-aqueous liquid carrier, and said composition is adapted for compatibility with glyphosate formulations without increasing the viscosity of said liquid oil composition. 2. A fungicidal liquid oil dispersion composition according to claim 1, characterized in that it additionally contains 2-ethylhexanol and said dithiocarbamate fungicide is suspended in a solution of fungicides in an agrochemically acceptable non-aqueous liquid carrier and 2-ethylhexanol. 3. A fungicidal liquid oil dispersion composition according to paragraphs 1 or 2, characterized in that it is stable when stored in a sealed container. 4. A fungicidal liquid oil dispersion composition according to any one of paragraphs 1-3, characterized in that the viscosity of said composition is maintained within the range of 500-2500 cP after storage in a sealed container for periods of time under conditions selected from: (i) two weeks at 54°C; (ii) eight weeks at 40°C; (iii) three months at room temperature; (iv) six months at room temperature; and (v) two weeks at 0°C. 5. A fungicidal liquid oil dispersion composition according to claim 1, characterized in that said dithiocarbamate fungicide and zinc oxide are suspended in a solution of fungicides dissolved in an agrochemically acceptable non-aqueous liquid carrier. 6. A fungicidal liquid oil dispersion composition according to claim 2, characterized in that said dithiocarbamate fungicide and zinc oxide are suspended in a solution of fungicides dissolved in an agrochemically acceptable non-aqueous liquid carrier and 2-ethylhexanol. 7. A fungicidal liquid oil dispersion composition according to any one of claims 1-6, characterized in that said non-aqueous liquid carrier is selected from the group consisting of aromatic hydrocarbons, alkyl amides, alkyl esters of vegetable oils, alcohols, any or all combinations of two or more carriers. 8. A fungicidal liquid oil dispersion composition according to any one of claims 1 to 6, characterized in that said non-aqueous liquid carrier contains an aromatic hydrocarbon selected from the group consisting of naphthalene, solvent naphtha aromatic heavy 200, solvent naphtha aromatic 150, solvent naphtha aromatic 100, aromatic hydrocarbon CAS 64742-94-5, aromatic hydrocarbon CAS 64742-95-6 and any and all combinations thereof. 9. A fungicidal liquid oil dispersion composition according to any one of paragraphs 1-8, characterized in that the content of zinc oxide in relation to the total content of the components is selected from the following: (a) 0.1-10 wt.%, (b) 0.1-5 wt.%, (in) 1-2 wt.%, (g) 1.5 wt.%, (d) 1.57 wt.%, (e) 1.6 wt.%, and (f) 1.61 wt.%, wherein each numerical value or range includes ±10% of the stated values in the range. 10. A fungicidal liquid oil dispersion composition according to any one of paragraphs. 1-9, characterized in that (i) the retention of the composition is 2% or less when tested by wet sieve analysis in accordance with CIPAC MT 185 using a 75 micron sieve after storage for 2 weeks at 54°C; and/or (ii) the density of the composition is 1-1.5 g/ ^cm3 when the density analysis is carried out in accordance with CIPAC MT 3.3.2 at a temperature of 20°C after storage for 6 months at room temperature.