Oily liquid fungicide formulations

Abstract

An antifungal oily liquid formulation comprising: a) at least one dithiocarbamate fungicide; b) at least one co-fungicide selected from triazole fungicides and methoxyacrylate fungicides; c) an agriculturally chemically acceptable non-aqueous liquid carrier; wherein the dithiocarbamate fungicide is suspended in the liquid carrier; wherein the triazole fungicide and the methoxyacrylate fungicide are dissolved in the liquid carrier; and wherein the liquid carrier optionally comprises an adjuvant.

Description

[0001] This application is a divisional application of Chinese patent application filed on May 24, 2017, with Chinese patent application number 201780031775.7 and the invention title "Oil-like Liquid Antifungal Preparation", and claims priority to US 62 / 340,610 and US62 / 456,175. Technical Field

[0002] This invention relates to insecticidal compositions for use in agricultural pest control. In particular, the invention provides a stable fungicidal oily liquid formulation comprising at least one dithiocarbamate fungicide suspended in a non-aqueous liquid carrier; at least one triazole fungicide and at least one methoxyacrylate fungicide dissolved in a non-aqueous liquid carrier. Background Technology

[0003] Dithiocarbamates are generally known to possess potent antifungal activity. However, a particular problem with these active ingredients is their relatively high instability. This is due to the low stability of the CS bond and the thiocarbamate functional groups, especially at low pH values ​​and in the presence of nucleophiles.

[0004] These active ingredients can be formulated into solid dosage forms to improve their stability. Known solid powder formulations include, for example, Manzate 75WG (DuPont's product), Polyram DF (Nufarm's product), and Vondozeb 75WG (Agrosimex's product). However, solid dosage forms, such as water-dispersible granules, have known disadvantages. Some of these disadvantages may include poor dispersibility in water, difficulty in dosage measurement, compatibility with other components in a mixing tank, and high cost of manufacturing such formulations.

[0005] In many cases, liquid products are superior to the aforementioned solid dosage forms. Liquid products have the advantage that they exhibit good miscibility with oil-based tank-mixed additives, even under ULV (ultra-low volume) conditions, in water / oil formulations or oil-phase formulations (see EP0435760 and EP0697171).

[0006] Agricultural chemical oil dispersions (ODs) are stable suspensions of agricultural chemical active ingredients (such as pesticides and crop protection chemicals) in non-aqueous fluids, which may contain other dissolved active ingredients. Oil dispersions are particularly used for formulating oil-insoluble solid active ingredients.

[0007] Oil dispersion formulations are concentrates that are diluted with water before use to produce an aqueous composition for crop protection. To enable dispersion in water, these formulations contain emulsifiers, dispersants, and other formulation components such as thickeners, defoamers, and solid carriers. Oil dispersions are typically chosen if the active ingredient is water-sensitive or if oil is required as an adjuvant to improve the biological properties of the pesticide. Oil dispersions are generally anhydrous. This is to prevent degradation of the active ingredient and to prevent phase separation of the formulation.

[0008] Oil-dispersed formulations offer certain advantages to farmers. Active ingredients that are unstable in water can now often be formulated into solid suspensions. Oil-based adjuvants can also be combined with these types of formulations to enhance efficacy. Furthermore, suspension of the active ingredient in a non-aqueous liquid carrier may produce formulations with higher active ingredient strength than other possible methods. This is because the active ingredient has a solubility limit to the amount that can be added to the formulation.

[0009] A drawback of existing oil dispersion formulations is that they often exhibit phase separation after storage. Therefore, even storage at ambient temperatures can lead to aggregation, clumping, or significant sedimentation of the suspended phase. Depending on the density of the active ingredient and the non-aqueous liquid carrier used, the active ingredient particles may also separate from the non-aqueous liquid carrier. In some cases, these effects are irreversible.

[0010] A common approach to solving this problem is to add an antisettling agent to the oil dispersion formulation. Antisettling agents may include thickeners, which increase the viscosity of the system and act as suspending agents by reducing the settling rate of particles.

[0011] As described in WO2009 / 004281, typical thickeners for physically stable oil dispersions include organoclays that are organophilic and therefore compatible with non-aqueous formulations, such as smectite, lithium montmorillonite, or montmorillonite. The uses of these thickeners are further described, for example, in EP 789999, GB 2067407, EP149459, and GB 2008949.

[0012] Other known thickeners are hydrophobically modified silica and synthetic polymers, described, for example, in WO2008135854 and US 5,599,768. However, these thickeners are difficult to dissolve and homogenize, and it is necessary to avoid the formation of gels or clumps and to continuously and carefully monitor the process.

[0013] WO2012 / 167322 relates to an agricultural oil-based suspension formulation comprising an active ingredient suspended in oil in the form of fine particles; and at least one surfactant selected from polyalkylene glycol-fatty acid condensates or polyalkylene glycol ether fatty acid condensates.

[0014] WO2012 / 167321 relates to an agricultural oil-based suspension formulation comprising an active ingredient suspended in oil in the form of fine particles; and at least one unsaturated rubber-type copolymer or mixture thereof, wherein the rubber-type copolymer contains at least styrene as a residue.

[0015] WO2012 / 080208 relates to a method for preparing an agricultural chemical oil dispersion comprising a thickener, said thickener being an amide obtained by reacting polyhydroxystearic acid with diethylenetriamine and / or triethylenetetramine.

[0016] WO2014 / 169363 relates to novel oil-dispersible agrochemical formulations comprising at least one active ingredient suspended in an oil phase, a dispersant, a clay-based rheology modifier, a cellulose-derived rheology modifier, and an emulsifier, and optionally at least one other active ingredient dissolved in the oil phase.

[0017] CN 104247712 relates to a dispersible oil suspension composed of azoxystrobin, mancozeb, emulsifier, dispersant, wetting agent, thickener, antifreeze, stabilizer and dispersion medium.

[0018] Over the past decade, the demand for novel, high-performance agrochemical compositions has been increasing, while the number of chemicals approved by regulatory agencies for use in agrochemical compositions has been decreasing due to stricter standards for the toxicological and ecological properties of these substances. Therefore, there is a need in the art for a fungicidal composition that allows for reduced application rates of a single active ingredient while maintaining increased efficacy. Furthermore, the combination of multi-site fungicides (such as dithiocarbamate fungicides) with two systemic fungicides (such as triazole fungicides and methoxyacrylate fungicides) in a stable formulation provides a solution that reduces disease resistance, lowers the application rate of the active ingredient, increases yield, and reduces costs.

[0019] Based on the above discussion, there is a need in the art for physically stable oily liquid formulations comprising a combination of a multi-site fungicide (e.g., a dithiocarbamate fungicide) and two systemic fungicides. Summary of the Invention

[0020] According to one aspect, the present invention provides a fungicidal oily liquid formulation comprising: a) at least one dithiocarbamate fungicide; b) at least one co-fungicide selected from triazole fungicides and methoxyacrylate fungicides; c) an agriculturally chemically acceptable non-aqueous liquid carrier; wherein the dithiocarbamate fungicide is suspended in the liquid carrier; wherein the co-fungicide is dissolved in the liquid carrier; and wherein the liquid carrier optionally comprises an adjuvant.

[0021] According to another aspect, the present invention provides a fungicidal oily liquid formulation comprising: a) at least one dithiocarbamate fungicide; b) at least one triazole fungicide; c) at least one methoxyacrylate fungicide; d) an agriculturally chemically acceptable non-aqueous liquid carrier; wherein the dithiocarbamate fungicide is suspended in the liquid carrier; wherein the triazole fungicide and the methoxyacrylate fungicide are dissolved in the liquid carrier; wherein the liquid carrier optionally comprises adjuvants.

[0022] According to another aspect, the present invention provides a fungicidal oily liquid formulation comprising: a) 20-60 wt% of at least one dithiocarbamate fungicide; b) 1-15 wt% of a combination of a triazole fungicide and a methoxyacrylate fungicide; c) 10-50 wt% of a non-aqueous liquid carrier; d) 1-40 wt% of at least one surfactant; wherein the dithiocarbamate fungicide is suspended in the liquid carrier; wherein the triazole fungicide and the methoxyacrylate fungicide are dissolved in the liquid carrier; wherein the liquid carrier optionally comprises an adjuvant.

[0023] According to another aspect, the present invention provides an antifungal suspension formulation comprising: a) the above-mentioned antifungal oily liquid formulation; and b) water.

[0024] According to another aspect, the present invention provides an antifungal oily liquid preparation for the control or prevention of pests on plants or their propagation material. Detailed Implementation

[0025] definition

[0026] 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 pertains. For clarity, the following definitions are provided.

[0027] As used herein, the term "pesticide" broadly refers to any agent that can be used to control and / or kill pests. This term should be understood to include, but is not limited to, fungicides, insecticides, nematicides, herbicides, acaricides, parasiteicides, or other control agents. For chemical categories and applications, and specific compounds in each category, see the "Pesticide Handbook, 13th Edition" (Crop Protection Council, Hampshire, UK, 2003) and the "Electronic Pesticide Handbook, 3rd Edition" (Crop Protection Council, Hampshire, UK, 2003-04), the contents of which are incorporated herein by reference in their entirety.

[0028] As used herein, the terms "plant" or "crop" include reference to the whole plant, plant organs (e.g., leaves, stems, twigs, roots, trunks, branches, shoots, fruits, etc.), plant cells, or plant seeds. The term also includes plant crops, such as fruits. In another embodiment, the term "plant" may include its propagation material, which may include all reproductive parts of the plant that can be used for plant propagation, such as seeds and viable plant material (e.g., cuttings and tubers). This includes seeds, tubers, spores, bulbs, seed heads, rhizomes, sprouts, basal buds, stolons, bud buds, and other parts of the plant (including seedlings and young plants) transplanted after germination or emergence from soil.

[0029] As used in this article, the term "site" includes not only areas where weeds may have grown, but also areas where weeds have not yet appeared, as well as cultivated areas.

[0030] As used herein, the terms “mixture” or “combination” refer to, but are not limited to, any combination of physical forms, such as mixtures, solutions, alloys, etc.

[0031] As used herein, the term “effective amount” refers to the amount of a compound that is sufficient to achieve a good level of control when ingested, exposed to, or sensed.

[0032] As used in this article, the phrase “enhancing crop plants” means improving one or more of the following: plant quality, vigor, nutrient uptake, root strength, and / or tolerance to stress factors, any of which can lead to increased yield.

[0033] As used in this article, the phrase “enhanced root system” means to improve the root system in terms of quality or quantity. Enhanced root system includes, but is not limited to: improved visual appearance and composition of the root system (i.e., improved color, density, uniformity, and visual appearance), enhanced root growth, more developed root system, stronger and healthier roots, improved plant density, and increased root weight.

[0034] As used in this article, the phrase “improved nutrient intake” or “increased nutrient intake” refers to improving the intake of one or more nutrients, either in quality or quantity. These nutrients include, but are not limited to, nitrogen, phosphorus, potassium, calcium, copper, zinc, sulfur, and magnesium.

[0035] As used herein, the phrase “improved plant quality” refers to improvements in one or more traits, either qualitatively or quantitatively. These traits include, but are not limited to: improved visual appearance and plant composition (i.e., improved color, density, uniformity, compactness), reduced ethylene (reduced production and / or inhibited absorption), improved visual appearance and composition of harvested products (i.e., seeds, fruits, leaves, vegetables), improved carbohydrate content (i.e., increased sugar and / or starch content, improved sugar-acid ratio, reduced reducing sugars, increased rate of sugar formation), improved protein content, improved oil content and composition, improved nutritional value, reduced anti-nutritional compounds, increased nutrient uptake, stronger and healthier roots, improved sensory characteristics (i.e., improved taste), improved consumer health benefits (i.e., increased vitamin and antioxidant content), improved post-harvest characteristics (i.e., extended shelf life and / or storage stability, easier processing, easier extraction of compounds), and / or improved seed quality (i.e., for the next season).

[0036] As used herein, the phrase “improved plant vigor” refers to improvements in one or more traits, either qualitatively or quantitatively. These traits include, but are not limited to: earlier and / or improved germination, improved emergence, ability to use fewer seeds, enhanced root growth, more developed root system, stronger and healthier roots, enhanced shoot growth, enhanced tillering, stronger tillering, more efficient tillering, increased or improved plant density, reduced lodging, improved plant height, increased plant weight (fresh or dry), larger leaves, greener leaf color, increased pigment content, enhanced photosynthesis, earlier flowering, uniform flowering, longer spikes, earlier grain maturity, increased seed production, increased fruit or pod size, increased number of pods or spikes, increased number of seeds per pod or spike, increased seed quality, increased seed filling, reduced basal leaf death, delayed senescence, improved plant vigor, and / or reduced inputs required (i.e., reduced fertilizer, water, and / or labor).

[0037] As used herein, the phrase “improved tolerance to stress factors” means improving one or more traits, either qualitatively or quantitatively. These traits include, but are not limited to: enhanced tolerance and / or resistance to abiotic stress factors that result in suboptimal growth conditions, such as drought (i.e., any stress that leads to insufficient water content, insufficient water uptake potential, or reduced water supply to the plant), cold exposure, heat exposure, osmotic stress, UV stress, flooding, increased salinity (i.e., in the soil), increased mineral exposure, ozone exposure, high exposure, and / or limited availability of nutrients (i.e., nitrogen and / or phosphorus nutrients).

[0038] As used herein, the phrase “improved plant yield” or “increased yield” refers to an increase in the yield of the corresponding plant product, where quantitative measurement is possible. Such an increase in yield includes, but is not limited to: (a) an increase in biomass yield, cereal yield (i.e., grain size, number of grains, grain density), starch content, oil content, and / or protein content, which may be due to (i) an increase in the amount produced by the plant itself, or (ii) an improved ability to harvest plant matter; (b) an improved composition of the harvest (i.e., an improved sugar-acid ratio, improved oil composition, increased nutritional value, reduced anti-nutritional compounds, increased consumer health benefits); and / or (c) an increased / promoted ability to harvest crops, improved crop processability, and / or better storage stability / shelf life.

[0039] As used herein, the phrase “agriculturally acceptable carrier” refers to a carrier known and accepted in the art for the formation of formulations for agricultural or horticultural use.

[0040] As used herein, the term "adjuvant" is broadly defined as any substance that is not itself a fungicide but enhances or is intended to enhance the effectiveness of a fungicide used with it. Adjuvants can be understood to include adhesives, spreading agents, surfactants, synergists, penetrants, compatibilizers, buffers, acidifiers, defoamers, thickeners, and drift inhibitors.

[0041] Unless otherwise specified, the terms “an” or “a” as used herein include both the singular and the plural. Therefore, the terms “an,” “a,” or “at least one” are used interchangeably in this application.

[0042] Throughout the application, the description of various embodiments uses the term "comprising"; however, those skilled in the art will understand that in certain specific cases, the language of "substantially consisting of" or "consisting of" may be used instead to describe the embodiments.

[0043] To better understand the invention and in no way limit its scope, all figures and other numerical values ​​used in the specification and claims to express quantities, percentages, or proportions should be understood to be modified by the term "about" in all cases, unless otherwise stated. Therefore, unless indicated to the contrary, the numerical parameters listed in the following specification and appended claims are approximate values ​​that may vary depending on the desired properties sought to be obtained. At a minimum, each numerical parameter should be interpreted based on the number of significant figures reported and by applying common rounding techniques. In this regard, the term "about" as used herein specifically includes ±10% of the indicated value within that range. Furthermore, the endpoints of all ranges relating to the same component or property herein include endpoints that can be independently combined and include all intermediate points and intermediate ranges.

[0044] Antifungal oily liquid preparation

[0045] The oily liquid formulation of the present invention has been found to be stable and has not exhibited phase separation, precipitation, or particle agglomeration during long-term storage. Furthermore, a key advantage of this formulation is its ability to suspend high concentrations of at least one dithiocarbamate fungicide in a non-aqueous liquid carrier, and to dissolve at least one triazole fungicide and at least one methoxyacrylate fungicide in a non-aqueous liquid carrier without compromising formulation stability. This allows for the combination of active ingredients with different physicochemical properties, typically formulated into formulations such as SC and WG, into a single formulation.

[0046] The combination of these different active ingredients in a single formulation is very important because:

[0047] (i) In agronomy, it is generally required that a combination of active ingredients be used for the proper chemical management of pests, providing the necessary efficacy and preventing the emergence of resistant species, and

[0048] (ii) Regarding the compatibility of active ingredients, compatibility issues often arise between different types of formulations of active ingredients when they are barrel-mixed for field application. These mixtures are typically prepared in spray cans, which leads to incompatibility issues between different types of formulations.

[0049] Furthermore, the economic advantage lies in the fact that oily liquid formulations can contain adjuvants, unlike those added in spray cans. This also provides farmers with logistical, packaging, and storage benefits, as a single product can replace two or more.

[0050] This invention relates to an antifungal oily liquid formulation comprising: (a) at least one dithiocarbamate fungicide; (b) at least one triazole fungicide; (c) at least one methoxyacrylate fungicide; and (d) an agriculturally chemically acceptable non-aqueous liquid carrier; wherein the dithiocarbamate fungicide is suspended in the liquid carrier; wherein the triazole fungicide and the methoxyacrylate fungicide are dissolved in the liquid carrier; and wherein the liquid carrier optionally comprises an adjuvant.

[0051] According to another embodiment, the present invention relates to a fungicidal oily liquid formulation comprising: (a) at least one dithiocarbamate fungicide; (b) at least one co-fungicide selected from triazole fungicides and methoxyacrylate fungicides; (c) an agrochemically acceptable non-aqueous liquid carrier; wherein the dithiocarbamate fungicide is suspended in the liquid carrier; wherein the co-fungicide is dissolved in the liquid carrier; and wherein the liquid carrier optionally comprises an adjuvant.

[0052] Dithiocarbamate fungicides may include, but are not limited to: ferrous sulfate, mancozeb, mancozeb, mancozeb, methyl mancozeb, thiram, thiamethoxam, zinc thiamethoxam, zinc thiocyanate, and zinc thiram.

[0053] Triazole fungicides may include, but are not limited to: azaconazole, bifenthrin, furazolidone, cyproconazole, difenoconazole, tebuconazole, fluconazole, eticonazole, cyproconazole, fluquinazole, flusilazole, fenazol, hexaconazole, imidacloprid, tebuconazole, cyproconazole, propiconazole, silfluzazole, tebuconazole, flufenoxuron, triadimefon, triadimefon, tebuconazole, and prothioconazole.

[0054] Methoxyacrylate fungicides may include, but are not limited to: azoxystrobin, eugenol, tebufenozide, fluopyram, pyraclostrobin, 2-[(2,5-dimethylphenoxy)methyl]-α-methoxy-N-methylphenylacetamide (mandestrobin), azoxystrobin, chlorpyrifos, fenpropathrin, oxadiazon, fenpropathrin, fenpropathrin, fenpropathrin, and fluopyram.

[0055] For the chemical categories of fungicides and the specific compounds in each category, see the Pesticide Handbook, 13th edition (Crop Protection Council, Hampshire, UK, 2003) and the Electronic Pesticide Handbook, 5.2 (Crop Protection Council, Hampshire, UK, 2008–2011), the contents of which are incorporated herein by reference in their entirety.

[0056] In a preferred embodiment, the present invention relates to an antifungal oily liquid formulation comprising: a) mancozeb suspended in a non-aqueous liquid carrier; and b) tebuconazole and azoxystrobin dissolved in a non-aqueous liquid carrier.

[0057] In another preferred embodiment, the present invention relates to a fungicidal oily liquid formulation comprising: a) mancozeb suspended in a non-aqueous liquid carrier; and b) prothioconazole and azoxystrobin dissolved in a non-aqueous liquid carrier.

[0058] In another preferred embodiment, the present invention relates to a fungicidal oily liquid formulation comprising: a) mancozeb suspended in a non-aqueous liquid carrier; and b) prothioconazole and oxadiazon dissolved in a non-aqueous liquid carrier.

[0059] In another preferred embodiment, the present invention relates to a fungicidal oily liquid formulation comprising: a) mancozeb suspended in a non-aqueous liquid carrier; and b) prothioconazole dissolved in a non-aqueous liquid carrier.

[0060] In one embodiment, the amount of the dithiocarbamate fungicide may be about 0.1-80% by weight or about 0.1-70% by weight, based on the total weight of the composition. In another embodiment, the dithiocarbamate fungicide may be present at a concentration of about 20-60% by weight, based on the total weight of the composition. In yet another embodiment, the dithiocarbamate fungicide may be present at a concentration of about 25-50% by weight, based on the total weight of the composition. In another embodiment, the dithiocarbamate fungicide may be present at a concentration of about 30-40% by weight, based on the total weight of the composition. In yet another embodiment, the dithiocarbamate fungicide may be present at a concentration of about 35-45% by weight, based on the total weight of the composition. In a specific embodiment, the dithiocarbamate fungicide may be present at a concentration of about 38% by weight, based on the total weight of the composition.

[0061] In one embodiment, the triazole fungicide and the methoxyacrylate fungicide together may be present at a concentration of about 0.1-30% by weight, based on the total weight of the composition. In another embodiment, the triazole fungicide and the methoxyacrylate fungicide together may be present at a concentration of about 1-15% by weight, based on the total weight of the composition. In another embodiment, the triazole fungicide and the methoxyacrylate fungicide together may be present at a concentration of about 1-10% by weight, based on the total weight of the composition. In another embodiment, the triazole fungicide and the methoxyacrylate fungicide together may be present at a concentration of about 3-8% by weight, based on the total weight of the composition. In a specific embodiment, the triazole fungicide and the methoxyacrylate fungicide together may be present at a concentration of about 5% by weight, based on the total weight of the composition.

[0062] In one embodiment, the amount of the co-fungicide may be present at a concentration of about 0.1-30% by weight, based on the total weight of the composition. In another embodiment, the amount of the co-fungicide may be present at a concentration of about 1-15% by weight, based on the total weight of the composition. In another embodiment, the amount of the co-fungicide may be present at a concentration of about 1-10% by weight, based on the total weight of the composition. In yet another embodiment, the amount of the co-fungicide may be present at a concentration of about 1-5% by weight, based on the total weight of the composition. In a specific embodiment, the amount of the co-fungicide may be present at a concentration of about 3% by weight, based on the total weight of the composition.

[0063] According to the implementation plan, the non-aqueous liquid carrier may include, but is not limited to: aromatic hydrocarbons (e.g., toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, isopropylbenzene, tert-butylbenzene, naphthalene, monoalkyl-substituted naphthalene or polyalkyl-substituted naphthalene), paraffin (e.g., octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane, dodecane, tridecane, tetradecane, pentadecane and their branched isomers), petroleum, Ketones (such as acetophenone, cyclohexanone), vegetable oils (such as 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, flaxseed oil, tung oil, sunflower seed oil, safflower oil, tall oil), alkyl esters of vegetable oils (such as rapeseed oil methyl ester or rapeseed oil ethyl ester, rapeseed oil propyl ester, rapeseed oil butyl ester, tall oil fatty acid esters, etc.), diesel oil, mineral oil, fatty acid amides (such as C1-C3 amines, alkylamines or alkanolamines and C6-C... 18 Fatty acid amides formed from carboxylic acids), fatty acids, tall oil fatty acids, fatty acid alkyl esters (such as C8-C) 22 C1-C4 monohydric alcohol esters of fatty acids, such as methyl oleate and ethyl oleate, modified vegetable oils and combinations thereof.

[0064] In a preferred embodiment, the non-aqueous liquid carrier may include, but is not limited to, aromatic hydrocarbons, fatty acid amides, alkyl esters of vegetable oils, and vegetable oils.

[0065] In one embodiment, the amount of the non-aqueous liquid carrier may be about 0.1-60% by weight, about 0.1-55% by weight, or about 0.1-50% by weight, based on the total weight of the composition. In another embodiment, the non-aqueous liquid carrier may be present at a concentration of about 10-50% by weight, based on the total weight of the composition. In another embodiment, the non-aqueous liquid carrier may be present at a concentration of about 15-50% by weight, based on the total weight of the composition. In another embodiment, the non-aqueous liquid carrier may be present at a concentration of about 20-40% by weight, based on the total weight of the composition. In another embodiment, the non-aqueous liquid carrier may be present at a concentration of about 25-40% by weight, based on the total weight of the composition. In another embodiment, the non-aqueous liquid carrier may be present at a concentration of about 30-35% by weight, based on the total weight of the composition. In a specific embodiment, the non-aqueous liquid carrier may be present at a concentration of about 34% by weight, based on the total weight of the composition.

[0066] According to the implementation plan, the adjuvants in the liquid carrier may include, but are not limited to: vegetable oils; alkyl esters of vegetable oils, such as soybean methyl ester, soybean ethyl ester, rapeseed oil methyl ester, or rapeseed oil ethyl ester; alkoxylated sorbitol esters, such as alkoxylated sorbitol monolaurate, such as polyoxyethylene (16) sorbitol monolaurate (TweenTM 24) Polyoxyethylene (20) dehydrated sorbitol monolaurate (Tween TM 20; PSML-20), polyoxyethylene (4) dehydrated sorbitol monolaurate (Tween) TM 21) Polyoxyethylene (8) dehydrated sorbitol monolaurate (Tween TM 22) Polyoxyethylene (12) dehydrated sorbitol monolaurate (Tween TM 23) Dehydrated sorbitol monolaurate ( S / 20, LK, LC 20), polyoxyethylene (20) sorbitan monostearate alkoxylate, such as polyoxyethylene (20) sorbitan monostearate (Tween TM 60), Polyoxyethylene (4) dehydrated sorbitan monostearate (Tween) TM 61) Sorbitol monostearate ( S / 90, S, 60), sorbitol monooleate alkoxylates, such as polyoxyethylene (20) sorbitol monooleate (Tween TM 80. SMO 20, T- 80. SMO 20U), polyoxyethylene (5) dehydrated sorbitol monooleate (Tween TM 81) Dehydrated sorbitan monooleate ( S / 80, 80) and their combinations.

[0067] In a preferred embodiment, the adjuvants in the liquid carrier include tall oil fatty acids (TOFA) and / or soybean methyl ester and / or sorbitol monolaurate alkoxylates, such as polyoxyethylene (16) sorbitol monolaurate (Tween TM twenty four).

[0068] In one embodiment, the adjuvant is present in the formulation at a concentration of at least 10% of the total weight of all components. In another embodiment, the adjuvant is present in the formulation at a concentration of at least 15% of the total weight of all components. In a further embodiment, the adjuvant is present in the formulation at a concentration of at least 20% of the total weight of all components. In another embodiment, the adjuvant is present in the formulation at a concentration of at least 30% of the total weight of all components. In one specific embodiment, the total amount of the adjuvant may be present at a concentration of about 17% by weight, based on the total weight of the composition. In another specific embodiment, the total amount of the adjuvant may be present at a concentration of about 35% by weight, based on the total weight of the composition.

[0069] According to the implementation scheme, the antifungal oily liquid formulation further comprises at least one surfactant. This at least one surfactant may include, but is not limited to: alkyl sulfonates, alkylbenzene sulfonates, alkylaryl sulfonates, alkylphenol alkoxylates, tristyrylphenol polyoxyethylene ethers, natural or synthetic fatty alcohol ethoxylate alcohols, natural or synthetic fatty acid alkoxylates, alkoxylated alcohols (e.g., n-butanol polyethylene glycol ether), block copolymers (e.g., ethylene oxide-propylene oxide block copolymers and ethylene oxide-butane block copolymers), or combinations thereof.

[0070] In a preferred embodiment, the surfactant may include, but is not limited to, tristyrene-phenylene phenol polyoxyethylene ether, alkylbenzene sulfonate, and n-butanol polyethylene glycol ether.

[0071] In one embodiment, the total amount of surfactant present in the formulation may be about 0.1-40% by weight, about 0.1-35% by weight, or about 0.1-30% by weight, based on the total weight of the composition. In another embodiment, the total amount of surfactant may be present at a concentration of about 1-40% by weight, based on the total weight of the composition. In another embodiment, the total amount of surfactant may be present at a concentration of about 10-40% by weight, based on the total weight of the composition. In another embodiment, the total amount of surfactant may be present at a concentration of about 15-25% by weight, based on the total weight of the composition. In one specific embodiment, the total amount of surfactant may be present at a concentration of about 24% by weight, based on the total weight of the composition. In another specific embodiment, the total amount of surfactant may be present at a concentration of about 9% by weight, based on the total weight of the composition.

[0072] In one embodiment, the surfactant is selected from, but is not limited to, tristyrene-phenol polyoxyethylene ether, alkylbenzene sulfonate and n-butanol polyethylene glycol ether, and the total amount of surfactant may be present at a concentration of about 1-40% by weight based on the total weight of the composition.

[0073] Other components, such as binders, neutralizers, thickeners, adhesives, sequestrates, antimicrobial agents, stabilizers, buffers, preservatives, antioxidants, or antifreeze agents, may also be added to the compositions of the present invention to increase the stability, density, and viscosity of the described compositions.

[0074] Furthermore, the agricultural compositions described herein can be used in combination with one or more other pesticides to control a wider range of unwanted pests. When used with other pesticides, the compositions described herein can be formulated with, mixed with, or applied sequentially with other pesticides. Additionally, the compositions described herein can optionally be combined with or blended with other pesticide compositions. Such pesticide mixtures can be used to control pests in both crop and non-crop environments.

[0075] In some embodiments, the agricultural compositions described herein may be used in combination with one or more other adjuvants.

[0076] How to use

[0077] The formulations described herein are suitable for controlling unwanted pests, such as plant pathogenic fungi. The method involves adding an oily, fungicidal liquid formulation to a carrier such as water, and using the resulting solution containing the fungicidal formulation for spray application to control plant pathogenic fungi in plants or their propagation material in crop or non-crop environments.

[0078] A suspension can be formed by diluting the antifungal oily liquid preparation in water.

[0079] The effective application rate of an insecticidal composition cannot usually be defined because it depends on various conditions, such as the type of pesticide, the target pest, weather conditions, soil properties, and crop type. In one embodiment, the fungicidal oily liquid formulation is typically applied at a rate of about 1 L / ha to about 5 L / ha (L / ha). In a preferred embodiment, the fungicidal oily liquid formulation is applied at a rate of about 2 L / ha to 3 L / ha. In one specific embodiment, the fungicidal oily liquid formulation is applied at a rate of about 2 L / ha. In another specific embodiment, the fungicidal oily liquid formulation is applied at a rate of about 3 L / ha. In yet another specific embodiment, the fungicidal oily liquid formulation is applied at a rate of about 2.5 L / ha.

[0080] In one embodiment, the antifungal oily liquid formulation can be diluted in a carrier such as water, in an amount of about 1-100 L of antifungal agent per 1000 L of water. In another embodiment, the composition can be diluted in a carrier such as water, in an amount of about 1-30 L of antifungal agent per 1000 L of water. In yet another embodiment, the composition can be diluted in a carrier such as water, in an amount of 5-15 L of antifungal agent per 1000 L of water.

[0081] The method of the present invention can be applied to any crop, including but not limited to: soybeans, grains, wheat, corn, papaya, melon, cocoa and coffee.

[0082] In another embodiment, the plant pathogenic fungi are one or more categories, including but not limited to: soybean rust (Phakopsora pachyrhizie), target spot (Corynesporacassiicola), late blight (Septoria glycines) and Cercosporakikuchii), maize large leaf spot (Exserohilum turcicum), yellow leaf spot (Dreshslera tritici-repentis), maize brown spot (Phaeosphaeriamaydis), anthracnose (Colletotrichum gloeosporioides), cereal smut, and common smut (Ustilago). Maydis), smut (Sphacelothecareiliana), false smut (Ustilaginoidea virens), stem smut (Usrocystis agropyri), wheat / barley loose smut (Ustilago nuda), hard smut (Ustilago segetum var. hordei), and oat loose smut (Ustilago avenae).

[0083] The agricultural composition described herein can be mixed with water and / or fertilizer and can be applied to the desired location by any means, such as aircraft spray cans, backpack spray cans, cattle dip buckets, farm equipment for ground spraying (e.g., boom sprayers, manual sprayers), etc. The desired location can be soil, vegetation, etc.

[0084] The agricultural composition described in this article can be applied to soybeans from the vegetative growth stage V2 (second ternate leaflets - two sets of unfolded ternate leaflets) to the reproductive growth stage R8 (fully mature - 95% of the pods have reached their full maturity color).

[0085] The compositions of the present invention may include other crop protectants, such as insecticides, herbicides, fungicides, bactericides, nematicides, molluscicides, growth regulators, biological agents, fertilizers, or mixtures thereof. When used in combination with other crop protectants, the compositions may be formulated together with these adjuvants, mixed in a tank with the adjuvants, or applied sequentially with the adjuvants.

[0086] Preparation method

[0087] The scope of this invention extends to a method for obtaining an antifungal oily liquid preparation, which includes the following steps:

[0088] (1) Dissolve at least one triazole fungicide and at least one methoxyacrylate fungicide in a non-aqueous liquid carrier;

[0089] (2) Stir the mixture in step (1);

[0090] (3) Add surfactant;

[0091] (4) Add at least one dithiocarbamate fungicide; and

[0092] (5) Continue stirring until a completely homogeneous formulation is obtained.

[0093] In one embodiment, an adjuvant may optionally be added in step (3). In another embodiment, a surfactant may also be added in step (2) and / or a non-aqueous liquid carrier may also be added in step (3).

[0094] Example 1

[0095] The formulation was prepared according to the following method:

[0096] Add Solvesso 200 (heavy aromatic naphthalene), N,N-dimethyldecylamide, TSP 16EO-tristyrene-phenol polyoxyethylene ether, and calcium dodecylbenzenesulfonate to a container. While stirring, add azoxystrobin and tebuconazole. Heat the mixture to 70-75°C while stirring. Continue stirring until azoxystrobin and tebuconazole are completely dissolved. Stop heating. While stirring, add n-butanol polyethylene glycol ether and soybean oil methyl ester to the container. Then add mancozeb and micronized hexamethylenetetramine to the mixture. Increase the stirring rate to 800 RPM. Continue stirring until a completely homogeneous formulation is obtained.

[0097] Formula I

[0098] Element g / L azoxystrobin 27 Tebuconazole 34 Mancozeb (85% AI) 471(400) Solvesso heavy aromatic naphthalene 150 Armid DM10-AkzoNobel:N,N-Dimethyldecylamide 50 TSP 16EO 16EO-Tristyrene-phenol polyoxyethylene ether 130 Ultraric 5000 n-Butanol Polyethylene Glycol Ether 65 Calcium dodecylbenzenesulfonate 105 Soybean oil methyl ester 214 Hexamethylenetetramine (HMTA) 1

[0099] Example 2

[0100] The formulation was prepared according to the following method:

[0101] Add Solvesso 200 (heavy aromatic naphthalene), N,N-dimethyldecylamide, TSP 16EO-tristyrene-phenol polyoxyethylene ether, and calcium dodecylbenzenesulfonate to a container. While stirring, add azoxystrobin and tebuconazole. Heat the mixture to 70-75°C while stirring. Continue stirring until azoxystrobin and tebuconazole are completely dissolved. Stop heating. While stirring, add n-butanol polyethylene glycol ether, soybean oil methyl ester, and TOFA to the container. Then add mancozeb and micronized hexamethylenetetramine to the mixture. Increase the stirring rate to 800 RPM. Continue stirring until a completely homogeneous formulation is obtained.

[0102] Formula II

[0103]

[0104]

[0105] Example 3

[0106] The formulation was prepared according to the following method:

[0107] Add Solvesso 200 (heavy aromatic naphthalene), Tween 24, TSP 16EO-tristyrene-phenol polyoxyethylene ether, and calcium dodecylbenzenesulfonate to a container. While stirring, add azoxystrobin and tebuconazole. Heat the mixture to 70-75°C while stirring. Continue stirring until azoxystrobin and tebuconazole are completely dissolved. Stop heating. While stirring, add ethoxy-propoxylated alcohol, soybean oil methyl ester, and TOFA to the container. Then add mancozeb, hexamethylenetetramine, and an antifoaming agent to the mixture. Increase the stirring rate to 800 RPM. Continue stirring until a completely homogeneous formulation is obtained.

[0108] Formula III

[0109] Element g / L azoxystrobin 27 Tebuconazole 34 Mancozeb (85% AI) 470(400) Solvesso heavy aromatic naphthalene 145 <![CDATA[Tween TM 24]]> 141 TSP 16EO 16EO-Tristyrene-phenol polyoxyethylene ether 20 Antarox B-848 Ethoxy-Propoxylated Alcohol 4 Calcium dodecylbenzenesulfonate 85 Soybean oil methyl ester 230 tall oil fatty acids 50 Hexamethylenetetramine 0.5 Defoamer (AE100) 0.5

[0110] Formulation III is a uniform, opaque yellow liquid.

[0111] Determination of dynamic viscosity

[0112] The dynamic viscosity of Formulation III was measured using a rotational viscometer (LVT) and a No. 63 rotor. The viscometer was adjusted to rotate clockwise (60 rpm) and the reading was taken 30 seconds after the red pointer stabilized. The dynamic viscosity of the formulation was measured twice: 1) at 20 ± 0.2 °C; 2) at 40 ± 0.2 °C. The dynamic viscosity of the formulation at 20 ± 0.2 °C was measured to be 1160 mPa·s, and the dynamic viscosity at 40 ± 0.2 °C was measured to be 560 mPa·s.

[0113] Determination of miscibility at 30℃

[0114] The formulation from Formula III was added to three different solvents: 1) standard water with a hardness of 20 ppm CaCO3; 2) acetone; and 3) ethanol. Each solution was prepared by transferring approximately 2 mL of the formulation to a 250 mL beaker and then diluting it with 50 mL of solvent (water, acetone, and ethanol). Each solution was mixed for 3 minutes and then transferred to a 100 mL graduated cylinder, bringing the volume to 90 mL with an appropriate solvent. The solution was then immersed in a bath at a controlled temperature of 30 ± 1 °C. After thermal equilibrium was reached, the graduated cylinder was filled to a final volume of 100 mL with an appropriate solvent. The graduated cylinder was inverted 30 times, once every 2 seconds, and returned to its original position. The solution was then immersed in a bath at a controlled temperature of 30 ± 1 °C and allowed to stand for 1 hour. The homogeneity of the solution was then tested, noting the presence or absence of solid-liquid phase separation.

[0115] Under the above conditions, precipitation in the standard aqueous solution was less than 1%; approximately 4% precipitation was observed in the acetone solution; and approximately 6% precipitation was observed in the ethanol solution. No liquid-phase separation was observed in any solution.

[0116] Stability test

[0117] Approximately 50 ml of the OD formulation of Formula III was added to three glass vials. The vials were sealed with rubber stoppers and aluminum seals. One vial was kept at room temperature, while the other two were kept in an oven at 55 ± 2 °C. After 14 days of incubation, the concentration of the active ingredient was determined by high-performance liquid chromatography (HPLC) and gas chromatography / FID. Thermal stability and air stability studies were conducted according to GLP procedure 50010 / Rev.04 – Determination of Thermal Stability and Air Stability. The percentage of degradation was calculated by comparing the concentrations of the active ingredient at room temperature and at elevated temperatures.

[0118] Based on the above tests, mancozeb decreased by only about 2%, azoxystrobin by about 0.2%, and tebuconazole by about 2.4%. Therefore, it can be considered that the OD formulation of Formula III is stable at room temperature and at higher temperatures (55°C).

[0119] Once formulated, the OD formulation of Formulation III prepared by the method of the present invention is expected to exhibit storage stability for up to 2 weeks at temperatures ranging from -5°C to 55°C, and stability at ambient temperature for up to 2 years.

[0120] The oil dispersion formulations of the present invention exhibit good stability over extended periods and at elevated temperatures. These dispersions are easy to pour and disperse in water.

[0121] Field Trial 1:

[0122] Formula I was applied to soybean crops to determine its efficacy against soybean rust (Phakopsorapachyrhizi). The formulation was applied at a rate of 3 L / ha.

[0123] For comparison, the same disease was also treated with a water-dispersible granule (WG) formulation of (i) azoxystrobin + tebuconazole + mancozeb (40+40+600g / Kg) at a dose of 2Kg / ha.

[0124] Table 1

[0125]

[0126] DA1 = Number of days after the first spray

[0127] DA2 = Number of days after the second spray

[0128] DA3 = Number of days after the third spray

[0129] Field Trial 2:

[0130] Formula III was applied to wheat crops to determine its efficacy against wheat yellow spot disease (Drechslera tritici-repentis). At the time of application, disease stress on the crop was considered high (high incidence). The formulation was applied at a rate of 3 L / ha.

[0131] For comparison, (i) a WG formulation of azoxystrobin + tebuconazole + mancozeb (40+40+600g / Kg) applied at a rate of 2 kg / ha and a formulation applied at a rate of 500 ml / ha were also used. (ii) Formulation III formulation with an application rate of 3 L / ha and formulation with an application rate of 500 ml / ha Treating the same disease.

[0132] Table 2

[0133]

[0134] Field trials 3-5:

[0135] In a series of three different field trials, Formulation III was applied to soybean crops to determine its efficacy against soybean rust (soybean rust fungus). The formulation was applied at a rate of 2.5 L / ha (67.5 g picoxy + 82.5 g tecoco + 1000 g MZB).

[0136] For comparison, the same disease was also treated with (i) a WG formulation of pyraclostrobin + tebuconazole + mancozeb (40+40+600g / Kg) at an application rate of 2 kg / ha.

[0137] Table 3

[0138]

[0139] For field trials 1-5, the efficacy of the OD formulation was calculated using the Abbott formula, defined by Abbott in his article entitled "Methods for Calculating the Effectiveness of Insecticides" published in the "Journal of Economic Entomology, 1925, vol. 18, pp. 265-267," which is incorporated herein by reference in its entirety. The efficacy of the fungicidal treatment can be calculated as follows: Where X represents the disease severity of the control (untreated crop) and Y represents the disease severity of the treated crop.

[0140] EC 50 Compare:

[0141] EC of the OD preparation of Formula III 50 EC with WG formulation 50 Comparison was conducted. Soybean leaves infected with *Pseudomonas beanus* rust were treated with either OD or WG formulations. EC values ​​of the OD formulation were compared. 50 The EC of the WG formulation was 4.3 ppm. 50 It is 15.5 ppm. EC 50 Defined as the dose that provides 50% inhibition of fungal isolates compared to a control not treated with a fungicide. EC 50 The lower the value, the more effective the fungicide or fungicide preparation.

[0142] in conclusion:

[0143] As described above, compared to an equivalent amount of WG formulation containing the same active ingredient, the formulation of the present invention either performs better or has the same performance. By exhibiting a higher level of efficacy, the OD formulation demonstrates superiority over the WG formulation at lower concentrations of the active ingredient.

[0144] Example 4

[0145] The formulation was prepared according to the following method:

[0146] Solvesso 200 (heavy aromatic naphthalene), 24. Add TSP 16EO-tristyrene-phenol polyoxyethylene ether, calcium dodecylbenzenesulfonate, acetophenone, and TOFA to a container. Add prothioconazole while stirring (300-400 rpm). While stirring, heat the mixture to 70-75°C. Continue stirring until the prothioconazole is completely dissolved. Stop heating. While stirring, add soybean oil methyl ester and silicone oil to the container. Then add mancozeb to the mixture. Increase the stirring speed to 800 RPM. Continue stirring until a completely homogeneous formulation is obtained.

[0147] Formula IV

[0148] Element g / L Manganese zinc 500 Prothioconazole 40 Solvesso heavy aromatic naphthalene 40 <![CDATA[Tween TM 24]]> 160 Atlas G5002LQ (Polyethylene glycol ether) 5 Calcium dodecylbenzenesulfonate 90 tall oil fatty acids 50 Acetophenone 140 silicone oil 0.2 Soybean oil methyl ester Up to 1000L (~170g)

[0149] EC of the OD preparation of formulation IV 50 EC with a barrel mixture containing prothioconazole and mancozeb 50 Comparison was conducted. Soybean leaves infected with *Pseudomonas beanus* rust were treated with either a mixture or an OD preparation. The EC value of the OD preparation was compared. 50 The EC value of the barrel mixture was 17.2 ppm. 50 It was 19.4 ppm.

[0150] As described above, the fungicidal oily liquid formulation has significant advantages compared to mixtures and formulations known in the art. This formulation is physically stable and easy to apply in the field.

[0151] To demonstrate that the fungicidal oily liquid formulation is at least as similar as mixtures and formulations known in the art, it can be applied to crops such as soybeans. Its control of diseases such as soybean rust can be determined by methods known in the art. The formulation can be applied in various dosages and / or can be applied to various applications.

[0152] While the invention has been shown and described with reference to its preferred embodiments, those skilled in the art will understand that many substitutions, modifications, and variations can be made therein without departing from the spirit and scope of this application. Therefore, this application is intended to cover all such substitutions, modifications, and variations falling within the spirit and broad scope of the appended claims.

[0153] All publications, patents and patent applications mentioned in this specification are incorporated herein by reference in their entirety as if each individual publication, patent or patent application were expressly and individually incorporated herein by reference.

Claims

1. A fungicidal oily liquid preparation, characterized in that... The formulation comprises: a. 20-60% by weight of mancozeb; b. 1-15% by weight of triazole fungicides; c. 10-50% by weight of a non-aqueous liquid carrier, wherein the non-aqueous liquid carrier is selected from aromatics, alkanes, petroleum, ketones, vegetable oils, vegetable oil alkyl esters, diesel oil, mineral oils, fatty acid amides, fatty acids, tall oil fatty acids, fatty acid alkyl esters, modified vegetable oils, and combinations thereof; d. 1-40% by weight of a surfactant, wherein the surfactant is selected from alkyl sulfonates, alkylbenzene sulfonates, alkylaryl sulfonates, alkylphenol alkoxylates, tristyrylphenol polyoxyethylene ethers, natural or synthetic aliphatic ethoxylated alcohols, natural or synthetic fatty acid alkoxylates, block copolymers, natural or synthetic fatty alcohol alkoxylates, alkoxylated alcohols, and combinations thereof. The manganese zinc is suspended in the liquid carrier; and The triazole fungicide is dissolved in the liquid carrier.

2. The antifungal oily liquid preparation according to claim 1, characterized in that... The liquid carrier includes naphthalene, N,N-dimethyldecanoamide, or combinations thereof.

3. The antifungal oily liquid preparation according to claim 1 or 2, characterized in that... The liquid carrier contains additives.

4. The antifungal oily liquid preparation according to claim 3, characterized in that... The adjuvants in the liquid carrier are selected from vegetable oils, alkyl esters of vegetable oils, alkoxylated sorbitol esters, or combinations thereof.

5. The antifungal oily liquid preparation according to claim 4, characterized in that... The alkoxylated sorbitol esters are selected from sorbitol monolaurate alkoxylate, sorbitol monostearate alkoxylate, sorbitol monooleate alkoxylate, or combinations thereof.

6. The antifungal oily liquid preparation according to claim 5, characterized in that... The adjuvants are selected from soybean oil methyl ester, tall oil fatty acids, and polyoxyethylene (16) dehydrated sorbitol monolaurate and mixtures thereof.

7. The antifungal oily liquid formulation according to claim 1 or 2, wherein the triazole antifungal agent is selected from: azaconazole, bifenthrin, furazolidone, cyproconazole, difenoconazole, tebuconazole, flutriafol, eticonazole, cyproconazole, fluquinazole, flusilazole, fenazol, hexaconazole, imidacloprid, tebuconazole, fenazol, cyproconazole, propiconazole, silfluzole, tebuconazole, flufenoxuron, triadimefon, triadimefon, tebuconazole, and prothioconazole.

8. The antifungal oily liquid preparation according to claim 1, characterized in that... The triazole fungicide mentioned is prothioconazole.

9. The antifungal oily liquid preparation according to claim 1, characterized in that... The triazole fungicide mentioned is tebuconazole.

10. The antifungal oily liquid preparation according to claim 1, characterized in that... The triazole fungicide mentioned is difenoconazole.

11. A fungicidal suspension emulsion, characterized in that... The antifungal suspension emulsion comprises: a) the antifungal oily liquid formulation of claim 1 or 2; and b) water.

12. A method for controlling or preventing plant pathogenic fungi on plants or their propagation material, the method comprising applying to the plant or its propagation material any of claims 1 to 2 an antifungal oily liquid preparation to control or prevent plant pathogenic fungi on the plant or its propagation material.

13. The method according to claim 12, characterized in that... The antifungal oily liquid preparation is applied at a rate of 1-5 L / ha.

14. The method according to claim 12, characterized in that The antifungal oily liquid preparation is applied at a rate of 2-3 L / ha.

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