Fungicidal compositions containing mancozeb, tebuconazole and difenoconazole, processes for their preparation and use

Abstract

The application discloses a fungicidal composition containing manganese edathamil-zinc, tebuconazole and difenoconazole as well as a preparation method and application thereof, relates to the field of pesticides, and includes the following as fungicidal effective components: manganese edathamil-zinc, tebuconazole and difenoconazole, wherein the weight ratio of the manganese edathamil-zinc, tebuconazole and difenoconazole is (0.1-99):(0.1-30):1. The application compounding the active ingredients of the drugs, namely the manganese edathamil-zinc, tebuconazole and difenoconazole, the three components do not produce mutual contradiction, the fungicidal spectrum is enlarged, the fungicidal efficiency is improved, obvious synergistic effect is shown, and the diseases in rice, soybean, wheat, peanut, corn, cotton, sunflower, vegetables and fruit trees can be prevented and treated, especially the diseases such as rust, sheath blight, anthracnose, leaf blight, target spot, brown spot and powdery mildew.

Description

Technical Field

[0001] This invention relates to the field of pesticide technology, and in particular to a fungicide composition containing mancozeb, tebuconazole and difenoconazole, its preparation method and application. Background Technology

[0002] Mancozeb is an excellent protective fungicide. It can be sprayed on the leaves, seedlings, young fruits, and during the flowering period of crops. After spraying, it forms a dense protective film on the crop surface, inhibiting the germination and invasion of pathogens. It is mainly used to control leaf spot, ring rot, downy mildew, black spot, anthracnose, and brown spot diseases in fruit trees and vegetables. The manganese and zinc trace elements in mancozeb products have a significant effect on promoting crop growth and increasing yield.

[0003] Tebuconazole is a highly effective, broad-spectrum, systemic triazole fungicide with protective, curative, and eradicative functions. It has a broad fungicidal spectrum and a long-lasting effect. Tebuconazole requires low dosage, has strong systemic activity, and is widely applicable. It effectively controls diseases caused by fungi of the genera *Powdery mildew*, *Stenophyllaria*, *Rhizoctonia*, *Sclerotium*, and *Syndrome*. It can be used for seed treatment or foliar spraying.

[0004] Difenoconazole is a highly effective, broad-spectrum, safe, long-lasting, and systemic triazole fungicide. It provides sustained protection and treatment against pathogens of Ascomycetes, Basidiomycetes, Alternaria, Alternaria, Cercospora, Colletotrichum, Stem-pollen, Cynosporium, Syngonium, and Neisseria. Foliar or seed treatment can improve crop yield and ensure quality.

[0005] The long-term and excessive use of single fungicides can easily lead to drug resistance in diseases, resulting in increased dosage, reduced efficacy, and shorter duration of effectiveness, which is detrimental to sustainable environmental development. One common method to delay the development of drug resistance is to combine active ingredients with different mechanisms of action. Extensive testing is needed to determine the optimal synergistic ratio to broaden the fungicidal spectrum and improve efficiency. Mancozeb has a different mechanism of action than tebuconazole and difenoconazole. A good combination of these three fungicides would overcome the shortcomings of single agents. However, there are currently no reports, either domestically or internationally, on the combination of mancozeb with tebuconazole and difenoconazole. Summary of the Invention

[0006] Purpose of the invention

[0007] To overcome the above shortcomings, the present invention aims to provide a fungicidal composition containing mancozeb, tebuconazole, and difenoconazole, its preparation method, and its application. The present invention combines the active pharmaceutical ingredients mancozeb, tebuconazole, and difenoconazole in a compound. The three components do not interact negatively with each other, and the combination broadens the fungicidal spectrum, improves the fungicidal efficiency, and exhibits a significant synergistic effect. It can effectively control diseases in rice, soybeans, wheat, peanuts, corn, cotton, sunflowers, vegetables, and fruit trees, especially rust, sheath blight, anthracnose, leaf blight, target spot, brown spot, and powdery mildew.

[0008] Solution

[0009] To achieve the objectives of this invention, the technical solution adopted is as follows:

[0010] In a first aspect, the present invention provides a bactericidal composition containing mancozeb, tebuconazole and difenoconazole, wherein the bactericidal active ingredients include mancozeb, tebuconazole and difenoconazole, and the weight ratio of mancozeb, tebuconazole and difenoconazole is (0.1-99):(0.1-30):1.

[0011] Further, the weight ratio of mancozeb, tebuconazole, and difenoconazole is (8-28):(1-3):1, optionally (10-25):(1-3):1, optionally (10-15):(1-3):1, optionally (15-25):

[0012] (1.5-3):1, optionally 10:1:1, 10:3:1, 15:1.5:1, 25:3:1.

[0013] Further, the active ingredient accounts for 1-99% of the total weight of the composition, optionally 10%-80%, optionally 30%-75%, optionally 30%-60%, and optionally 40%-60%.

[0014] Furthermore, the formulation of the bactericidal composition is one or more of the following: dry suspension, aqueous suspension, dispersible oil suspension, wettable powder, water-dispersible granules, granules, and seed treatment agent.

[0015] Furthermore, in addition to the active pharmaceutical ingredient, the above-mentioned bactericidal composition also contains excipients. According to prior art reports, it can be formulated into various agriculturally permissible dosage forms, such as water-dispersible granules, wettable powders, dry suspensions, dispersible oil suspensions, and aqueous suspensions. The excipients selected vary depending on the dosage form. Excipients can be selected from those reported in the prior art, but different excipients may cause differences in dosage form performance and bactericidal effect.

[0016] Furthermore, the bactericidal composition further includes adjuvants, optionally selected from one or more of dispersants, wetting agents, fillers, emulsifiers, thickeners, dispersion media, disintegrants, solvents, preservatives, antifreeze agents, specific gravity regulators, defoamers, oil-phase wall materials, aqueous-phase wall materials, and water.

[0017] Furthermore, based on the aforementioned active pharmaceutical ingredients, this invention has conducted further research and successfully developed dry suspension and dispersible oil suspension formulations suitable for the ternary bactericidal components of mancozeb, tebuconazole, and difenoconazole. Moreover, through extensive research and experimentation, excipients such as dispersants and emulsifiers were screened, resulting in excellent performance and bactericidal effects for both the dry suspension and the dispersible oil suspension.

[0018] Furthermore, the bactericidal composition is in the form of a dry suspension.

[0019] Furthermore, the bactericidal composition comprises the following raw materials in weight percentages:

[0020] The effective bactericidal ingredient is 20-75%, optionally 30%-75%, optionally 30%-65%, optionally 40%-60%, optionally 45%-55%;

[0021] Dispersant 2-20%, optionally 5-10%, optionally 5-9%;

[0022] Wetting agent 2-10%, optionally 3-5%;

[0023] The disintegrant is 1-10%, optionally 2-5%, optionally 2-4.5%, optionally 3-4.5%;

[0024] Defoamer 0.1-2%, optionally 0.1-1%, optionally 0.4-1%, optionally 0.4-0.9%, optionally 0.4-0.8%;

[0025] The filler content is 12-40%, and can be optionally increased to 100%.

[0026] Furthermore, the bactericidal composition comprises the following components in weight percentage: 20-75% (preferably 30%-65%, more preferably 45%-55%) of active pharmaceutical ingredient, 5-10% of dispersant, 3-5% of wetting agent, 2-5% of disintegrant, 0.1-1% of defoamer, and the balance of filler;

[0027] Further, the dispersant is one or more of the following: sodium lignosulfonate, sodium polycarboxylate, sodium maleic acid-acrylic acid copolymer, sodium ethylene oxide-propylene oxide block copolymer, sodium alkyl naphthalene sulfonate formaldehyde condensate, sodium naphthalene sulfonate formaldehyde condensate, alkylphenol polyoxyethylene ether formaldehyde condensate, fatty alcohol polyoxyethylene ether sulfate, and alkylphenol polyoxyethylene ether succinate sulfonate; optionally, the dispersant is selected from sodium naphthalene sulfonate formaldehyde condensate, sodium polycarboxylate, sodium lignosulfonate, sodium alkyl naphthalene sulfonate formaldehyde condensate, and alkylphenol polyoxyethylene ether formaldehyde condensate. The dispersant comprises at least three of the following: aldehyde condensate, fatty alcohol polyoxyethylene ether sulfate, and alkylphenol polyoxyethylene ether succinate sulfonate; optionally, the dispersant is selected from sodium naphthalene sulfonate formaldehyde condensate, sodium polycarboxylate, and sodium lignosulfonate; optionally, the weight ratio of sodium naphthalene sulfonate formaldehyde condensate, sodium polycarboxylate, and sodium lignosulfonate is (2-5):(1-2):(1-2), optionally (3-5):(1-2):(1-2), optionally (2-3):1:1; the function of the dispersant is to uniformly disperse the active ingredient particles and prevent agglomeration.

[0028] Further, the wetting agent includes one or more of sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium alkylnaphthalene sulfonate, sodium α-olefin sulfonate, sodium alkylphenol polyoxyethylene ether sulfate, sodium salt of sulfonic acid formaldehyde condensate, sodium salt of dialkyl succinate sulfonate, sodium lignin sulfonate, and pull-out powder BX; optionally, the wetting agent includes sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium alkylnaphthalene sulfonate, sodium α-olefin sulfonate, sodium alkylphenol polyoxyethylene ether sulfate, sodium salt of sulfonic acid formaldehyde condensate, and dialkyl succinate. The wetting agent comprises one or more of sodium sulfonate salts and sodium lignin sulfonate; optionally, the wetting agent comprises sodium dodecyl sulfate and sodium alkylnaphthalene sulfonate; optionally, the weight ratio of sodium dodecyl sulfate and sodium alkylnaphthalene sulfonate is (1-2):(2-3), optionally 1:(1-2); the function of the wetting agent is to improve the hydrophilicity of the surface of the active ingredient particles, increase the affinity with water, and at the same time reduce the surface tension of the solution. The performance is optimal when the wetting agent is a mixture of sodium dodecyl sulfate and sodium alkylnaphthalene sulfonate in a mass ratio of 1:1-2.

[0029] Further, the disintegrant is one or more selected from ammonium sulfate, potassium sulfate, urea, diammonium hydrogen phosphate, and sodium methylcellulose; optionally, the disintegrant includes ammonium sulfate and urea, and optionally the weight ratio of ammonium sulfate to urea is (1-2):

[0030] (1-3), optionally 1: (1-2);

[0031] Furthermore, the defoamer is one or more of the following: organosilicones, organosiloxanes, higher alcohol fatty acid ester complexes, C10-C20 saturated aliphatic carboxylic acids, and C10-C20 saturated aliphatic carboxylic acid esters;

[0032] Furthermore, the filler is one or more of kaolin, light calcium carbonate, diatomaceous earth, bentonite, and barium sulfate.

[0033] When the above-mentioned excipient components and contents are selected for the dry suspension, a dry suspension formulation with good stability and excellent performance can be obtained, and the efficacy of mancozeb, tebuconazole, and difenoconazole can be fully exerted. The preparation method of the above-mentioned dry suspension can be carried out according to the dry suspension preparation methods disclosed in the prior art. In a specific embodiment of the present invention, a dry suspension preparation method is provided as follows:

[0034] (1) Mancozeb, tebuconazole and difenoconazole, dispersant, wetting agent, disintegrant, defoamer, filler and water are mixed to obtain a slurry;

[0035] (2) Grind the well-mixed slurry in a sand mill until the particle size is 3-5μm;

[0036] (3) After sand milling, the mixture is spray dried and granulated to obtain 80-120 mesh mancozeb, tebuconazole and difenoconazole dry suspension.

[0037] Furthermore, the amount of water used is 45-50% of the total mass of the material.

[0038] Furthermore, the spray drying is carried out in a pressure spray drying device, such as a pressure spray drying tower or a pressure spray dryer. In the preferred embodiment of the present invention, the spray pressure during spray drying is 3.6 MPa, the inlet temperature of the drying gas is 100°C, and the outlet temperature is 60°C. Of course, other spray parameters can also be used.

[0039] Furthermore, the dry suspension obtained by granulation consists of uniform particles of 80-120 mesh.

[0040] Furthermore, the bactericidal composition is in the form of a dispersible oil suspension;

[0041] Furthermore, the bactericidal composition comprises the following raw materials in weight percentages:

[0042] The effective bactericidal ingredient content is 20-75%, optionally 20%-60%, optionally 25%-60%, optionally 30%-55%, optionally 35%-55%, and optionally 35%-52.5%.

[0043] Emulsifier 10-35%, optionally 12-35%, optionally 12-20%;

[0044] The dispersant is 1-5%, optionally 2-5%, optionally 2-4%, optionally 2-3%;

[0045] Thickener 0.5-5%, optionally 1-3%, optionally 1.5-3%;

[0046] The dispersion medium is 13.5-41.5%, optionally 31-40.5%, and optionally filled to 100%;

[0047] Optionally, the bactericidal composition comprises the following components by weight percentage: 20-60% (preferably 25%-60%, more preferably 30%-55%) of bactericidal active ingredient, 12-30% of emulsifier, 2-5% of dispersant, 1-3% of thickener, and dispersion medium to make up to 100%;

[0048] Optionally, the emulsifier includes one or more of fatty amine polyoxyethylene ether, polyarylphenol polyoxyethylene ether, calcium alkylbenzene sulfonate, castor oil polyoxyethylene ether, polyoxyethylene dehydrated sorbitan monooleate, styrene-based phenol polyoxyethylene ether, and polyoxyethylene ether phosphate; optionally, the emulsifier includes calcium alkylbenzene sulfonate and castor oil polyoxyethylene ether; optionally, the weight ratio of calcium alkylbenzene sulfonate to castor oil polyoxyethylene ether is (4-6):(8-16), optionally 1:(2-4);

[0049] Optionally, the dispersant is selected from one or more of alkyl naphthalene sulfonate formaldehyde condensate, sodium succinate diester sulfonate, polyoxyethylene-polyoxypropylene block copolymer, calcium lignosulfonate, and modified polyacrylic acid copolymer; optionally, the dispersant includes alkyl naphthalene sulfonate formaldehyde condensate and polyoxyethylene-polyoxypropylene block copolymer; optionally, the weight ratio of alkyl naphthalene sulfonate formaldehyde condensate to polyoxyethylene-polyoxypropylene block copolymer is (1-1.5):(1-2), optionally 1:

[0050] (1-2);

[0051] Optionally, the thickener is one or more of fumed silica, organobentonite, and urea; optionally, the thickener includes fumed silica and organobentonite; optionally, the weight ratio of fumed silica to organobentonite is (1-2):1, optionally 2:1;

[0052] Optionally, the dispersion medium is one or more selected from methyl oleate, castor oil, rapeseed oil methyl ester, and solvent oil. The dispersion media used in this invention are all environmentally friendly green solvents, which are more environmentally friendly and have good compatibility with various components, thus improving product stability.

[0053] When the above-mentioned excipient components and contents are selected for the dispersible oil suspension, a dispersible oil suspension formulation with good stability and excellent performance can be obtained, and the efficacy of mancozeb, tebuconazole and difenoconazole can be fully utilized.

[0054] Secondly, a method for preparing the bactericidal composition (dry suspension) is provided, comprising mixing mancozeb, tebuconazole and difenoconazole, dispersant, wetting agent, disintegrant, defoamer, filler and water to obtain a slurry; grinding the uniformly mixed slurry to the required particle size, and spray drying and granulating the mixture to obtain a mancozeb, tebuconazole and difenoconazole dry suspension.

[0055] Thirdly, a method for preparing the bactericidal composition (dispersible oil suspension) is provided, wherein a dispersion medium, a thickener, an emulsifier and a dispersant are mixed and dispersed evenly, then mancozeb, tebuconazole and difenoconazole are added, and the mixture is thoroughly sheared and mixed evenly, and then the mixture is ground to the desired particle size to obtain a mancozeb, tebuconazole and difenoconazole dispersible oil suspension.

[0056] In the above preparation method, grinding is performed to a particle size D 90 A particle size of less than 6 μm yields a dispersible oil suspension.

[0057] In the above preparation method, the shearing speed is 1000-10000 r / min. At this shearing speed, thorough mixing and emulsification can be achieved quickly. The faster the shearing speed, the shorter the time required. The shearing time is generally 10-30 minutes.

[0058] In the above preparation method, mancozeb is thoroughly mixed with other materials through homogenization, and the homogenization time is generally 20-30 minutes.

[0059] In the above preparation method, grinding can be performed using any grinding method disclosed in the prior art, such as grinding under zirconia bead milling media. After grinding, the particle size is measured using a laser particle size analyzer until the particle size D is reached. 90 Up to 6μm.

[0060] Fourthly, the application of the bactericidal composition described in the first aspect, or the preparation prepared by the method described in the second or third aspect, in the prevention and control of crop diseases.

[0061] Furthermore, the crop diseases include diseases of rice, soybeans, wheat, peanuts, corn, cotton, sunflowers, vegetables, and fruit trees; optionally, the crop diseases include at least one of leaf rust, sheath blight, anthracnose, leaf blight, target spot, brown spot, and powdery mildew.

[0062] Beneficial effects

[0063] (1) This invention combines the active pharmaceutical ingredients mancozeb, tebuconazole and difenoconazole. The three ingredients do not interact with each other and the fungicidal spectrum is broadened and the fungicidal efficiency is improved. It shows a significant synergistic effect and can effectively control diseases in rice, soybeans, wheat, peanuts, corn, cotton, sunflowers, vegetables and fruit trees, especially rust, sheath blight, anthracnose, leaf blight, target spot, brown spot and powdery mildew.

[0064] (2) The ternary bactericidal composition of mancozeb, tebuconazole and difenoconazole of the present invention has a good synergistic effect in a specific ratio, the efficacy is higher than that of single agents, the dosage is small, the disease resistance is avoided, the drug's duration of effect is extended, and it is conducive to environmental sustainable development.

[0065] (3) The composition of the present invention can be made into dry suspension and dispersible oil suspension. By selecting excipients, dry suspension and dispersible oil suspension with good stability and excellent performance can be obtained, which can greatly promote the efficacy of the active pharmaceutical ingredient.

[0066] (4) The present invention improves product stability and can withstand high and low temperature ranges from -15℃ to 65℃, effectively solving the impact of environmental changes on product quality during transportation.

[0067] (5) By optimizing the additives, this invention improves product stability, enabling it to withstand high and low temperature ranges and effectively solving the problem of environmental changes during transportation affecting product quality. Furthermore, this invention can withstand different water qualities such as C-water, D-water, and 3WHO-water, and has a high product suspension rate, meeting the needs of different countries and regions, thus facilitating its widespread application. Detailed Implementation

[0068] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0069] Furthermore, to better illustrate the present invention, numerous specific details are provided in the following detailed embodiments. Those skilled in the art should understand that the present invention can be practiced without certain specific details. In some embodiments, materials, methods, means, etc., well-known to those skilled in the art, are not described in detail in order to highlight the spirit of the present invention.

[0070] Unless otherwise expressly stated, throughout the specification and claims, the term "comprising" or its variations such as "including" or "comprises" shall be understood to include the stated elements or components without excluding other elements or other components.

[0071] Unless otherwise specified, all percentages below are by weight.

[0072] In the following examples, mancozeb, tebuconazole, and difenoconazole are all commercially available, as are other adjuvants.

[0073] The present invention will be further described in detail below through some embodiments.

[0074] Test Example 1: Indoor Toxicity Determination

[0075] The synergistic bactericidal effects of mancozeb, tebuconazole, and difenoconazole were determined using an indoor toxicity assay. The Sun Yunpei method was employed to determine the co-toxicity coefficient (CTC) of the agents when mixed in a specific ratio. A CTC < 80 indicated antagonistic effects, 80 ≤ CTC ≤ 120 indicated additive effects, and CTC > 120 indicated synergistic effects.

[0076] Test reagents: Mancozeb technical, Tebuconazole technical, and Difenoconazole technical were provided by Shandong Weifang Runfeng Chemical Co., Ltd.

[0077] Experimental Design: After preliminary testing to determine the effective inhibition concentration range of each pesticide, a series of concentration treatments were set for each pesticide according to the content of its active ingredient, with a water control included. The experiment was conducted in accordance with industry standard SY / T1156.15-2008 "Guidelines for Indoor Bioassay Testing of Pesticides - Fungicides - Part 15: Tests for Control of Wheat Leaf Rust - Pot Method". The pot method was used to determine the EC of the pesticides and their mixtures. 50 The co-toxicity coefficient was calculated using the method proposed by Sun Yunpei et al. (1960) for calculating co-toxicity.

[0078] The calculation formula is as follows (using mancozeb as the standard agent, with a toxicity index of 100).

[0079] Tebuconazole toxicity index (TI) = mancozeb EC5 50 EC of tebuconazole 50 ×100.

[0080] The toxicity index (TI) of difenoconazole is equal to the EC5 of mancozeb. 50 EC of difenoconazole 50 ×100.

[0081] The Actual Toxicity Index (ATI) of M = EC5 of mancozeb 50 / M of EC 50 ×100.

[0082] Theoretical toxicity index (TTI) of mancozeb = TTI × P 代森锰锌 +Tebuconazole TI×P 戊唑醇 + Diphenoxymethyl TI×P 苯醚甲环唑 .

[0083] Cotoxicity coefficient (CTC) of M = ATI of M / TTI of M × 100.

[0084] In the formula: M is a mixture of mancozeb, tebuconazole and difenoconazole in different proportions;

[0085] P 代森锰锌 This refers to the proportion of mancozeb in the compound composition;

[0086] P 戊唑醇 This refers to the proportion of tebuconazole in the compound composition;

[0087] P 苯醚甲环唑 This represents the proportion of difenoconazole in the compound composition.

[0088] This invention relates to a composition of three active pharmaceutical ingredients. The theoretical toxicity index (TTI) of M can also be calculated by adding the toxicity index of the binary mixture to the toxicity index of the other single agent: Theoretical toxicity index (TTI) of M = ATI of the binary mixture × P 二元混剂 +Another single-dose TI×P 另一混剂 (In this formula, the binary mixture ATI is the ATI of components A+B (or B+C or C+A) used together (= EC of mancozeb) 50 EC of component (A+B) (or B+C or C+A) 50 ×100), P 二元混剂 The TI is the proportion of component A+B (or B+C or C+A) in the compound composition; the other single agent TI is the TI of component C (or A or B), P 另一混剂 The proportion of component C (or A or B) in the compound composition is used to illustrate the synergistic effect of the ternary composition of the present invention from multiple perspectives.

[0089] The experimental results are shown in Table 1:

[0090] Table 1. Results of toxicity assay of the combination of mancozeb, tebuconazole and difenoconazole against wheat leaf rust.

[0091]

[0092]

[0093] Table 1 shows that mancozeb, tebuconazole, and difenoconazole have different effects on the EC50 of wheat leaf rust. 50The concentrations were 77.05 mg / L, 43.18 mg / L, and 51.22 mg / L, respectively. When the mass ratio of mancozeb, tebuconazole, and difenoconazole was within the range of (10-25):(1-3):1, and optionally at (10-15):(1-3):1, (15-25):(1.5-3):1, (15):(1-2):1, (10:1:1), (10:3:1), (15:1.5:1), and (25:3:1), the co-toxicity coefficient of the compound composition was greater than 120, indicating a synergistic effect. However, when the mass ratio of mancozeb, tebuconazole, and difenoconazole was 9:1:1, 8:3:1, and 28:2:1, the co-toxicity coefficients were only 116.09, 112.98, and 115.26, respectively, indicating an additive effect.

[0094] Preparation Examples

[0095] Example 1: Dry suspension

[0096] This embodiment provides a dry suspension agent with the following component contents (wt%): 20% active ingredient, 1% sodium lignosulfonate dispersant, 0.5% sodium polycarboxylate, 0.5% alkylphenol polyoxyethylene ether succinate sulfonate, 1% sodium dodecyl sulfate wetting agent, 1% BX disintegrant, 1% ammonium sulfate disintegrant, 1% diammonium hydrogen phosphate, 0.1% defoamer (organosilicone), and 100% filler (kaolin). The active ingredient is a mixture of mancozeb, tebuconazole, and difenoconazole in a mass ratio of 10:1:1.

[0097] The preparation method of the above-mentioned dry suspension is as follows: mancozeb, tebuconazole and difenoconazole, dispersant, wetting agent, disintegrant, defoamer, filler and water are mixed to obtain a slurry; the uniformly mixed slurry is sand-milled to a particle size of 3-5μm; after sand milling, the mixture is spray-dried and granulated to obtain a mancozeb, tebuconazole and difenoconazole dry suspension of 80-120 mesh.

[0098] Examples 2-10 and Comparative Example 1: Dry Suspension

[0099] Following the method of Example 1, dry suspension formulations of Examples 2-10 and Comparative Example 1 were prepared respectively. The raw material composition of Examples 2-10 and Comparative Example 1 is shown in Table 2.

[0100] Table 2. Dry suspension formulations (wt%) for Examples 2-10 and Comparative Example 1

[0101]

[0102]

[0103] Test Example 2: Physicochemical Indicators of Dry Suspension Formulations

[0104] The performance of the products prepared in Examples 1-10 and Comparative Example 1 were tested, and the results are shown in the table below. The testing methods for each performance index are as follows: wetting time was determined according to GB / T 5451-2001, the wettability test method for pesticide wettable powders; suspension rate was determined according to GB / T14825-2023, the suspension rate test method for pesticides; sieving was determined according to GB / T16150-1995, the fineness test method for pesticide powders and wettable powders; persistent foaming was determined according to CIPACMT 47, "Determination of Persistent Foaming"; and thermal storage stability (performance before and after thermal storage) was tested according to GB / T19136-2003, the thermal storage stability test method for pesticides.

[0105] Table 3. Performance of the dry suspension products in Examples 1-10 and comparative examples

[0106]

[0107] As shown in Table 4, the dry suspension concentrates prepared by this invention all exhibit high suspension rate, short wetting time, low foaming, good sieveability, and good thermal storage stability. Comparative Example 1 showed poor quality both before and after thermal storage. After being stored at 54℃ for 14 days and then transferred to room temperature, the sample showed a decrease in suspension rate, unsatisfactory sieveability, and a wetting time exceeding 60 seconds. Examples 1-4 showed a slight deterioration in quality after thermal storage, while Examples 5-10 showed good quality both before and after thermal storage. The preferred additives play a crucial role in product quality.

[0108] Example 11: Dispersible oil suspension

[0109] This embodiment provides a dispersible oil suspension with the following components in wt% (%): 20% active ingredient, 6% emulsifier polyarylphenol polyoxyethylene ether, 4% alkylbenzene sulfonate calcium, 1% dispersant sodium succinate diester sulfonate, 1% thickener organobentonite, 4% fumed silica, and 100% dispersing medium rapeseed oil methyl ester. The active ingredient is a mixture of mancozeb, tebuconazole and difenoconazole in a mass ratio of 10:1:1.

[0110] The preparation method of the above-mentioned dispersible oil suspension is as follows: the dispersion medium, thickener, emulsifier and dispersant are mixed and dispersed evenly, then mancozeb, tebuconazole and difenoconazole are added, and the mixture is fully sheared and mixed evenly. Then the mixture is ground until the particle size D90 is less than 6μm to obtain the mancozeb, tebuconazole and difenoconazole dispersible oil suspension.

[0111] Examples 12-20 and Comparative Example 2: Dispersible oil suspension

[0112] Following the method of Example 11, dispersible oil suspensions of Examples 12-20 and Comparative Example 2 were prepared respectively. The raw material composition of Examples 12-20 and Comparative Example 2 is shown in Table 4.

[0113] Table 4. Formulations (wt%) of dispersible oil suspensions for Examples 12-20 and Comparative Example 2

[0114]

[0115]

[0116] Test Example 3: Physicochemical Indicators of Dispersible Oil Suspension Formulations

[0117] The performance of the products prepared in Examples 11-20 and Comparative Example 2 of the above-mentioned dispersible oil suspensions was tested, and the results are shown in Table 5 below. The suspension rate was tested according to GB / T14825-2023, the method for determining the suspension rate of pesticides; the pourability (residue after pouring) was tested according to GB / T31737-2015, the method for determining the pourability of pesticides; the dispersion stability was tested according to CIPAC MT 180, "Determination of dispersion stability of suspension emulsions"; and the thermal storage stability (performance before and after thermal storage) was tested according to GB / T19136-2003, the method for determining the thermal storage stability of pesticides.

[0118] Table 5. Performance of dispersible oil suspension products in Examples 11-20 and Comparative Example 2

[0119]

[0120] As shown in Table 5, the dispersible oil suspension products prepared by this invention all have the characteristics of high suspension rate, low residual amount after pouring, good dispersion stability, and good thermal storage stability. Comparative Example 2 showed poor quality before and after thermal storage. After being stored at 54℃ for 14 days, the suspension rate of the sample decreased and the oil separation rate reached 15% after being transferred to room temperature. Examples 11-14 showed slightly worse quality after thermal storage, while Examples 15-20 showed good quality before and after thermal storage. The preferred additives play a key role in product quality.

[0121] Field trial examples and efficacy trials of soybean rust treatment

[0122] This experiment was conducted in a farmland on the outskirts of Hanting District, Weifang City, Shandong Province. The terrain was flat and level, with complete irrigation and drainage facilities, consistent field management, and uniform to moderate fertility. The pesticide was applied at the early stage of soybean rust disease. The experiment included eight treatments (using Example 2, Example 8, Example 12, Example 18, Comparative Example 1, Comparative Example 2, 64% Mancozeb·Difenoconazole wettable powder (commercially available), and a water control), with three replicates for each treatment, totaling 24 plots, each plot measuring 40 m².2 The experiment was conducted in a randomized block design. The water control group was sprayed with water without any pesticide, while the remaining experimental areas were pesticide-treated areas. The application method was as follows: two applications were made using a Gongnong-16 backpack manual sprayer. The pesticide solution was prepared by diluting 450 kg of water per hectare of the formulation dosage, and the calculated pesticide solution volume for each plot was then uniformly sprayed. All water used for pesticide solution preparation during the experiment was 3WHO water prepared in the laboratory.

[0123] Before applying the pesticide, the initial incidence rate was investigated. The control effect was investigated 14 days after the second application. The control efficacy was calculated, and the safety of the test pesticide on the crop was observed.

[0124] Survey Method: Twenty plants were sampled at five diagonal points in each plot. Four leaves from the upper, middle, and lower parts of each plant were examined. The total number of leaves and the number of diseased leaves at each level were recorded. Disease incidence was recorded leaf by leaf according to the following nine-level grading standard:

[0125] Level 0: No disease;

[0126] Grade 1: The lesion area accounts for less than 5% of the total leaf area;

[0127] Grade 3: Lesions cover 6-25% of the total leaf area;

[0128] Level 5: Lesions cover 26-50% of the total leaf area;

[0129] Level 7: Lesions cover 51-75% of the total leaf area;

[0130] Level 9: The lesion area accounts for more than 75% of the total leaf area.

[0131] Methods for calculating drug efficacy:

[0132] Disease index = Σ(number of diseased leaves at each level × corresponding level value) / total number of surveys × 9 × 100;

[0133] Control effect (%) = (1 - Disease index before treatment in control area × Disease index after treatment in treatment area / Disease index after treatment in control area × Disease index before treatment in treatment area) × 100.

[0134] The results of the control of soybean rust are shown in Table 4 below:

[0135] Table 6. Results of field efficacy trials of various treatments for controlling soybean rust.

[0136]

[0137]

[0138] As can be seen from the experimental results in Table 6 above, the combination of mancozeb, tebuconazole and difenoconazole can effectively control soybean rust. 14 days after the last application, the control effects of Examples 2, 8, 12 and 18 on soybean rust were significantly better than the control agent and Comparative Examples 1 and 2, showing a synergistic effect.

[0139] Based on observations throughout the field trial, soybeans grew well within the experimental dosage range, and no phytotoxicity was observed in any of the treatments, indicating that they are safe for soybeans.

[0140] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A bactericidal composition containing mancozeb, tebuconazole, and difenoconazole, characterized in that, The bactericidal composition is in the form of a dispersible oil suspension. Its bactericidal active ingredients include mancozeb, tebuconazole and difenoconazole, wherein the weight ratio of mancozeb, tebuconazole and difenoconazole is (10-25):(1-3):1; The bactericidal composition comprises the following raw materials in weight percentages: 20-75% bactericidal active ingredient, 10-35% emulsifier, 1-5% dispersant, 0.5-5% thickener, and 13.5-41.5% dispersion medium. The emulsifier comprises calcium alkylbenzene sulfonate and castor oil polyoxyethylene ether; the weight ratio of calcium alkylbenzene sulfonate to castor oil polyoxyethylene ether is (4-6):(8-16). The dispersant comprises an alkyl naphthalene sulfonate formaldehyde condensate and a polyoxyethylene-polyoxypropylene block copolymer; the weight ratio of the alkyl naphthalene sulfonate formaldehyde condensate and the polyoxyethylene-polyoxypropylene block copolymer is (1-1.5):(1-2); The thickener comprises fumed silica and organobentonite; the weight ratio of fumed silica to organobentonite is (1-2):

1.

2. The bactericidal composition according to claim 1, characterized in that, The effective bactericidal ingredient content is 20%-60%.

3. The bactericidal composition according to claim 1, characterized in that, The effective bactericidal ingredient content is 25%-60%.

4. The bactericidal composition according to claim 1, characterized in that, The effective bactericidal ingredient is 30%-55%.

5. The bactericidal composition according to claim 1, characterized in that, The effective bactericidal ingredient is 35%-55%.

6. The bactericidal composition according to claim 1, characterized in that, The effective bactericidal ingredient is 35%-52.5%.

7. The bactericidal composition according to claim 1, characterized in that, The emulsifier content is 12-35%.

8. The bactericidal composition according to claim 1, characterized in that, The emulsifier content is 12-20%.

9. The bactericidal composition according to claim 1, characterized in that, The dispersant content is 2-5%.

10. The bactericidal composition according to claim 1, characterized in that, The dispersant content is 2-4%.

11. The bactericidal composition according to claim 1, characterized in that, The dispersant content is 2-3%.

12. The bactericidal composition according to claim 1, characterized in that, The thickener content is 0.5-5%.

13. The bactericidal composition according to claim 1, characterized in that, Thickener content is 1-3%.

14. The bactericidal composition according to claim 1, characterized in that, The thickener content is 1.5-3%.

15. The bactericidal composition according to claim 1, characterized in that, The dispersion medium is 31-40.5%.

16. The bactericidal composition according to claim 1, characterized in that, The dispersion medium is filled to 100%.

17. The bactericidal composition according to claim 1, characterized in that, The bactericidal composition consists of the following components by weight percentage: 20-60% bactericidal active ingredient, 12-30% emulsifier, 2-5% dispersant, 1-3% thickener, and dispersion medium to make up to 100%.

18. The bactericidal composition according to claim 17, characterized in that, The effective bactericidal ingredient content is 25%-60%.

19. The bactericidal composition according to claim 17, characterized in that, The effective bactericidal ingredient is 30%-55%.

20. The bactericidal composition according to any one of claims 1 to 19, characterized in that, In the emulsifier, the weight ratio of calcium alkylbenzene sulfonate and castor oil polyoxyethylene ether is 1:(2-4).

21. The bactericidal composition according to any one of claims 1 to 19, characterized in that, In the dispersant, the weight ratio of alkyl naphthalene sulfonate formaldehyde condensate and polyoxyethylene-polyoxypropylene block copolymer is 1:(1-2).

22. The bactericidal composition according to any one of claims 1 to 19, characterized in that, The thickener contains fumed silica and organobentonite in a weight ratio of 2:

1.

23. The bactericidal composition according to any one of claims 1 to 19, characterized in that, The dispersion medium is one or more of methyl oleate, castor oil, rapeseed oil methyl ester, and solvent oil.

24. The bactericidal composition according to any one of claims 1 to 19, characterized in that, The weight ratio of mancozeb, tebuconazole and difenoconazole is (10-15):(1-3):

1.

25. The bactericidal composition according to any one of claims 1 to 19, characterized in that, The weight ratio of mancozeb, tebuconazole and difenoconazole is (15-25):(1.5-3):

1.

26. The bactericidal composition according to any one of claims 1 to 19, characterized in that, The weight ratio of mancozeb, tebuconazole, and difenoconazole is 10:1:

1.

27. The bactericidal composition according to any one of claims 1 to 19, characterized in that, The weight ratio of mancozeb, tebuconazole, and difenoconazole is 10:3:

1.

28. The bactericidal composition according to any one of claims 1 to 19, characterized in that, The weight ratio of mancozeb, tebuconazole and difenoconazole is 15:1.5:

1.

29. The bactericidal composition according to any one of claims 1 to 19, characterized in that, The weight ratio of mancozeb, tebuconazole, and difenoconazole is 25:3:

1.

30. A method for preparing the bactericidal composition according to any one of claims 1 to 29, characterized in that, The dispersion medium, thickener, emulsifier and dispersant are mixed and dispersed evenly. Then, mancozeb, tebuconazole and difenoconazole are added and thoroughly sheared and mixed evenly. The mixture is then ground to the desired particle size to obtain a mancozeb, tebuconazole and difenoconazole dispersible oil suspension.

31. The use of a bactericidal composition according to any one of claims 1 to 29, or an formulation prepared by the preparation method according to claim 30, in the prevention and control of crop diseases.

32. The application according to claim 31, characterized in that, The crop diseases mentioned include those in rice, soybeans, wheat, peanuts, corn, cotton, sunflowers, vegetables, and fruit trees.

33. The application according to claim 31, characterized in that, The crop diseases mentioned include at least one of leaf rust, sheath blight, anthracnose, leaf blight, target spot, brown spot, and powdery mildew.

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