Bactericidal composition containing mancozeb, tebuconazole and difenoconazole as well as preparation method and application of bactericidal composition

Abstract

The invention discloses a bactericidal composition containing mancozeb, tebuconazole and difenoconazole as well as a preparation method and application of the bactericidal composition, and relates to the field of pesticides, the bactericidal composition comprises the effective bactericidal components of mancozeb, tebuconazole and difenoconazole, and the weight ratio of mancozeb to tebuconazole to difenoconazole is (0.1-99): (0.1-30): 1. According to the bactericidal composition disclosed by the invention, the active pharmaceutical ingredients mancozeb, tebuconazole and difenoconazole are compounded and are mutually mixed without conflict, the bactericidal spectrum is expanded, the bactericidal efficiency is improved, an obvious synergistic effect is shown, and the bactericidal composition can be used for preventing and treating diseases in rice, soybeans, wheat, peanuts, corn, cotton, sunflowers, vegetables and fruit trees and has a good application prospect in prevention and treatment of diseases of rice, soybeans, wheat, peanuts, corn, cotton, sunflowers, vegetables and fruit trees. Particularly, the bactericidal composition has very good prevention and treatment effects on rust diseases, banded sclerotial blight, anthracnose, leaf blight, target leaf spot, brown spot and powdery mildew.

Description

Technical Field

[0001] The invention relates to the technical field of pesticides, and in particular to a fungicide composition containing mancozeb, tebuconazole and difenoconazole, and a preparation method and application thereof. Background Art

[0002] Mancozeb is an excellent protective fungicide. It can be used for spraying on the leaves, seedlings, young fruits and flowering period of crops. After spraying, a dense protective film is formed on the surface of the crop to inhibit the germination and invasion of pathogens. It is mainly used to prevent and treat leaf spot disease, ring rot, downy mildew, black spot, anthracnose, brown spot disease, etc. of fruit trees and vegetables. The trace elements of manganese and zinc in mancozeb products have obvious effects on promoting the growth and increasing the yield of crops.

[0003] Tebuconazole is a highly effective, broad-spectrum, systemic triazole fungicide with three functions: protection, treatment, and eradication. It has a broad fungicide spectrum and a long lasting effect. Tebuconazole has low dosage, strong systemicity, and a wide range of applications. It can effectively prevent and control diseases caused by powdery mildew, rust, rhinoceros, pyrenophora, and septoria, and 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 has a long-lasting protective and therapeutic effect on pathogens such as Ascomycetes, Basidiomycetes, Alternaria, Ascochyta, Cercospora, Colletotrichum, Phoma, Septoria, Septoria, and Venturia. Spraying on stems and leaves or treating seeds can increase crop yields and ensure quality.

[0005] The long-term and large-scale use of a single fungicide can easily cause the disease to develop resistance, resulting in increased dosage, reduced prevention effect, and shortened duration, which is not conducive to environmental sustainable development. One of the common methods to delay the development of resistance in diseases is to compound active ingredients with different mechanisms of action. Through a large number of experiments, the optimal synergistic compounding ratio is determined to expand the fungicide spectrum and improve fungicide efficiency. Mancozeb has different mechanisms of action from tebuconazole and difenoconazole. How to compound the three to achieve a good effect will overcome the shortcomings of a single fungicide. However, there are no related reports on the compounding of mancozeb with tebuconazole and difenoconazole at home and abroad. Summary of the invention

[0006] Purpose of the Invention

[0007] In order to overcome the above disadvantages, the object of the present invention is to provide a bactericidal composition containing mancozeb, tebuconazole and difenoconazole, and a preparation method and application thereof. The present invention compound the three active ingredients of mancozeb, tebuconazole and difenoconazole, which will not conflict with each other when mixed, and can expand the bactericidal spectrum, improve the bactericidal efficiency, show obvious synergistic effect, and can be used for diseases in rice, soybean, wheat, peanut, corn, cotton, sunflower, vegetables and fruit trees, especially for rust, sheath blight, anthrax, leaf blight, target spot, brown spot and powdery mildew. It has a good control effect.

[0008] Solution

[0009] To achieve the purpose of the present invention, the technical solution adopted by the present invention is as follows:

[0010] In a first aspect, the present invention provides a fungicide composition containing mancozeb, tebuconazole and difenoconazole, wherein the fungicide 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] Furthermore, 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] Furthermore, the active ingredient accounts for 1 to 99% of the total weight of the composition, optionally 10% to 80%, optionally 30% to 75%, optionally 30% to 60%, optionally 40% to 60%.

[0014] Furthermore, the formulation of the bactericidal composition is one or more of a dry suspension, an aqueous suspension, a dispersible oil suspension, a wettable powder, a water dispersible granule, a granule, and a seed treatment agent;

[0015] Furthermore, the above-mentioned bactericidal composition, in addition to the active pharmaceutical ingredient, also contains excipients. According to reports in the prior art, it can be made into any dosage form allowed in agriculture, such as water dispersible granules, wettable powders, dry suspensions, dispersible oil suspensions, water suspensions, etc. Depending on the dosage form, the selected excipients are different. The excipients can be selected from the excipients reported in the prior art, but the difference in excipients may cause differences in dosage form performance and bactericidal effects.

[0016] Furthermore, the bactericidal composition also includes an auxiliary agent. Optionally, the auxiliary agent is selected from one or more of a dispersant, a wetting agent, a filler, an emulsifier, a thickener, a dispersion medium, a disintegrant, a solvent, a preservative, an antifreeze agent, a specific gravity regulator, a defoaming agent, an oil phase wall material, an aqueous phase wall material, and water.

[0017] Furthermore, on the basis of obtaining the above-mentioned active pharmaceutical ingredients, the present invention has conducted further research and successfully developed a dry suspension and dispersible oil suspension formulation suitable for the ternary bactericidal components of mancozeb, tebuconazole and difenoconazole. In addition, through a large number of studies and experiments, auxiliary materials such as dispersants and emulsifiers have been screened out, so that the performance and bactericidal effect of the dry suspension and the dispersible oil suspension are very good.

[0018] Further, the dosage form of the bactericidal composition is a dry suspension;

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

[0020] Bactericidal active ingredient 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] Disintegrant 1-10%, optionally 2-5%, optionally 2-4.5%, optionally 3-4.5%;

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

[0025] Filler 12-40%, optional supplement to 100%;

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

[0027] Further, the dispersant is one or more of sodium lignin sulfonate, sodium salt of polycarboxylic acid, sodium salt of maleic acid-acrylic acid copolymer, sodium salt of ethylene oxide-propylene oxide block copolymer, sodium salt of alkylnaphthalenesulfonic acid formaldehyde condensate, sodium salt of naphthalenesulfonic acid 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 salt of naphthalenesulfonic acid formaldehyde condensate, sodium salt of polycarboxylic acid, sodium lignin sulfonate, sodium salt of alkylnaphthalenesulfonic acid formaldehyde condensate, alkylphenol polyoxyethylene ether formaldehyde condensate At least three of aldehyde condensation products, fatty alcohol polyoxyethylene ether sulfates, and alkylphenol polyoxyethylene ether succinate sulfonates; optionally, the dispersant is selected from naphthalenesulfonic acid formaldehyde condensation product sodium salt, polycarboxylic acid sodium salt and sodium lignin sulfonate, optionally, the weight ratio of naphthalenesulfonic acid formaldehyde condensation product sodium salt, polycarboxylic acid sodium salt and sodium lignin sulfonate 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 evenly disperse the particles of the active ingredient and prevent agglomeration.

[0028] Further, the wetting agent includes one or more of sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium alkyl naphthalene 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 opening powder BX; optionally, the wetting agent includes sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium alkyl naphthalene sulfonate, sodium α-olefin sulfonate, sodium alkylphenol polyoxyethylene ether sulfate, sodium salt of sulfonic acid formaldehyde condensate, sodium salt of dialkyl succinate One or more of sodium sulfonate, sodium lignin sulfonate; optionally, the wetting agent includes sodium dodecyl sulfate and sodium alkyl naphthalene sulfonate; optionally, the weight ratio of sodium dodecyl sulfate and sodium alkyl naphthalene 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 reduce the surface tension of the solution. The performance is best when the wetting agent is a mixture of sodium dodecyl sulfate and sodium alkyl naphthalene sulfonate in a mass ratio of 1:1-2.

[0029] Further, the disintegrant is one or more of 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] Further, the defoaming agent is one or more of organic silicones, organic siloxanes, high-carbon 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 dry suspension selects the above auxiliary material components and contents, a dry suspension dosage form 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 dry suspension can be prepared according to the preparation method of the dry suspension disclosed in the prior art. In a specific embodiment of the present invention, a preparation method of a dry suspension is provided as follows:

[0034] (1) mixing mancozeb, tebuconazole, difenoconazole, a dispersant, a wetting agent, a disintegrant, a defoaming agent, a filler and water to obtain a slurry;

[0035] (2) grinding the mixed slurry to a particle size of 3-5 μm by a sand mill;

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

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

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

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

[0040] Further, the formulation of the bactericidal composition is a dispersible oil suspension;

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

[0042] Bactericidal active ingredient 20-75%, optionally 20%-60%, optionally 25%-60%, optionally 30%-55%, optionally 35%-55%, optionally 35%-52.5%;

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

[0044] Dispersant 1-5%, optionally 2-5%, optionally 2-4%, optionally 2-3%;

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

[0046] Dispersing medium 13.5-41.5%, optionally 31-40.5%, optionally filled to 100%;

[0047] Optionally, the bactericidal composition is composed of the following components in weight percentage: bactericidal active ingredient 20-60% (preferably 25%-60%, more preferably 30%-55%), emulsifier 12-30%, dispersant 2-5%, thickener 1-3%, and dispersion medium supplemented 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 sorbitan monooleate, styrylphenol 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), and optionally 1:(2-4);

[0049] Optionally, the dispersant is selected from one or more of alkylnaphthalene sulfonate formaldehyde condensate, sodium succinate diester sulfonate, polyoxyethylene-polyoxypropylene block copolymer, calcium lignin sulfonate and modified polyacrylic acid copolymer; Optionally, the dispersant comprises alkylnaphthalene sulfonate formaldehyde condensate and polyoxyethylene-polyoxypropylene block copolymer; Optionally, the weight ratio of alkylnaphthalene sulfonate formaldehyde condensate and 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, organic bentonite, and urea; Optionally, the thickener includes fumed silica and organic bentonite; Optionally, the weight ratio of fumed silica to organic bentonite is (1-2):1, optionally 2:1;

[0052] Optionally, the dispersion medium is one or more of methyl oleate, castor oil, rapeseed oil methyl ester and solvent oil. The dispersion medium used in the present invention is an environmentally friendly green solvent, which is more environmentally friendly and has good compatibility with various components, thereby improving the stability of the product.

[0053] When the dispersible oil suspension selects the above auxiliary material components and contents, a dispersible oil suspension dosage form with good stability and excellent performance can be obtained, and the efficacy of mancozeb, tebuconazole and difenoconazole can be fully exerted.

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

[0055] In a third aspect, 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 uniformly, and then mancozeb, tebuconazole and difenoconazole are added, and the mixture is fully sheared and mixed uniformly, and then the mixture is ground to a desired particle size to obtain a dispersible oil suspension of mancozeb, tebuconazole and difenoconazole.

[0056] In the above preparation method, the particle size D 90 Less than 6μm, it can be dispersed in oil suspension.

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

[0058] In the above preparation method, mancozeb and other materials are fully mixed by homogenization, and the homogenization time is generally 20-30 minutes.

[0059] In the above preparation method, grinding can be performed by any grinding method disclosed in the prior art, for example, grinding can be performed under a zirconia bead grinding medium. After grinding, a laser particle size distribution analyzer is used to detect until the particle size D 90 Less than 6μm.

[0060] In a fourth aspect, there is provided a use of the fungicidal composition described in the first aspect or a preparation prepared by the preparation method described in the second aspect or the third aspect in preventing and controlling crop diseases.

[0061] Furthermore, the crop diseases include diseases of rice, soybean, wheat, peanut, corn, cotton, sunflower, 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) The present invention compounds the active ingredients of mancozeb, tebuconazole and difenoconazole, which do not conflict with each other, expand the bactericidal spectrum, improve the bactericidal efficiency, and show obvious synergistic effect. The invention can control diseases in rice, soybean, wheat, peanut, corn, cotton, sunflower, vegetables and fruit trees, especially rust, sheath blight, anthracnose, leaf blight, target spot, brown spot and powdery mildew, and has a good control effect.

[0064] (2) The ternary fungicidal composition of mancozeb, tebuconazole and difenoconazole of the present invention has a good synergistic effect within a specific ratio, and the prevention effect is higher than that of a single agent, the dosage is small, the drug resistance of the disease is avoided, the drug lasting period is extended, and it is beneficial to environmental sustainable development.

[0065] (3) The composition of the present invention can be made into a dry suspension and a dispersible oil suspension. By selecting the auxiliary materials, a dry suspension and a dispersible oil suspension with good stability and excellent performance can be obtained, and the efficacy of the active ingredients of the medicine can be well promoted.

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

[0067] (5) The present invention improves product stability by optimizing auxiliary agents, can tolerate high and low temperature ranges, and effectively solves the impact of environmental changes on product quality during transportation. At the same time, the present invention can tolerate different water qualities such as C water, D water, and 3WHO water, and the product has a high suspension rate, which meets the use of different countries and regions and is conducive to large-scale promotion and application. DETAILED DESCRIPTION

[0068] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention will be described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0069] In addition, in order to better illustrate the present invention, numerous specific details are provided in the specific embodiments below. It should be understood by those skilled in the art that the present invention can be implemented without certain specific details. In some embodiments, raw materials, schemes, methods, means, etc. well known to those skilled in the art are not described in detail, so as to highlight the main purpose of the present invention.

[0070] Unless explicitly stated otherwise, throughout the specification and claims, the term “comprise” or variations such as “include” or “comprising”, etc., will be understood to include the stated elements or components but not to exclude other elements or components.

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

[0072] In the following examples, mancozeb, tebuconazole and difenoconazole can all be obtained from commercial sources, and other auxiliary agents are also commercially available products.

[0073] The present invention is further described in detail below through some examples.

[0074] Test Example 1 Indoor Toxicity Determination

[0075] The fungicidal and synergistic effects of mancozeb, tebuconazole and difenoconazole were determined by indoor toxicity determination. According to the Sun Yunpei method, the co-toxicity coefficient (CTC) of the drugs after compounding in a certain proportion was determined. CTC < 80 was antagonistic, 80 ≤ CTC ≤ 120 was additive, and CTC > 120 was synergistic.

[0076] Test agents: Mancozeb technical, tebuconazole technical, and difenoconazole technical were provided by Shandong Weifang Runfeng Chemical Co., Ltd.

[0077] Experimental design: After the effective inhibition concentration range of each agent is determined by preliminary test, a series of concentration treatments are set for each agent according to the content of active ingredients, and a water control is set. The test is carried out in accordance with the industry standard SY / T1156.15-2008 "Guidelines for Indoor Bioassay Tests of Pesticides·Fungicides·Part 15: Tests for Control of Wheat Leaf Rust·Pot Method", and the pot method is used to determine the EC of the agents and the mixtures. 50 The co-toxicity coefficient was calculated using the method for calculating the combined toxicity proposed by Sun Yunpei et al. (1960).

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

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

[0080] Toxicity index (TI) of difenoconazole = EC of mancozeb 50 / EC of difenoconazole 50 ×100.

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

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

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

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

[0085] P 代森锰锌 is the proportion of mancozeb in the compound composition;

[0086] P 戊唑醇 is the proportion of tebuconazole in the compound composition;

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

[0088] The present invention is a combination of three original drugs, and can also be calculated by the toxicity index of the binary mixture + the toxicity index of another single agent: Theoretical toxicity index (TTI) of M = binary mixture ATI × P 二元混剂 + another single dose of 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) when used together (= EC of mancozeb) 50 / EC of component (A+B) (or B+C or C+A) 50 ×100), P 二元混剂 is the proportion of component A+B (or B+C or C+A) in the composite composition; the other single dose TI is the TI of component C (or A or B), P 另一混剂 is the proportion of component C (or A or B) in the compound composition), so as to illustrate from multiple angles that the ternary composition of the present invention has a synergistic effect.

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

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

[0091]

[0092]

[0093] As shown in Table 1, the EC values ​​of mancozeb, tebuconazole and difenoconazole against wheat leaf rust were 50The mass ratios of mancozeb, tebuconazole and difenoconazole are within the range of (10-25):(1-3):1, the optional weight ratio is (10-15):(1-3):1, the optional weight ratio is (15-25):(1.5-3):1, the optional weight ratio is 15:(1-2):1, the optional weight ratio is 10:1:1, 10:3:1, 15:1.5:1, 25:3:1, the co-toxicity coefficients of the composite composition are all greater than 120, showing a synergistic effect. When the mass ratios of mancozeb, tebuconazole and difenoconazole are 9:1:1, 8:3:1, 28:2:1, the co-toxicity coefficients are only 116.09, 112.98 and 115.26, showing an additive effect.

[0094] Preparation Example

[0095] Example 1, dry suspension

[0096] The present embodiment provides a dry suspension concentrate, wherein the contents of the components are as follows (wt%): 20% of active ingredient, 1% of sodium lignin sulfonate as a dispersant, 0.5% of sodium polycarboxylate, 0.5% of alkylphenol polyoxyethylene ether succinate sulfonate, 1% of sodium lauryl sulfate as a wetting agent, 1% of pull-opening powder BX, 1% of ammonium sulfate as a disintegrant, 1% of diammonium hydrogen phosphate, 0.1% of organic silicone as a defoaming agent, and 100% of kaolin as a filler, wherein 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 dry suspension is as follows: mancozeb, tebuconazole, difenoconazole, a dispersant, a wetting agent, a disintegrant, a defoaming agent, a filler and water are mixed to obtain a slurry; the slurry after uniform mixing is sand-milled to a particle size of 3-5 μm; after sand-milling, the mixture is spray-dried and granulated to obtain a mancozeb, tebuconazole and difenoconazole dry suspension of 80-120 meshes.

[0098] Examples 2-10 and Comparative Example 1, dry suspension

[0099] Referring to the method of Example 1, dry suspension preparations of Examples 2-10 and Comparative Example 1 were prepared respectively. The raw material compositions of Examples 2-10 and Comparative Example 1 are shown in Table 2.

[0100] Table 2, dry suspension formulations of Examples 2-10 and Comparative Example 1 (wt%)

[0101]

[0102]

[0103] Test Example 2: Physical and Chemical Indicators of Dry Suspension Preparations

[0104] The performance of the products obtained from the above dry suspension examples 1-10 and comparative example 1 was tested, and the results are shown in the table below. The testing methods for various performance indicators are as follows: the wetting time was tested using the wettability test method for pesticide wettable powders in GB / T 5451-2001, the suspension rate was tested using the suspension rate test method for pesticides in GB / T14825-2023, the sieving condition was tested using the fineness test method for pesticide powders and wettable powders in GB / T16150-1995, the persistent foaming property was tested using the test method of CIPACMT 47 "Determination of persistent foaming property", and the hot storage stability (performance before and after hot storage) was tested using the hot storage stability test method for pesticides in GB / T19136-2003.

[0105] Table 3. Product performance of dry suspension concentrates of Examples 1-10 and Comparative Examples

[0106]

[0107] As shown in Table 4, the finished dry suspension concentrates prepared by the present invention have the characteristics of high suspension rate, short wetting time, low foaming, good sieving property and good thermal storage stability. The quality of Comparative Example 1 is poor before and after thermal storage. After being stored at 54°C for 14 days and then transferred to room temperature, the suspension rate of the sample decreases, the sieving property is unqualified, and the wetting time exceeds 60s. The quality of Examples 1-4 deteriorates slightly after thermal storage, while the quality of Examples 5-10 is good before and after thermal storage. The preferred auxiliary agent plays a key role in product quality.

[0108] Example 11, dispersible oil suspension

[0109] The present embodiment provides a dispersible oil suspension, wherein the contents of the components are as follows (wt%): 20% of active ingredient, 6% of polyarylphenol polyoxyethylene ether as emulsifier, 4% of calcium alkylbenzene sulfonate, 1% of sodium succinate diester sulfonate as dispersant, 1% of organic bentonite as thickener, 4% of fumed silica, and 100% of rapeseed oil methyl ester as dispersion medium, wherein 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 dispersible oil suspension is as follows: a dispersion medium, a thickener, an emulsifier and a dispersant are mixed and dispersed uniformly, then mancozeb, tebuconazole and difenoconazole are added, the mixture is fully sheared and mixed uniformly, and then the mixture is ground until the particle size D90 is less than 6 μm, so as to obtain a dispersible oil suspension of mancozeb, tebuconazole and difenoconazole.

[0111] Examples 12-20 and Comparative Example 2, dispersible oil suspension

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

[0113] Table 4, Dispersible Oil Suspension Concentrate Formulations of Examples 12-20 and Comparative Example 2 (wt%)

[0114]

[0115]

[0116] Test Example 3: Physical and Chemical Indicators of Dispersible Oil Suspension Preparations

[0117] The performance of the products obtained from the above dispersible oil suspension examples 11-20 and comparative example 2 was tested, and the results are shown in Table 5. Among them, the suspension rate was tested according to the GB / T14825-2023 pesticide suspension rate determination method, the pourability (residue after pouring) was tested according to the GB / T31737-2015 pesticide pourability determination method, the dispersion stability was tested according to the International Pesticide Analysis Cooperation Committee CIPAC MT 180 "Dispersion Stability Determination of Suspoemulsions", and the hot storage stability (performance before and after hot storage) was tested according to the GB / T19136-2003 pesticide hot storage stability determination method.

[0118] Table 5. Product performance of dispersible oil suspensions of Examples 11-20 and Comparative Example 2

[0119]

[0120] As shown in Table 5, the dispersible oil suspension concentrates prepared by the present invention have the characteristics of high suspension rate, small amount of dumping residue, good dispersion stability and good heat storage stability. The quality of Comparative Example 2 is poor before and after heat storage. After being stored at 54°C for 14 days and then transferred to room temperature, the suspension rate of the sample decreases and the oil separation rate reaches 15%. The quality of Examples 11-14 deteriorates slightly after heat storage, while the quality of Examples 15-20 is good before and after heat storage. The preferred additive plays a key role in product quality.

[0121] Field test examples, soybean field rust efficacy test

[0122] This experiment was arranged in a farmland in the suburbs of Hanting District, Weifang City, Shandong Province. The terrain is flat, the land is level, the irrigation and drainage facilities are complete, the field management level is consistent, and the fertility is uniform and medium. The application of pesticides was at the early stage of soybean rust. The experiment set up 8 treatments (using Example 2, Example 8, Example 12, Example 18, Comparative Example 1, Comparative Example 2, 64% mancozeb·difenoconazole wettable powder (commercially available), and clear water as a control), each treatment was repeated 3 times, a total of 24 plots, each plot area was 40m2 , randomized block arrangement. The clean water control refers to the use of clean water spray without spraying pesticides, and the rest of the test areas are pesticide treatment areas. The pesticide application method is: spray the pesticide twice with a Gongnong-16 backpack manual sprayer, and prepare the pesticide solution by diluting 450kg of water per hectare, and evenly spray the pesticide solution in the converted area. During the test, the water used for the preparation of the pesticide solution was 3WHO water prepared in the laboratory.

[0123] Investigate the disease base before applying the pesticide, investigate the control effect 14 days after the second application of the pesticide, calculate the control effect, and observe the safety of the test agent on crops.

[0124] Survey method: 20 plants were sampled at 5 diagonal points in each plot, and 4 leaves were surveyed on the top, middle and bottom of each plant. The total number of leaves and the number of diseased leaves at each level were recorded. The disease situation was recorded leaf by leaf according to the following 9-level classification standard:

[0125] Level 0: no disease;

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

[0127] Level 3: The lesion area accounts for 6-25% of the entire leaf area;

[0128] Level 5: The lesion area accounts for 26-50% of the entire leaf area;

[0129] Level 7: The lesion area accounts for 51-75% of the entire leaf area;

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

[0131] Calculation method of 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 of control area before treatment × disease index of treated area after treatment / disease index of control area after treatment × disease index of treated area before treatment) × 100.

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

[0135] Table 6. Field efficacy test results of each treatment agent for controlling soybean rust

[0136]

[0137]

[0138] It can be seen from the test results in Table 6 above that mancozeb, tebuconazole and difenoconazole can effectively prevent and control soybean rust after compounding. 14 days after the last application of the pesticide, the control effects of Examples 2, 8, 12, and 18 on soybean rust are significantly better than those of the control agent and Comparative Example 1 and Comparative Example 2, showing a synergistic effect.

[0139] According to the observation of the whole process of field test, soybeans grew well within the test dosage range, and no pesticide damage occurred in any treatment agent, indicating that it is 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, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A fungicidal composition containing mancozeb, tebuconazole and difenoconazole, characterized in that: The bactericidal active ingredients include mancozeb, tebuconazole and difenoconazole, and the weight ratio of the mancozeb, tebuconazole and difenoconazole is (0.1-99): (0.1-30):

1.

2. The bactericidal composition according to claim 1, characterized in that 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):(1.5-3):1, optionally 10:1:1, 10:3:1, 15:1.5:1, 25:3:

1.

3. The bactericidal composition according to claim 1 or 2, characterized in that The active ingredient accounts for 1-99% of the total weight of the composition, optionally 10%-80%, optionally 30%-75%, optionally 30%-60%, optionally 40%-60%.

4. The bactericidal composition according to any one of claims 1 to 3, characterized in that The dosage form of the bactericidal composition is one or more of a dry suspension, a water suspension, a dispersible oil suspension, a wettable powder, a water dispersible granule, a granule, and a seed treatment agent; Optionally, the bactericidal composition further comprises an auxiliary agent, and the auxiliary agent is selected from one or more of a dispersant, a wetting agent, a filler, an emulsifier, a thickener, a dispersion medium, a disintegrant, a solvent, a preservative, an antifreeze agent, a specific gravity regulator, a defoaming agent, an oil phase wall material, an aqueous phase wall material, and water.

5. The bactericidal composition according to any one of claims 1 to 4, characterized in that: The dosage form of the bactericidal composition is a dry suspension; Optionally, the bactericidal composition comprises the following raw materials in percentage by weight: Bactericidal active ingredient 20-75%, optionally 30%-75%, optionally 30%-65%, optionally 40%-60%, optionally 45%-55%; Dispersant 2-20%, optionally 5-10%, optionally 5-9%; Wetting agent 2-10%, optionally 3-5%; Disintegrant 1-10%, optionally 2-5%, optionally 2-4.5%, optionally 3-4.5%; Defoaming agent 0.1-2%, optionally 0.1-1%, optionally 0.4-1%, optionally 0.4-0.9%, optionally 0.4-0.8%; Filler 12-40%, optional supplement to 100%; Preferably, the bactericidal composition is composed of 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 defoaming agent, and the balance of filler; Optionally, the dispersant is one or more of sodium lignin sulfonate, sodium salt of polycarboxylate, sodium salt of maleic acid-acrylic acid copolymer, sodium salt of ethylene oxide-propylene oxide block copolymer, sodium salt of alkylnaphthalenesulfonic acid formaldehyde condensate, sodium salt of naphthalenesulfonic acid formaldehyde condensate, alkylphenol polyoxyethylene ether formaldehyde condensate, fatty alcohol polyoxyethylene ether sulfate and alkylphenol polyoxyethylene ether succinate sulfonate; Optionally, the dispersant is selected from at least three of sodium salt of naphthalenesulfonic acid formaldehyde condensate, sodium salt of polycarboxylate, sodium lignin sulfonate, sodium salt of alkylnaphthalenesulfonic acid 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 salt of naphthalenesulfonic acid formaldehyde condensate, sodium salt of polycarboxylate and sodium lignin sulfonate, and optionally, the weight ratio of sodium salt of naphthalenesulfonic acid formaldehyde condensate, sodium salt of polycarboxylate and sodium lignin sulfonate is (2-5):(1-2): (1-2), optionally (3-5): (1-2): (1-2), optionally (2-3): 1:1; Optionally, 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 opening powder BX; Optionally, 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, and sodium lignin sulfonate; Optionally, the wetting agent includes sodium dodecyl sulfate and sodium alkylnaphthalene sulfonate; Optionally, the weight ratio of sodium dodecyl sulfate and sodium alkylnaphthalene sulfonate is (1-2):(2-3), and optionally 1:(1-2); Optionally, the disintegrant is one or more of ammonium sulfate, potassium sulfate, urea, diammonium hydrogen phosphate, and sodium methylcellulose; Optionally, the disintegrant comprises ammonium sulfate and urea, and the weight ratio of ammonium sulfate to urea is (1-2):(1-3), and optionally 1:(1-2); Optionally, the defoaming agent is one or more of organic silicones, organic siloxanes, high-carbon alcohol fatty acid ester complexes, C10-C20 saturated aliphatic carboxylic acids, and C10-C20 saturated aliphatic carboxylic acid esters; Optionally, the filler is one or more of kaolin, light calcium carbonate, diatomaceous earth, bentonite and barium sulfate.

6. The bactericidal composition according to any one of claims 1 to 4, characterized in that: The dosage form of the bactericidal composition is a dispersible oil suspension; Optionally, the bactericidal composition comprises the following raw materials in percentage by weight: Bactericidal active ingredient 20-75%, optionally 20%-60%, optionally 25%-60%, optionally 30%-55%, optionally 35%-55%, optionally 35%-52.5%; Emulsifier 10-35%, optionally 12-35%, optionally 12-20%; Dispersant 1-5%, optionally 2-5%, optionally 2-4%, optionally 2-3%; Thickener 0.5-5%, optionally 1-3%, optionally 1.5-3%; Dispersing medium 13.5-41.5%, optionally 31-40.5%, optionally filled to 100%; Optionally, the bactericidal composition is composed of the following components in weight percentage: bactericidal active ingredient 20-60% (preferably 25%-60%, more preferably 30%-55%), emulsifier 12-30%, dispersant 2-5%, thickener 1-3%, and dispersion medium supplemented to 100%; Optionally, the emulsifier includes one or more of fatty amine polyoxyethylene ether, polyarylphenol polyoxyethylene ether, calcium alkylbenzene sulfonate, castor oil polyoxyethylene ether, polyoxyethylene sorbitan monooleate, styrylphenol 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), and optionally 1:(2-4); Optionally, the dispersant is selected from one or more of alkylnaphthalene sulfonate formaldehyde condensate, sodium succinate diester sulfonate, polyoxyethylene-polyoxypropylene block copolymer, calcium lignin sulfonate and modified polyacrylic acid copolymer; Optionally, the dispersant comprises alkylnaphthalene sulfonate formaldehyde condensate and polyoxyethylene-polyoxypropylene block copolymer; Optionally, the weight ratio of alkylnaphthalene sulfonate formaldehyde condensate and polyoxyethylene-polyoxypropylene block copolymer is (1-1.5):(1-2), optionally 1:(1-2); Optionally, the thickener is one or more of fumed silica, organic bentonite, and urea; Optionally, the thickener includes fumed silica and organic bentonite; Optionally, the weight ratio of fumed silica to organic bentonite is (1-2):1, optionally 2:1; Optionally, the dispersion medium is one or more of methyl oleate, castor oil, rapeseed oil methyl ester and solvent oil.

7. A method for preparing the bactericidal composition according to claim 5, characterized in that: Mancozeb, tebuconazole, difenoconazole, a dispersant, a wetting agent, a disintegrant, a defoaming agent, a filler and water are mixed to obtain a slurry; the uniformly mixed slurry is sand-milled to a desired particle size, and the mixture is spray-dried and granulated to obtain a dry suspension of mancozeb, tebuconazole and difenoconazole.

8. A method for preparing the bactericidal composition according to claim 6, characterized in that: The dispersion medium, thickener, emulsifier and dispersant are mixed and dispersed uniformly, and then mancozeb, tebuconazole and difenoconazole are added, and the mixture is fully sheared and mixed uniformly, and then the mixture is ground to a desired particle size to obtain a dispersible oil suspension of mancozeb, tebuconazole and difenoconazole.

9. Use of the fungicidal composition according to any one of claims 1 to 6, or the preparation prepared by the preparation method according to claim 7 or 8 in preventing and controlling crop diseases.

10. The use according to claim 9, characterized in that: The crop diseases include diseases of rice, soybean, wheat, peanut, corn, cotton, sunflower, 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.

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