A fungicide composition containing pyraclostrobin and mancozeb

Abstract

This invention relates to the field of pesticide technology, specifically to a fungicide composition containing pyraclostrobin and mancozeb. The pyraclostrobin comprises 3-15% by weight of the fungicide composition; the mancozeb comprises 20-75% by weight of the fungicide composition; and the fungicide composition further comprises alkoxylated shea butter alcohol.

Description

Technical Field

[0001] This invention relates to the field of pesticide technology, and specifically to a fungicide composition containing pyraclostrobin and mancozeb. Background Technology

[0002] Pyraclostrobin, also known as azoxystrobin, is mainly used on various crops such as wheat, peanuts, rice, vegetables, fruit trees, tobacco, tea trees, ornamental plants, and lawns to control a variety of diseases caused by ascomycetes, basidiomycetes, deuteromycetes, and oomycetes, including leaf blight, rust, powdery mildew, downy mildew, blight, anthracnose, scab, brown spot, and damping-off. It also shows good control effects against powdery mildew and downy mildew in cucumbers, black spot and leaf spot in bananas, downy mildew, anthracnose, and powdery mildew in grapes, and early blight, late blight, powdery mildew, and leaf blight in tomatoes and potatoes. It can control most diseases of ascomycetes, basidiomycetes, deuteromycetes, and oomycetes. It has a strong inhibitory effect on spore germination and mycelial growth within leaves, exhibiting both protective and curative activity. It has penetrating and systemic activity, a long residual effect, and is resistant to rain washout. It is widely used to control diseases in wheat, rice, peanuts, grapes, vegetables, potatoes, bananas, lemons, coffee, fruit trees, walnuts, tea trees, tobacco, ornamental plants, lawns, and other field crops.

[0003] However, due to the development of pathogen resistance to pyraclostrobin as a single fungicide component after long-term use, the antibacterial and control efficacy of pyraclostrobin is severely affected. Furthermore, existing fungicides formulated with pyraclostrobin and other components have stability issues, easily leading to instability and affecting drug efficacy, especially during periods of frequent climate change, where their control effect differs significantly from that obtained in laboratory tests. Summary of the Invention

[0004] To address the aforementioned technical problems, a first aspect of the present invention provides a fungicide composition containing pyraclostrobin and mancozeb, wherein the weight ratio of pyraclostrobin to mancozeb is (3-20):(5-80); the fungicide composition further includes alkoxylated tallow alcohol.

[0005] As a preferred technical solution, the bactericide composition further includes polyether-modified siloxane.

[0006] As a preferred technical solution, the formulation of the bactericidal composition includes wettable powder, seed coating agent, dispersible oil suspension, and water-dispersible granules.

[0007] As a preferred technical solution, the raw materials for preparing the dispersible oil suspension include 1-5 wt% antifreeze, 1-5 wt% thickener, 1-4 wt% stabilizer, 30-35 wt% mancozeb, 5-10 wt% pyraclostrobin, 1-10 wt% alkoxylated shea butter, 1-10 wt% polyether-modified siloxane, and the balance being a dispersion medium; the antifreeze is selected from one or more of ethylene glycol, propylene glycol, glucose, glycerol, and polyethylene glycol.

[0008] As a preferred technical solution, the preparation method of the dispersible oil suspension includes the following steps:

[0009] The dispersion medium, stabilizer, alkoxylated tallow alcohol and polyether-modified siloxane are added to the reaction vessel and mixed and dispersed; pyraclostrobin and mancozeb technical, thickener and antifreeze are added under high-speed shearing, and the mixture is ground by sand mill until the particle size is less than 5 micrometers.

[0010] As a preferred technical solution, the weight ratio of the alkoxylated shea butter alcohol and the polyether modified siloxane is (1:4) to (4:1).

[0011] As a preferred technical solution, the raw materials for preparing the polyether-modified siloxane include unsaturated polyethers and hydrogen-containing silicone oils; the unsaturated polyethers include allyl alcohol polyethers and allyl polyoxyethylene polyoxypropylene epoxy ethers.

[0012] As a preferred technical solution, the weight ratio of the allyl alcohol polyether and the allyl polyoxyethylene polyoxypropylene epoxy ether is (2-3):1.

[0013] As a preferred technical solution, the bactericide composition further includes potassium dismutate rosinate.

[0014] A second aspect of the invention provides the application of the fungicide composition containing pyraclostrobin and mancozeb as described above in the control of scab, downy mildew and blight in vegetables and fruit trees.

[0015] This invention utilizes a combination of pyraclostrobin and mancozeb to prepare a fungicide composition, leveraging their synergistic effect to enhance the control of scab, downy mildew, and blight in vegetables and fruit trees. Simultaneously, the synergistic effect of adjuvants such as alkoxylated tallow alcohol and polyether-modified organosiloxanes improves the stability of the composition, as well as the suspension rate, fungicidal and control efficacy, and leaf spread of the prepared dispersible oil suspension. Detailed Implementation

[0016] The technical features of the present invention will be further clearly and completely described below with reference to specific embodiments, but this is not intended to limit the scope of protection.

[0017] The terms "preferred," "more preferably," and "more suitable" used in this invention refer to embodiments of the invention that provide certain beneficial effects under certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, the description of one or more preferred embodiments does not imply that other embodiments are unavailable, nor is it intended to exclude other embodiments from the scope of this invention.

[0018] It will be understood by those skilled in the art that, unless otherwise defined, all terms used herein (including technical and scientific terms) have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. It should also be understood that terms such as those defined in general dictionaries should be understood to have the same meaning as in the context of the prior art, and should not be interpreted in an idealized or overly formal sense unless defined as herein.

[0019] A first aspect of the present invention provides a fungicide composition containing pyraclostrobin and mancozeb, wherein the weight ratio of pyraclostrobin to mancozeb is (3-20):(5-80); the fungicide composition further includes alkoxylated tallow alcohol.

[0020] Preferably, the alkoxylated shea butter alcohol accounts for 1 to 10 wt% of the bactericide composition.

[0021] More preferably, the weight ratio of pyraclostrobin to mancozeb is (5-10):(30-35).

[0022] The chemical name of the pyraclostrobin described in this invention is N-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]phenyl]-N-methoxycarbamate, and its molecular structure is as follows:

[0023]

[0024] Pyraclostrobin belongs to the methoxyacrylate fungicide class and is a mitochondrial respiration inhibitor. It inhibits mitochondrial respiration by blocking electron transfer between mitochondrial pigments b and C1, preventing mitochondria from producing and providing the energy (ATP) needed for normal cellular metabolism, ultimately leading to cell death. Pyraclostrobin has a strong ability to inhibit fungal spore germination and effectively inhibits mycelial growth within leaves. It has a long residual effect and potential therapeutic activity. While its translocation and fumigation effects within leaves are weak, its translocation activity within the plant is strong. Pyraclostrobin possesses protective, curative, systemic, and rain-washable properties, and has a wide range of applications. Although pyraclostrobin inhibits the activity of tested resistant strains of pathogens, it should be used at the recommended dosage and mixed in a container with other fungicides without cross-resistance, or the mixture should be applied directly. The number of applications per growing season should be strictly limited to delay the development and progression of resistance.

[0025] The chemical name of the manganese zinc described in this invention is a complex salt of manganese and zinc ethylene dithiocarbamate, CAS number 8010-01-7, molecular formula (C4H6MnN2S4)xZny, relative molecular mass (265.24)x+(65.38)y, and molecular structure is as follows:

[0026]

[0027] The mancozeb in this invention can be purchased commercially or prepared by the manufacturer. The synthesis steps are as follows: 1) Carbon disulfide is slowly added dropwise to an aqueous solution of ethylenediamine and sodium hydroxide to produce sodium mancozeb; 2) MnSO4 is added to sodium mancozeb to produce mancozeb; 3) ZnSO4 is added to produce mancozeb zinc. After the reaction is complete, the obtained wet mancozeb zinc is mixed with an organic solvent and distilled to remove water.

[0028] The alkoxylated shea butter alcohol described in this invention is a compound containing long aliphatic carbon chains and alkoxy groups in its structure, resulting from the alkoxylation treatment of shea butter alcohol through a reaction between monomers containing epoxy groups. The applicant discovered that adding a certain amount of alkoxylated shea butter alcohol to a fungicide composition combining pyraclostrobin and mancozeb can resist rain washout and improve the inhibition of citrus scab, cucumber downy mildew, cucumber blight, and grape downy mildew to a certain extent. Even after spraying and subsequent rain washout, the efficacy of the fungicide composition is not significantly affected. This is likely because the alkoxylated shea butter alcohol has good interaction with pyraclostrobin and mancozeb. The long carbon chains and hydrophilic alkoxy groups on the shea butter alcohol molecule effectively disperse pyraclostrobin and mancozeb, allowing them to spread well on the surface of crop leaves. Meanwhile, due to the balance between the hydrophobic effect of the large carbon chain of shea butter and the hydrophilic effect of the alkoxy group, the surface tension of the fungicide composition can be very low, which further improves the wetting and spreading ability of the composition. It can penetrate into the surface of crop leaves better and form a film on the leaf surface, thereby increasing the adhesion between the film and the leaf surface and prolonging the fungicide time of the composition.

[0029] The present invention does not impose any special limitation on the source of alkoxylated tallow alcohol. It can be prepared by alkoxylation reaction methods of alcohols known to those skilled in the art, or it can be purchased from the market, such as Winwin Degussa.

[0030] In some preferred embodiments, the bactericide composition further includes polyether-modified siloxanes. Preferably, the raw materials for preparing the polyether-modified siloxanes include unsaturated polyethers and hydrogen-containing silicone oils; the unsaturated polyethers include allyl alcohol polyethers and allyl polyoxyethylene polyoxypropylene epoxy ethers.

[0031] The polyether-modified siloxane in this invention utilizes the reaction between the unsaturated double bonds in the polyether and the terminal hydrogen atoms in the organosiloxane to graft polyether segments onto the organosiloxane backbone, increasing the polar groups on the organosiloxane molecular chain. Because mancozeb contains strongly polar imino and sulfur groups, its intramolecular forces are very strong, making it prone to aggregation, dissolution, and dispersion. The interaction between mancozeb and pyraclostrobin molecules needs improvement. The applicant discovered that by adding a certain amount of polyether-modified organosiloxane to the compounded pyraclostrobin and mancozeb, along with a certain amount of alkoxylated shea butter alcohol, the intramolecular forces of mancozeb can be effectively broken, improving its interaction with pyraclostrobin. This also improves the dispersibility and stability of these components in the dispersion medium, facilitating the spread of the fungicidal composition on the surface of the treated organisms such as vegetables and fruit trees. Furthermore, it helps prevent drift during use, promotes film formation on crop surfaces, prolongs the fungicidal time, and increases the fungicide rate.

[0032] The polyether-modified siloxane in this invention is prepared by the following method:

[0033] 1) Add 100g of octamethylcyclotetrasiloxane, 7.2g of hexamethyldisiloxane, 28.5g of high-hydrogen-content silicone oil with a hydrogen content of 1.56% and 6g of acidic clay to a reaction vessel, heat to 60℃ and react for 4 hours to obtain low-hydrogen-content silicone oil with a hydrogen content of 0.3%;

[0034] 2) Add 50g of the low-hydrogen silicone oil, 95g of unsaturated polyether, 20g of diethylene glycol and 6.8mg of platinum-rhodium complex solution to the reaction vessel, and react for 5 hours at a reaction temperature of 110℃ and normal pressure. After there are no more excess Si-H bonds, cool down to obtain the final product.

[0035] Preferably, the weight ratio of the allyl alcohol polyether to the allyl polyoxyethylene polyoxypropylene epoxy ether is (2-3):1; more preferably, the weight ratio of the allyl alcohol polyether to the allyl polyoxyethylene polyoxypropylene epoxy ether is 2.5:1. In this invention, the allyl alcohol polyether is HMS-232R (hydroxyl value approximately 75 mg KOH / g) from Zhejiang Huangma Chemical Co., Ltd., and the allyl polyoxyethylene polyoxypropylene epoxy ether is a HY series product from Nanjing Zhongshan Chemical Co., Ltd., with an average molecular weight of 1000.

[0036] The applicant discovered that by adjusting the weight ratio of allyl alcohol polyether and allyl polyoxyethylene polyoxypropylene epoxy ether, the dispersion stability, low-temperature stability, and high-temperature stability of the dispersible oil suspension in the bactericidal composition can be significantly improved. This is likely because the two monomers can effectively control the cohesive energy density of the polyether-modified siloxane, increasing the interaction between the polyether-modified organosiloxane and pyraclostrobin, mancozeb, etc., promoting the full dispersion of these drugs along with the polyether-modified siloxane and other components, and avoiding problems such as agglomeration and flocculation of drug particles due to changes in temperature and other factors.

[0037] In some embodiments, the formulation of the bactericidal composition includes wettable powder, seed coating agent, dispersible oil suspension, and water-dispersible granules.

[0038] Preferably, the raw materials for preparing the dispersible oil suspension further include 1-5 wt% antifreeze, 1-5 wt% thickener, and 1-4 wt% stabilizer; the antifreeze is selected from one or more of ethylene glycol, propylene glycol, glucose, glycerol, and polyethylene glycol.

[0039] The thickener used in this invention is not specifically limited and can be selected from fumed silica, polyvinyl alcohol, bentonite, attapulgite, lithium magnesium silicate, etc.

[0040] The stabilizer is not specifically limited in this invention and can be selected from organic acids, organic bases, esters, alcohols, ethers (such as castor oil polyoxyethylene ether), etc.

[0041] In some embodiments, the method for preparing the dispersible oil suspension includes the following steps:

[0042] The dispersion medium, stabilizer, alkoxylated tallow alcohol and polyether-modified siloxane are added to the reaction vessel and mixed and dispersed; pyraclostrobin and mancozeb technical, thickener and antifreeze are added under high-speed shearing, and the mixture is ground by sand mill until the particle size is less than 5 micrometers.

[0043] Preferably, the dispersible oil suspension is prepared by grinding the particles to a particle size of less than 1 micrometer using a sand mill.

[0044] The dispersion medium is the solvent, including but not limited to methyl oleate or soybean oil.

[0045] In some embodiments, the weight ratio of the alkoxylated shea butter to the polyether-modified siloxane is (1:4) to (4:1); preferably, the weight ratio of the alkoxylated shea butter to the polyether-modified siloxane is 2:3.

[0046] The second aspect of the present invention provides a method for using the above-mentioned dispersible oil suspension. In addition to the conventional method, low-volume spraying technology can also be used to spray the above-mentioned dispersible oil suspension onto the corresponding crops.

[0047] The main difference between low-volume spraying technology and high-volume spraying in this invention lies in the diameter of the nozzle used. Generally, high-volume spraying refers to a sprayer with a nozzle diameter of 1.3 mm, while low-volume spraying is a method of spraying with a lower unit volume of liquid than usual. In this invention, by reducing the nozzle diameter of the sprayer, under constant pressure, the smaller nozzle results in finer droplets, increased coverage area, and a significant reduction in the amount of liquid used per unit area, even down to one-tenth of the conventional spraying volume. This method significantly improves application efficiency, reduces unnecessary labor and energy consumption, and effectively reduces pesticide usage while achieving better control effects, avoiding environmental pollution and cost pressures.

[0048] In some embodiments, the bactericide composition further includes potassium dismutate; preferably, the amount of potassium dismutate is 20-50 wt% of the mass of the alkoxylated tallow alcohol.

[0049] The potassium disproportionated rosinate in this invention is obtained by disproportionation reaction of rosin in the presence of a catalyst, which causes rearrangement between acid molecules of the acid resin through hydrogen transfer, thereby eliminating the conjugated double bond system. Its structural formula is:

[0050]

[0051] The applicant discovered that adding a certain amount of potassium dismutate to the bactericidal composition of this invention can significantly improve the efficacy of the composition and, to a certain extent, help increase the antibacterial rate. When the above-mentioned bactericidal composition is prepared as a dispersible oil suspension, and alkylated tallow alcohol and polyether-modified siloxane are used simultaneously, the dispersible oil suspension maintains good dispersion stability even after grinding components such as pyraclostrobin and mancozeb to particles with a diameter of less than 1 micrometer and dispersing them in dispersion media such as methyl oleate or soybean oil. It can be sprayed evenly using WFB-18A and 3MF-4 ultra-low volume sprayers, with appropriate droplet size, achieving good settling and coverage on plant surfaces, and exhibiting good penetration in plant thickets due to its relatively small size. Furthermore, the interaction between the above components improves the low-temperature and high-temperature stability of the dispersible oil suspension, while significantly improving the control rate against scab, downy mildew, and blight in vegetables and fruit trees. It is possible that the interaction of potassium disproportionate, alkylated shea butter, and polyether-modified siloxane can form micelles with small particle size and high thickness in the dispersion medium of the dispersible oil suspension, encapsulating pyraclostrobin and mancozeb within the micelles, ensuring their full dispersion and preventing aggregation and sedimentation. Meanwhile, because mancozeb is a complex of organic molecules and metal ions, it is highly sensitive to the acidity, alkalinity, and temperature of the system, and is prone to aggregation and clumping with environmental changes. However, through the synergistic effect of potassium disproportionate, alkylated shea butter, and polyether-modified siloxane, mancozeb is encapsulated within micelles of a specific particle size. Utilizing the charge characteristics of these three components, the micelle surface carries a specific charge, preventing frictional aggregation between adjacent micelles, further improving the stability of the dispersible oil suspension, and thus significantly improving the bactericidal effect of the bactericide composition.

[0052] The present invention will now be described in detail through embodiments. It should be noted that the following embodiments are for further illustration only and should not be construed as limiting the scope of protection of the present invention. Non-essential improvements and adjustments made by those skilled in the art based on the above description of the present invention still fall within the scope of protection of the present invention. Furthermore, unless otherwise stated, all raw materials used are commercially available products.

[0053] Example

[0054] Example 1 provides a dispersible oil suspension comprising a fungicide composition containing pyraclostrobin and mancozeb.

[0055] The preparation method of the dispersible oil suspension includes the following steps:

[0056] 2 wt% castor oil polyoxyethylene ether, 5 wt% alkoxylated tallow alcohol and 7 wt% polyether modified siloxane were added to the reaction vessel and mixed and dispersed; 6 wt% pyraclostrobin and 25 wt% mancozeb technical, 3 wt% bentonite and 2 wt% ethylene glycol and the balance methyl oleate were added under high-speed shearing and ground until the particle size was less than 3 micrometers.

[0057] The preparation method of the polyether-modified siloxane includes the following steps:

[0058] 1) Add 100g of octamethylcyclotetrasiloxane, 7.2g of hexamethyldisiloxane, 28.5g of high-hydrogen-content silicone oil with a hydrogen content of 1.56% and 6g of acidic clay to a reaction vessel, heat to 60℃ and react for 4 hours to obtain low-hydrogen-content silicone oil with a hydrogen content of 0.3%;

[0059] 2) Add 50g of the low-hydrogen silicone oil, 95g of allyl alcohol polyether (HMS-232R of allyl alcohol polyether from Zhejiang Huangma Chemical Co., Ltd.), 20g of diethylene glycol and 6.8mg of platinum-rhodium complex solution to the reaction vessel. React at 110℃ and atmospheric pressure for 5 hours. After there are no more excess Si-H bonds, cool down to obtain the final product.

[0060] Example 2 provides a dispersible oil suspension comprising a fungicide composition containing pyraclostrobin and mancozeb.

[0061] The preparation method of the dispersible oil suspension includes the following steps:

[0062] 2 wt% castor oil polyoxyethylene ether, 8 wt% alkoxylated tallow alcohol and 4 wt% polyether modified siloxane were added to the reaction vessel and mixed and dispersed; under high-speed shearing, 10 wt% pyraclostrobin and 35 wt% mancozeb technical, 3 wt% bentonite and 2 wt% ethylene glycol and the balance methyl oleate were added and ground until the particle size was less than 3 micrometers.

[0063] The polyether-modified siloxane described therein is the same as that in Example 1.

[0064] Example 3 provides a dispersible oil suspension comprising a fungicide composition containing pyraclostrobin and mancozeb.

[0065] The preparation method of the dispersible oil suspension includes the following steps:

[0066] Add 3 wt% castor oil polyoxyethylene ether, 4 wt% alkoxylated tallow alcohol, 1.6 wt% disproportionated rosinate potassium and 6 wt% polyether modified siloxane to a reaction vessel and mix and disperse; under high-speed shearing, add 5 wt% pyraclostrobin, 30 wt% mancozeb technical, 3 wt% bentonite, 2 wt% ethylene glycol and the balance methyl oleate and grind until the particle size is less than 3 micrometers to obtain the final product.

[0067] The polyether-modified siloxane described therein is the same as that in Example 1.

[0068] Example 4 provides a dispersible oil suspension comprising a fungicide composition containing pyraclostrobin and mancozeb.

[0069] The preparation method of the dispersible oil suspension includes the following steps:

[0070] Add 3 wt% castor oil polyoxyethylene ether, 4 wt% alkoxylated tallow alcohol, 1.6 wt% disproportionated rosinate potassium and 6 wt% polyether modified siloxane to a reaction vessel and mix and disperse; under high-speed shearing, add 5 wt% pyraclostrobin, 30 wt% mancozeb technical, 3 wt% bentonite, 2 wt% ethylene glycol and the balance methyl oleate and grind until the particle size is less than 3 micrometers to obtain the final product.

[0071] The preparation method of the polyether-modified siloxane includes the following steps:

[0072] 1) Add 100g of octamethylcyclotetrasiloxane, 7.2g of hexamethyldisiloxane, 28.5g of high-hydrogen-content silicone oil with a hydrogen content of 1.56% and 6g of acidic clay to a reaction vessel, heat to 60℃ and react for 4 hours to obtain low-hydrogen-content silicone oil with a hydrogen content of 0.3%;

[0073] 2) Add 50g of the low-hydrogen silicone oil, 95g of unsaturated polyether (a mixture of allyl alcohol polyether and allyl polyoxyethylene polyoxypropylene epoxy ether in a weight ratio of 2.5:1), 20g of diethylene glycol and 6.8mg of platinum-rhodium complex solution to a reaction vessel. React at 110℃ and atmospheric pressure for 5 hours. After there are no excess Si-H bonds, cool down to obtain the final product.

[0074] Example 5 provides a dispersible oil suspension comprising a fungicide composition containing pyraclostrobin and mancozeb.

[0075] The preparation method of the oil-dispersible suspension includes the following steps:

[0076] Add 3 wt% castor oil polyoxyethylene ether, 4 wt% alkoxylated tallow alcohol, 1.6 wt% disproportionated rosinate potassium and 6 wt% polyether modified siloxane to a reaction vessel and mix and disperse; under high-speed shearing, add 5 wt% pyraclostrobin and 20 wt% mancozeb technical, 3 wt% bentonite and 2 wt% ethylene glycol and the balance methyl oleate and grind until the particle size is less than 5 micrometers to obtain the final product.

[0077] The polyether-modified siloxane described therein is the same as that in Example 4.

[0078] Example 6 provides a dispersible oil suspension comprising a fungicide composition containing pyraclostrobin and mancozeb.

[0079] The preparation method of the oil-dispersible suspension includes the following steps:

[0080] Add 3 wt% castor oil polyoxyethylene ether, 4 wt% alkoxylated tallow alcohol, 1.6 wt% disproportionated rosinate potassium and 6 wt% polyether modified siloxane to a reaction vessel and mix and disperse; under high-speed shearing, add 5 wt% pyraclostrobin and 10 wt% mancozeb technical, 3 wt% bentonite and 2 wt% ethylene glycol and the balance methyl oleate and grind until the particle size is less than 5 micrometers to obtain the final product.

[0081] The polyether-modified siloxane described therein is the same as that in Example 4.

[0082] Example 7 provides a dispersible oil suspension comprising a fungicide composition containing pyraclostrobin and mancozeb.

[0083] The preparation method of the dispersible oil suspension includes the following steps:

[0084] Add 3 wt% castor oil polyoxyethylene ether, 4 wt% alkoxylated tallow alcohol, 1.6 wt% disproportionated rosinate potassium and 6 wt% polyether modified siloxane to a reaction vessel and mix and disperse; under high-speed shearing, add 5 wt% pyraclostrobin and 5 wt% mancozeb technical, 3 wt% bentonite and 2 wt% ethylene glycol and the balance methyl oleate and grind until the particle size is less than 5 micrometers to obtain the final product.

[0085] The polyether-modified siloxane described therein is the same as that in Example 4.

[0086] Example 8 provides a dispersible oil suspension comprising a fungicide composition containing pyraclostrobin and mancozeb.

[0087] The preparation method of the dispersible oil suspension includes the following steps:

[0088] Add 3 wt% castor oil polyoxyethylene ether, 4 wt% alkoxylated tallow alcohol, 1.6 wt% disproportionated rosinate potassium and 6 wt% polyether modified siloxane to a reaction vessel and mix and disperse; under high-speed shearing, add 3 wt% pyraclostrobin and 24 wt% mancozeb technical, 3 wt% bentonite and 2 wt% ethylene glycol and the balance methyl oleate and grind until the particle size is less than 5 micrometers to obtain the final product.

[0089] The polyether-modified siloxane described therein is the same as that in Example 4.

[0090] Example 9 provides a dispersible oil suspension comprising a fungicide composition containing pyraclostrobin and mancozeb.

[0091] The preparation method of the dispersible oil suspension includes the following steps:

[0092] Add 3 wt% castor oil polyoxyethylene ether, 4 wt% alkoxylated tallow alcohol, 1.6 wt% disproportionated rosinate potassium and 6 wt% polyether modified siloxane to a reaction vessel and mix and disperse; under high-speed shearing, add 3 wt% pyraclostrobin, 30 wt% mancozeb technical, 3 wt% bentonite, 2 wt% ethylene glycol and the balance methyl oleate and grind until the particle size is less than 5 micrometers to obtain the final product.

[0093] The polyether-modified siloxane described therein is the same as that in Example 4.

[0094] Example 10 provides a dispersible oil suspension comprising a fungicide composition containing pyraclostrobin and mancozeb.

[0095] The preparation method of the oil-dispersible suspension includes the following steps:

[0096] Add 3 wt% castor oil polyoxyethylene ether, 1.6 wt% potassium dismutate and 6 wt% polyether-modified siloxane to a reaction vessel and mix and disperse; under high-speed shearing, add 5 wt% pyraclostrobin, 20 wt% mancozeb technical, 3 wt% bentonite and 2 wt% ethylene glycol and the balance methyl oleate and grind until the particle size is less than 5 micrometers to obtain the final product.

[0097] The polyether-modified siloxane described therein is the same as that in Example 4.

[0098] Example 11 provides a dispersible oil suspension comprising a fungicide composition containing pyraclostrobin and mancozeb.

[0099] The preparation method of the dispersible oil suspension includes the following steps:

[0100] Add 3 wt% castor oil polyoxyethylene ether, 4 wt% alkoxylated tallow alcohol, and 1.6 wt% disproportionated rosinate to a reaction vessel and mix and disperse. Under high-speed shearing, add 5 wt% pyraclostrobin, 20 wt% mancozeb technical, 3 wt% bentonite, 2 wt% ethylene glycol, and the balance methyl oleate and grind until the particle size is less than 5 micrometers to obtain the final product.

[0101] The polyether-modified siloxane described therein is the same as that in Example 4.

[0102] Example 12 provides a dispersible oil suspension comprising a fungicide composition containing pyraclostrobin and mancozeb.

[0103] The preparation method of the dispersible oil suspension includes the following steps:

[0104] Add 3 wt% castor oil polyoxyethylene ether, 4 wt% alkoxylated tallow alcohol and 6 wt% polyether modified siloxane to a reaction vessel and mix and disperse; under high-speed shearing, add 5 wt% pyraclostrobin and 20 wt% mancozeb technical, 3 wt% bentonite and 2 wt% ethylene glycol and the balance methyl oleate and grind until the particle size is less than 5 micrometers to obtain the final product.

[0105] The polyether-modified siloxane described therein is the same as that in Example 4.

[0106] Example 13 provides a dispersible oil suspension comprising a fungicide composition containing pyraclostrobin and mancozeb.

[0107] The preparation method of the dispersible oil suspension includes the following steps:

[0108] Add 3 wt% castor oil polyoxyethylene ether, 4 wt% alkoxylated tallow alcohol, 1.6 wt% disproportionated rosinate potassium and 6 wt% polyether modified siloxane to a reaction vessel and mix and disperse; under high-speed shearing, add 5 wt% pyraclostrobin and 20 wt% mancozeb technical, 3 wt% bentonite and 2 wt% ethylene glycol and the balance methyl oleate and grind until the particle size is less than 5 micrometers to obtain the final product.

[0109] The preparation method of the polyether-modified siloxane includes the following steps:

[0110] 1) Add 100g of octamethylcyclotetrasiloxane, 7.2g of hexamethyldisiloxane, 28.5g of high-hydrogen-content silicone oil with a hydrogen content of 1.56% and 6g of acidic clay to a reaction vessel, heat to 60℃ and react for 4 hours to obtain low-hydrogen-content silicone oil with a hydrogen content of 0.3%;

[0111] 2) Add 50 g of the low-hydrogen-content silicone oil, 95 g of unsaturated polyether (allyl polyoxyethylene polyoxypropylene epoxy ether), 20 g of diethylene glycol, and 6.8 mg of platinum-rhodium complex solution to a reaction kettle. React at a reaction temperature of 110°C and normal pressure for 5 hours. After there are no excess Si—H bonds, cool down to obtain the product.

[0112] Performance evaluation

[0113] According to the standards of NY / T 1156.2 - 2006 and NY / T 1156.2 - 2006 specified in the "Pesticide Bioassay Experimental Guidelines for Fungicides in the Laboratory", the toxicity tests of the bactericidal compositions in the examples against Phytophthora melonis, Plasmopara viticola, Pseudoperonospora cubensis, and Elsinoe fawcettii were determined by the method of drug-containing culture. Specifically:

[0114] 1) Referring to the bioassay standard method NY / T 1156.2 - 2006, using the method of drug-containing culture medium: Take 3 mL of the liquid medicine of each single agent and mixture series concentration, add it to 27 mL of PDA culture medium cooled to 45°C, and make a drug-containing culture medium plate with the required final concentration. Then, take a 6-mm-diameter mycelium block from the edge of the Elsinoe fawcettii colony cultured for 7 days, transfer it to each series of drug-containing culture media, with the mycelium side facing down, and repeat 4 times for each treatment. After the treatment is completed, place it in a constant-temperature biochemical incubator at 28°C for culture.

[0115] Statistical analysis method: Measure the colony diameter 7 days after the experimental treatment, and calculate the growth inhibition rate (%).

[0116] [[ID=I5]]D = D1 - D2;

[0117] Where: D represents the colony growth diameter; D1 represents the colony diameter; D2 represents the diameter of the fungal cake.

[0118] I(%) = (D0 - D t ) / D0 * 100

[0119] Where: I represents the mycelial growth inhibition rate; D0 represents the colony growth diameter of the blank control; D t represents the colony growth diameter of the drug-treated colony.

[0120] Referring to the bioassay standard NY / T 1156.6 - 2006, the synergistic effect of the mixed use of drugs was evaluated according to the co-toxicity coefficient method (CTC) of Sun & Johnson (1960), that is, CTC ≤ 80 is antagonistic effect, 80 < CTC < 120 is additive effect, and CTC ≥ 120 is synergistic effect.

[0121] Actual toxicity index (ATI) = (standard drug EC 50 / test drug EC 50 ) * 100

[0122] The theoretical toxicity index (TTI) of the mixture = the toxicity index of agent A * the percentage (%) of agent A in the mixture + the toxicity index of agent B * the percentage (%) of agent B in the mixture

[0123] The co-toxicity coefficient (CTC) = [(the actual toxicity index (ATI) of the mixture / the theoretical toxicity index (TTI) of the mixture)] * 100. The test results are shown in Table 1.

[0124] 2) Refer to the acoustic detection standard method NY / T 1156.3 - 2006 and adopt the petri dish leaf method.

[0125] Preparation of sporangium suspension: Select diseased cucumber leaves, wash the sporangia of downy mildew on the back of the leaves with distilled water at 4 °C, and prepare a suspension (the concentration is controlled at 1×10 5 to 1×10 7 sporangia per milliliter), and store it at 4 °C for later use.

[0126] Spray the prepared liquid medicine evenly on the back of the treated leaves. After the liquid medicine dries naturally, place the back of each treated leaf upward and arrange them in a humidity box according to the treatment marks. 24 hours after the drug treatment, drop 10 μL of the prepared fresh sporangium suspension onto the back of the leaves. Inoculate 4 drops on each leaf, and use 5 leaves for each treatment. Set a treatment without the medicine as a blank control. After inoculation, cover the petri dish lid and place it in an artificial climate chamber, and culture it under the conditions of 12 h alternating of continuous light / darkness every day, a temperature of 17 - 22 °C, and a relative humidity of more than 90%.

[0127] Statistical method: After culturing for 7 days, measure and record the diameter of the disease spots according to the disease situation of the blank control, and calculate the control effect (%).

[0128] P = (D0 - D1 / D0) * 100

[0129] Where: P represents the prevention effect, D0 represents the diameter of the disease spots in the blank control, and D1 represents the diameter of the disease spots in the treatment.

[0130] Refer to the bioassay standard NY / T 1156.6 - 2006, and evaluate the synergistic effect of the mixed agents according to the co-toxicity coefficient method (CTC) of Sun & Johnson (1960), that is, CTC ≤ 80 is antagonistic effect, 80 < CTC < 120 is additive effect, and CTC ≥ 120 is synergistic effect.

[0131] The actual toxicity index (ATI) = (the EC of the standard agent 50 / the EC of the tested agent 50 ) * 100

[0132] The theoretical toxicity index (TTI) of the mixture = the toxicity index of agent A * the percentage (%) of agent A in the mixture + the toxicity index of agent B * the percentage (%) of agent B in the mixture

[0133] The co-toxicity coefficient (CTC) = [(the actual toxicity index (ATI) of the mixture / the theoretical toxicity index (TTI) of the mixture)] * 100. The test results are shown in Table 2

[0134] 3) Referring to the acoustic measurement standard method NY / T 1156.3-2006, using the method of medicated medium: Take 3 mL of the liquid medicine of each single agent and the series concentrations of the mixture, add it to 27 mL of PDA medium cooled to 45 degrees Celsius, and make a medicated medium plate with the required final concentration. Then, take a 6-mm diameter mycelial block from the edge of the Phytophthora melonis colony cultured for 7 days, transfer it to each series of medicated media, with the mycelial surface facing down, and repeat 4 times for each treatment. After the treatment, place it in a constant temperature biochemical incubator at 28 degrees Celsius for cultivation

[0135] Statistical analysis method: Measure the colony diameter 5 days after the experimental treatment and calculate the growth inhibition rate (%)

[0136] D = D1 - D2

[0137] Where: D represents the colony growth diameter; D1 represents the colony diameter; D2 represents the diameter of the mycelial cake

[0138] I(%) = (D0 - D t ) / D0 * 100

[0139] Where: I represents the mycelial growth inhibition rate; D0 represents the colony growth diameter of the blank control; D t represents the colony growth diameter of the agent-treated

[0140] Referring to the bioassay standard NY / T 1156.6-2006, according to the co-toxicity coefficient method (CTC) of Sun & Johnson (1960) to evaluate the synergistic effect of the mixture of agents, that is, CTC ≤ 80 is antagonistic effect, 80 < CTC < 120 is additive effect, and CTC ≥ 120 is synergistic effect

[0141] The actual toxicity index (ATI) = (the EC of the standard agent 50 / the EC of the tested agent 50 ) * 100

[0142] The theoretical toxicity index (TTI) of the mixture = the toxicity index of agent A * the percentage (%) of agent A in the mixture + the toxicity index of agent B * the percentage (%) of agent B in the mixture

[0143] Coefficient of Toxicity (CTC) = [Actual Toxicity Index of Mixture (ATI) / Theoretical Toxicity Index of Mixture (TTI)] * 100. The test results are shown in Table 3.

[0144] 4) Refer to the standard method of bioassay NY / T 1156.3 - 2006 and adopt the petri dish leaf method.

[0145] Preparation of sporangium suspension: Select diseased leaves of grapes, wash the sporangia of downy mildew on the back of the leaves with distilled water at 4 °C, and prepare a suspension (the concentration is controlled at 1×10 5 to 1×10 7 sporangia per milliliter), and store it for later use at 4 °C.

[0146] Spray the prepared liquid medicine evenly on the back of the applied leaves. After the liquid medicine dries naturally, place the back of each treated leaf upward and arrange them in a moisture box according to the treatment marks. 24 hours after the chemical treatment, drop 10 μL of the prepared fresh sporangium suspension onto the back of the leaves for inoculation. Inoculate 4 drops per leaf, 5 leaves per treatment, and set a treatment without medicine as a blank control. After inoculation, cover the petri dish lid and place it in an artificial climate box, and culture it under the conditions of continuous light / dark 12 h alternation every day, temperature of 17 - 22 °C, and relative humidity of more than 90%.

[0147] Statistical method: After culturing for 7 days, measure and record the diameter of the disease spots according to the disease occurrence of the blank control, and calculate the control effect (%).

[0148] P = (D0 - D1 / D0) * 100

[0149] Where: P represents the control effect, D0 represents the diameter of the disease spots of the blank control, and D1 represents the diameter of the disease spots of the treatment.

[0150] Refer to the bioassay standard NY / T 1156.6 - 2006, and evaluate the synergistic effect of the mixture of medicaments according to the Coefficient of Toxicity (CTC) method of Sun & Johnson (1960), that is, CTC ≤ 80 is antagonistic effect, 80 < CTC < 120 is additive effect, and CTC ≥ 120 is synergistic effect.

[0151] Actual Toxicity Index (ATI) = (EC of standard medicament 50 / EC of test medicament 50 ) * 100

[0152] Theoretical Toxicity Index of Mixture (TTI) = Toxicity Index of Medicament A * Percentage of Medicament A in the mixture (%) + Toxicity Index of Medicament B * Percentage of Medicament B in the mixture (%)

[0153] Co-toxicity coefficient (CTC) = [Actual toxicity index (ATI) of the mixture / Theoretical toxicity index (TTI) of the mixture] * 100. The test results are shown in Table 4.

[0154] Table 1. Results of toxicity tests of the fungicidal composition against *Citrus resinosis* (scab).

[0155]

[0156] Indoor bioassay results showed that mixtures of pyraclostrobin and mancozeb at ratios of 1:1, 1:2, 1:4, 1:6, 1:8, and 1:10 exhibited a synergistic effect against citrus resin pathogens, with the most significant synergistic effects observed at ratios of 1:6, 1:8, and 1:10. However, in actual production, specific environmental conditions, processing techniques, virulence, and other factors need to be considered comprehensively.

[0157] Table 2. Results of toxicity test of the fungicidal composition against cucumber downy mildew.

[0158]

[0159] Indoor bioassay results showed that mixtures of pyraclostrobin and mancozeb at ratios of 1:1, 1:2, 1:4, 1:6, 1:8, and 1:10 exhibited a synergistic effect against cucumber downy mildew, with the most significant synergistic effects observed at ratios of 1:6, 1:8, and 1:10. However, in actual production, specific environmental conditions, processing techniques, virulence, and other factors need to be considered comprehensively.

[0160] Table 3. Results of toxicity tests of the bactericidal composition against *Phytophthora infestans* (Cucumber blight pathogen).

[0161]

[0162]

[0163] Indoor bioassay results showed that pyraclostrobin mixed with mancozeb at ratios of 1:1, 1:2, 1:4, 1:6, 1:8, and 1:10 exhibited a synergistic effect against *Phytophthora indusiata*, with the most significant synergistic effects observed at ratios of 1:6, 1:8, and 1:10. However, in actual production, specific environmental conditions, processing techniques, virulence, and other factors need to be considered comprehensively.

[0164] Table 4. Results of toxicity tests of the fungicidal compositions against *Botrytis cinerea*.

[0165]

[0166]

[0167] Indoor bioassay results showed that pyraclostrobin and mancozeb at ratios of 1:1, 1:2, 1:4, 1:6, 1:8, and 1:10 all exhibited synergistic effects against Grape downy mildew, with the most significant synergistic effects observed at ratios of 1:6, 1:8, and 1:10. However, in actual production, specific environmental conditions, processing techniques, virulence, and other factors need to be considered comprehensively.

[0168] In addition, the applicant conducted dispersion stability tests, low-temperature stability tests, and high-temperature stability tests on the dispersible oil suspension in the embodiments of the present invention. Specifically:

[0169] 1. The high-temperature stability test method is conducted according to the "Liquid Preparations" test method in GB / T 19136-2003: After heat storage at 54℃ for 4 weeks, the dispersible oil suspension prepared in the example is tested. If the dispersible oil suspension is a stable liquid and there are no phenomena such as layering, solidification, or precipitation, it is qualified; otherwise, it is unqualified.

[0170] 2. Dispersion stability test: The test was conducted according to the method described in HG / T 2467.11-2003. The main steps involved preparing a dispersion at the specified concentration, placing it upright in two graduated emulsion tubes and allowing it to stand for a period of time, then tilting the tubes several times. The dispersibility of the dispersion was observed initially, after a period of standing, and after redispersing.

[0171] Superior grade: Initial dispersibility - complete dispersion; 30 min dispersibility - sediment < 5.0 ml, cream or floating oil < 3.0 ml; Redispersibility - 24 h sediment < 1.0 ml, cream or floating oil < 2.0 ml.

[0172] Good grade: Initial dispersibility - complete dispersion; 30 min dispersibility - sediment < 8.0 ml, cream or floating oil < 5.0 ml; Redispersibility 24 h sediment < 1.5 ml, cream or floating oil < 3.0 ml.

[0173] Unacceptable: Initial dispersibility - incomplete dispersion; 30-minute dispersibility - sediment > 8.0 ml, cream or floating oil > 5.0 ml; redispersibility - 24-hour sediment > 1.5 ml, cream or floating oil > 3.0 ml.

[0174] 3. Low-temperature stability is tested according to "Oil Suspension" in GB / T 19137-2003: If no precipitation or stratification occurs, and the initial properties can be reproduced after restoring to room temperature and stirring, it is qualified; otherwise, it is unqualified.

[0175] Table 5. Physical and Chemical Properties Test Table

[0176] High temperature stability Dispersion stability freeze-thaw stability Example 3 qualified good Unqualified Example 4 qualified excellent qualified Example 5 qualified excellent qualified Example 6 qualified excellent qualified Example 7 qualified excellent qualified Example 8 qualified excellent qualified Example 9 qualified excellent qualified Example 10 Unqualified good Unqualified Example 11 Unqualified good Unqualified Example 12 Unqualified good Unqualified Example 13 Unqualified excellent Unqualified

[0177] field trials

[0178] The applicant commissioned Sichuan Heben Technology Co., Ltd. to conduct field trials on the pyraclostrobin and mancozeb compound dispersible oil suspension of this invention to observe its control effects on apple leaf spot and citrus resinosis, as detailed below:

[0179] I. Apple tree leaf spot disease

[0180] 1.1 Crops and Targets: Crops / Apple Trees / Red Fuji

[0181] Target / spot leaf spot disease [Alternaria mali; Marssonina coronaria]

[0182] 1.2 Experimental Conditions: The experiment was conducted from July 19, 2019 to August 9, 2019 in an apple orchard in Taiping Village, Fulin Town, Hanyuan County, Sichuan Province. The experimental plot covered 1.5 mu (approximately 0.067 hectares). The apple variety was Red Fuji, cultivated without pesticides, with trees aged 8 years. 60 apple trees were planted per mu (approximately 0.067 hectares). Pesticide application was performed during the fruit enlargement stage. The soil was reddish-brown sandy loam with a pH of 6.1 and an organic matter content of 24.5 g / kg. No pesticides were applied prior to the experiment.

[0183] 2. Experimental Design and Arrangement

[0184] 2.1.1 Test reagents

[0185] 410 g / L pyraclostrobin·mancozeb dispersible oil suspension (Shanghai Yuelian Biotechnology Co., Ltd.)

[0186] 2.1.2 Control reagent

[0187] 30% Pyraclostrobin Suspension Concentrate (Shanghai Yuelian Biotechnology Co., Ltd.)

[0188] 80% Mancozeb Wettable Powder (Shanghai Yuelian Chemical Co., Ltd.)

[0189] 2.1.3 Test Treatment

[0190] Table 6 2.1.3 Test Treatment

[0191]

[0192] 2.2 Community Arrangement

[0193] 2.2.1 Cell Arrangement Method: Cells are arranged in random blocks, as shown below.

[0194] Table 7 2.1.3 Layout of Cell Blocks

[0195] A1 C1 B1 D1 F1 E1 D2 B2 E2 F2 C2 A2 F3 E3 C3 B3 A3 D3 E4 F4 D4 A4 B4 C4

[0196] 2.2.2 Area and Repetition: 4 repetitions, 2 trees per area, with protection rows between areas.

[0197] 2.3 Application Method

[0198] 2.3.1 Application time and frequency: Apply the pesticide before the apple trees develop symptoms, and apply it twice consecutively. Specific dates: July 19, 2019 and July 30, 2019.

[0199] 2.3.2 Equipment and Application Method: The pesticide solution was prepared using a two-stage dilution method. The main equipment used included a balance, graduated cylinder, pipette, and glass rod. A PB-16 sprayer was used for spraying at a pressure of 0.2-0.4 MPa and a nozzle diameter of 1 mm. Approximately 1.25 liters of water were used per tree.

[0200] 2.3.4 Soil data: Red-brown sandy loam, pH 6.1, organic matter content 24.5 g / kg.

[0201] 2.3.5 Control of non-target organisms: No other agents were used during the experiment.

[0202] 3. Survey and Results

[0203] 3.1 Survey Method: Two trees were surveyed in each plot. Two new shoots (spring and autumn shoots) were fixed in each of the five directions (east, west, south, north, and center) of each tree. All leaves were surveyed periodically, and the total number of leaves and the number of diseased leaves at each level were recorded. Grading method: Grade 0: No lesions; Grade 1: Lesions cover less than 10% of the total leaf area; Grade 3: Lesions cover 11%–25% of the total leaf area; Grade 5: Lesions cover 26%–40% of the total leaf area; Grade 7: Lesions cover 41%–65% of the total leaf area; Grade 9: Lesions cover more than 66% of the total leaf area.

[0204] 3.2 Survey Time and Frequency: One survey was conducted when the symptoms were obvious in the water control group. Specific time: August 9, 2019.

[0205] 3.3 This experiment followed the "Good Manufacturing Practice for Pesticide Registration Trials", "Guidelines for Pesticide Field Efficacy Trials" GB / T17980.124-2004, and SOP-TM-149a "Apple Tree Spot Leaf Drop Disease Trial". The calculation formula is as follows:

[0206]

[0207]

[0208] 3.4 Effects on other organisms: No significant effects of the test agent on other organisms were observed during the experiment.

[0209] 3.5 Test Results

[0210] 3.5.1 Control effect: The average control effect is shown in Table 8.

[0211] Table 8. Average control efficacy of 410 g / L pyraclostrobin·mancozeb dispersible oil suspension for controlling apple leaf spot disease.

[0212] deal with disease finger % efficacy A 5.75 76.5bA B 4.39 82abA C 3.59 85.3aA D 4.15 83aA E 8.07 67cB F 24.44

[0213] The data in the table are the average of four replicates. The analysis of variance was performed by DPS (v7.05). The letters indicate the significance of the differences (uppercase 0.01 level, lowercase 0.05 level, DMRT method).

[0214] 3.5.2 Safety: The apple trees grew normally during the experiment, and no symptoms of pesticide damage were observed.

[0215] 4. Evaluation and Discussion

[0216] The efficacy of 410 g / L pyraclostrobin·mancozeb dispersible oil suspension at dilutions of 800, 1000, and 1200 times for controlling apple leaf spot disease was 85.3%, 82%, and 76.5% respectively when symptoms were obvious in the water control. The control agents, 30% pyraclostrobin suspension at dilution of 2500 times and 80% mancozeb wettable powder at dilution of 600 times, showed efficacy of 83% and 67% respectively when symptoms were obvious in the water control. Analysis of variance showed that the efficacy of the tested agents at dilutions of 1000 times was comparable to that at dilutions of 800 and 1200 times. Compared with the control agents, the efficacy of the tested agents at dilutions of 800 and 1000 times was not significantly different from that of 30% pyraclostrobin suspension at dilution of 2500 times, but the efficacy of all dosages of the tested agents was significantly higher than that of 80% mancozeb wettable powder at dilution of 600 times.

[0217] The experimental results showed that the efficacy of 410 g / L pyraclostrobin·mancozeb dispersible oil suspension in controlling apple leaf spot disease increased with decreasing multiplier concentration. In the water control, when symptoms were obvious, the control efficacy was 76.5-85.3%, and the disease index was controlled below 5.75, significantly lower than the 24.44 of the water control, thus reducing the damage caused by apple leaf spot disease and demonstrating good control efficacy. During the experiment, the apple trees grew normally, and no phytotoxicity symptoms were observed. 410 g / L pyraclostrobin·mancozeb dispersible oil suspension can be used to control apple leaf spot disease.

[0218] According to the results of this year's trials, the 410 g / L pyraclostrobin·mancozeb dispersible oil suspension provided by Shanghai Yuelian Biotechnology Co., Ltd. is recommended to be diluted 800-1200 times (active ingredient 341.7-512.5 mg / kg) for the control of apple tree leaf spot disease. It should be applied before or at the early stage of the disease, with an interval of 7-10 days, for two consecutive applications.

[0219] II. Citrus resinosis

[0220] 1.1 Crops and Targets: Crops / Citrus Trees / Wogan Oranges

[0221] Target / resinosis [Phomopsis cytosporella]

[0222] 1.2 Experimental Conditions: The experiment was conducted from April 20, 2019 to May 30, 2019 at Ziyun Orchard in Xiaogu Town, Qianwei County, Sichuan Province. The soil was yellow soil with a pH of 5.8 and an organic matter content of 21.6 g / kg. The experimental plot covered an area of ​​1.5 mu (approximately 0.067 hectares). The orchard had been in production for 4 years after transplanting. The variety was Wogan mandarin orange, with a plant spacing of 3 m × 4 m and a planting density of 55 trees per mu. No fungicides were used in the 50 days prior to the experiment.

[0223] 2. Experimental Design and Arrangement

[0224] 2.1.1 Test reagents

[0225] 410 g / L pyraclostrobin-mancozeb dispersible oil suspension (Shanghai Yuelian Biotechnology Co., Ltd.)

[0226] 2.1.2 Control reagent

[0227] 30% Pyraclostrobin Suspension Concentrate (Shanghai Yuelian Biotechnology Co., Ltd.)

[0228] 80% Mancozeb Wettable Powder (Shanghai Yuelian Chemical Co., Ltd.)

[0229] 2.1.3 Test Treatment

[0230] Table 9 2.1.3 Test Treatment

[0231]

[0232] 2.3 Application Method

[0233] 2.3.1 Application Time and Frequency: Apply once every 10 days during the second / third of the flowering period, the young fruit stage, and the fruit enlargement stage, for a total of 3 applications. 2.3.2 Equipment and Application Method: Prepare the pesticide solution using a two-stage dilution method. The main tools used include: a balance, graduated cylinder, pipette, and glass rod. Use an HD400 sprayer with a spray pressure of 0.2-0.4 MPa and a nozzle diameter of 1 mm. Approximately 1.5 liters of water are used per tree.

[0234] 2.3.4 Soil data: Yellow soil, pH 5.8, organic matter content 21.6 g / kg.

[0235] 2.3.5 Control of non-target organisms: No other agents were used during the experiment.

[0236] 3. Survey and Results

[0237] 3.1 Survey Method: Two plants were sampled per plot. A five-point sampling method (east, west, south, north, and center) was used. Two shoots were surveyed at each point. For each branch, four leaves below the top leaf and all fruits were examined. The disease index and control effect were calculated. Grading Method: Grade 0: No lesions on leaves or fruit; Grade 1: Less than 5% of the leaf and fruit area covered by brown spots; Grade 3: 6%-10% of the leaf and fruit area covered by brown spots; Grade 5: 11%-25% of the leaf and fruit area covered by brown spots; Grade 7: 26%-50% of the leaf and fruit area covered by brown spots; Grade 9: More than 51% of the leaf and fruit area covered by brown spots.

[0238] 3.2 Survey Time and Frequency: Surveys were conducted twice, once before medication and once 20 days after three doses of medication. Specific dates: April 20, 2019 and May 30, 2019.

[0239] 3.3 Experimental Basis and Calculations: This experiment followed the "Good Manufacturing Practice for Pesticide Registration Trials," "Guidelines for Pesticide Field Efficacy Trials," and SOP-TM-073a "Citrus Resinosis Trial." The calculation formula is as follows:

[0240]

[0241]

[0242] 3.4 Effects on other organisms: No significant effects of the test agent on other organisms were observed during the experiment.

[0243] 3.5 Test Results

[0244] 3.5.1 Control effect: The average control effect is shown in Table 10.

[0245] Table 1. Average control efficacy of 10410 g / L pyraclostrobin-mancozeb dispersible oil suspension for controlling citrus resinosis.

[0246]

[0247] The data in the table are the average of four replicates. The analysis of variance was performed by DPS (v7.05). The letters indicate the significance of the differences (uppercase 0.01 level, lowercase 0.05 level, DMRT method).

[0248] 3.5.2 Safety: The citrus trees grew normally during the experiment, and no symptoms of pesticide damage were observed.

[0249] 4. Evaluation and Discussion

[0250] During this experimental investigation, the fruit was in its swelling stage and did not show symptoms of resinosis; therefore, only the leaves were investigated for disease incidence analysis. For the control of citrus resinosis, 410 g / L pyraclostrobin·mancozeb dispersible oil suspension at dilutions of 800, 1000, and 1200 times showed leaf control efficacy of 85.1%, 83.0%, and 78.3% respectively 20 days after three applications. In contrast, the control efficacy of the 30% pyraclostrobin suspension at dilution of 2500 times and the 80% mancozeb wettable powder at dilution of 600 times were 78.6% and 79.0% respectively 20 days after three applications. Analysis of variance showed that the tested agents at dilutions of 800 and 1000 times were significantly more effective than the 1200-fold dilution. Compared with the control agents, the tested agents at dilutions of 800 and 1000 times were significantly more effective than the two control groups, while the 1200-fold dilution was comparable in efficacy.

[0251] The experimental results showed that the efficacy of 410 g / L pyraclostrobin·mancozeb dispersible oil suspension in controlling citrus resinosis increased with decreasing dilution ratio. After three applications at dilutions of 800-1200 times, the leaf control efficacy reached 78.3-85.1% 20 days later, with the leaf disease index controlled below 4.06, significantly lower than the 18.02 of the water control, effectively mitigating the damage caused by citrus resinosis and demonstrating good control efficacy. During the experiment, citrus growth was normal, and no phytotoxicity symptoms were observed. Therefore, 410 g / L pyraclostrobin·mancozeb dispersible oil suspension can be used to control citrus resinosis.

[0252] According to the results of this year's trials, the 410 g / L pyraclostrobin·mancozeb dispersible oil suspension provided by Shanghai Yuelian Biotechnology Co., Ltd. is recommended to be diluted 800-1200 times and applied 3 times consecutively at intervals of 7-14 days during the various new shoot emergence periods of citrus trees, when 2 / 3 of the flowers have withered, before the onset of the disease in young fruits, or at the early stage of the disease.

[0253] In addition, to ensure the reproducibility of the technical solution in this invention, the applicant commissioned the College of Agriculture of Shanxi Agricultural University to conduct field trials on the pyraclostrobin·mancozeb dispersible oil suspension of this invention, as detailed below:

[0254] Experimental crop: Apple tree; Target disease: Apple leaf spot disease (Alternaria alternata)

[0255] Test reagent: 410 g / L pyraclostrobin·mancozeb dispersible oil suspension

[0256] 3. Environmental and Facility Cultivation Conditions

[0257] 3.1 Location of the test site

[0258] Huima Village, Yangyi Township, Taigu County, Shanxi Province.

[0259] 3.2 Test target conditions

[0260] Apple trees have been affected by leaf spot disease in previous years. In this experiment, the first application of the pesticide at the early stage of the disease resulted in scattered lesions in the field.

[0261] 3.3 Experimental crop varieties and growth status

[0262] Experimental crop variety: Fuji; growth conditions: apple trees aged 8 years, planting density of 50 trees / acre.

[0263] 3.4 Soil types at the experimental site

[0264] The experimental field consisted of loam soil with a pH of approximately 7.2 and no intercropping crops were used.

[0265] 3.5 Water and fertilizer management in the experimental field

[0266] The management conditions, such as fertilizer and water, were uniform and consistent, and the management level of drainage and irrigation was moderate. Conventional agricultural operations were carried out before and after the experiment.

[0267] 3.6 Meteorological Data

[0268] The first application (July 21st) was cloudy to overcast, with temperatures ranging from 23-34℃, an average temperature of 26.9℃, and a relative humidity of 66%. The second application (July 31st) was sunny, with temperatures ranging from 20-33℃, an average temperature of 26.2℃, and a relative humidity of 64%. The third application (August 10th) was sunny, with temperatures ranging from 18-30℃, an average temperature of 24.6℃, and a relative humidity of 69%. There were 8 days of effective rainfall during the experiment, with a total rainfall of 79.1 mm. The heaviest rainfall occurred on July 29th, 2019, at 27.9 mm. The highest temperature during the experiment was 36℃, and the lowest was 13℃. There were no particularly disastrous weather events affecting the efficacy of the pesticide, but the weather was drier than in previous years, leading to a later onset of disease.

[0269] 3.7 Information on pesticides for controlling other diseases and pests

[0270] No fungicides or insecticides were used during the experiment, and this had no impact on the results.

[0271] 4. Experimental Design and Arrangement

[0272] 4.1 Dosage and numbering of test reagents

[0273] Table 11 Experimental Design of Test Reagents

[0274]

[0275] 4.2 Community Arrangement

[0276] The experiment consisted of 6 treatments, with 4 cells per treatment, and the cells were arranged in a randomized block design for a total of 24 cells.

[0277] Table 12 Residential Area Ranking List

[0278]

[0279]

[0280] 4.2.2 Area and Duplication

[0281] Community size: 2 mature apple trees per community.

[0282] Number of repetitions: 4.

[0283] 4.3 Application Method

[0284] 4.3.1 Timing and Method of Application

[0285] Apply the pesticide at the initial stage of apple leaf spot disease. Weigh the pesticide according to the dosage required for each treatment, dilute it with water, and spray as usual, ensuring uniform and consistent spraying without overlapping or missing areas. The blank control is sprayed with plain water.

[0286] 4.3.2 Application equipment

[0287] Instrument serial number: SP-F-003

[0288] Instrument model: Haiyan brand backpack electric sprayer, model 3WBD-16, working pressure is 0.2-0.4MPa.

[0289] 4.3.3 Application time and frequency

[0290] The drug was administered three times in this experiment: the first administration was on July 21, 2019; the second administration was on July 31, 2019; and the third administration was on August 10, 2019.

[0291] 4.3.4 Application volume

[0292] Spray 2 liters of pesticide solution on each tree.

[0293] 4.4 Survey methods, time and frequency

[0294] Referring to the Ministry of Agriculture's "Guidelines for Field Efficacy Testing of Pesticides (II): Control of Apple Spot Leaf Disease with Fungicides" (GB / T17980.124-2004), the test was conducted in accordance with the SOP of this testing unit, "Control of Apple Spot Leaf Disease with Fungicides" (SXAU-SOP-F-015).

[0295] 4.4.1 Survey time and number of times

[0296] First survey: On July 21, 2019, a survey was conducted before the first application of pesticides. At this time, there were scattered lesions on the apple trees, and the disease index was recorded as zero.

[0297] Second survey: The control effect was investigated 12 days after the last application of the pesticide on August 22, 2019, and the disease incidence was recorded according to the grading standards.

[0298] 4.4.2 Survey Methods

[0299] Two plants were surveyed in each plot. Two new shoots were fixed in each of the five directions (east, south, west, north, and center) of each plant. All leaves of each plant were surveyed, and the total number of leaves and the number of leaves at each disease level were recorded. Each leaf was graded and recorded according to the percentage of leaf area covered by disease spots.

[0300] Classification method for leaf damage (by leaf):

[0301] Grade 0: No lesions;

[0302] Grade 1: Lesions cover less than 10% of the total leaf area;

[0303] Grade 3: Lesions cover 11%-25% of the total leaf area;

[0304] Level 5: Lesions cover 26%-40% of the total leaf area;

[0305] Level 7: Lesions cover 41%-65% of the total leaf area;

[0306] Level 9: Lesions cover more than 66% of the total leaf area.

[0307] 4.4.3 Method for Calculating Drug Efficacy

[0308] The efficacy calculation methods and formulas used are as follows: the disease index and control effect of each plot were calculated, the average control effect of each treatment was calculated, and the DMRT method of SPSS 17.0 software was used to analyze the significance of differences between treatments.

[0309]

[0310]

[0311] 4.5 Direct impacts on crops

[0312] One day, three days, and five days after each application, the pesticide was observed to have no phytotoxic effects on the apple trees and fruits.

[0313] 4.6 Product output and quality

[0314] At the end of the experiment, yield and quality were not investigated.

[0315] 4.7 Impacts on other organisms

[0316] 4.7.1 Impact on other pests and diseases

[0317] No other diseases were found in the apple trees during the experiment, and there was no impact on pests.

[0318] 4.7.2 Impacts on other non-target organisms and surrounding crops

[0319] The experiment had no effect on other non-target organisms or surrounding crops.

[0320] 5. Experimental Results and Analysis

[0321] The efficacy survey results 10 days after the last application of the test agent (Table 2) showed that: when the effective ingredient dosage of the test agent 410 g / L pyraclostrobin·mancozeb dispersible oil suspension was 341.7 mg / kg, 410 mg / kg and 512.5 mg / kg, the efficacy was 81.23%, 85.83% and 86.70%, respectively; when the effective ingredient dosage of the control agent 30% pyraclostrobin suspension was 200 mg / kg, the efficacy was 84.22%; and when the effective ingredient dosage of the control agent 80% mancozeb wettable powder was 1000 mg / kg, the efficacy was 82.92%.

[0322] The results of the experiment, analyzed using Duncan's new multiple range method, showed that at the 0.05 and 0.01 levels, there were no significant differences in the control efficacy among the high, medium, and low concentrations of the test agent 410 g / L pyraclostrobin·mancozeb dispersible oil suspension and the control agent.

[0323] Table 1. Efficacy test results of 13410 g / L pyraclostrobin·mancozeb dispersible oil suspension for controlling apple scab leaf spot disease.

[0324]

[0325] 6 Conclusions

[0326] It is recommended to promote the use of 410 g / L pyraclostrobin·mancozeb dispersible oil suspension in production, applying it before or at the early stage of apple leaf spot disease, at intervals of 7-14 days, for 3 applications. The effective ingredient dosage is 341.7-512.5 mg / kg (formulation diluted 800-1200 times) for spraying control. The tested dosage of the tested agent is safe for apple trees and fruits.

[0327] The foregoing examples are merely illustrative, serving to explain some features of this disclosure. The appended claims are intended to claim the broadest possible scope, and the embodiments presented herein are merely illustrative of selected implementations based on combinations of all possible embodiments. Therefore, the applicant intends that the appended claims are not limited by the selection of examples illustrating the features of the invention. Moreover, technological advancements will result in possible equivalents or sub-equivalents not currently considered due to inaccuracies in linguistic expression, and these variations should also be interpreted as being covered by the appended claims where possible.

Claims

1. A fungicide composition containing pyraclostrobin and mancozeb, characterized in that, The bactericide composition is in the form of a dispersible oil suspension. The preparation method of the dispersible oil suspension includes the following steps: 3 wt% castor oil polyoxyethylene ether, 4 wt% alkoxylated tallow alcohol, 1.6 wt% disproportionated rosinate potassium and 6 wt% polyether modified siloxane were added to a reaction vessel and mixed and dispersed; 5 wt% pyraclostrobin, 30 wt% mancozeb technical, 3 wt% bentonite, 2 wt% ethylene glycol and the balance methyl oleate were added under high-speed shearing and ground until the particle size was less than 3 micrometers. The preparation method of the polyether-modified siloxane includes the following steps: 1) Add 100g of octamethylcyclotetrasiloxane, 7.2g of hexamethyldisiloxane, 28.5g of high-hydrogen-content silicone oil with a hydrogen content of 1.56% and 6g of acidic clay to a reaction vessel, heat to 60℃ and react for 4 hours to obtain low-hydrogen-content silicone oil with a hydrogen content of 0.3%; 2) Add 50g of the low-hydrogen silicone oil, 95g of unsaturated polyether, 20g of diethylene glycol and 6.8mg of platinum-rhodium complex solution to the reaction vessel, and react for 5 hours at a reaction temperature of 110℃ and normal pressure. After there are no more excess Si-H bonds, cool down to obtain the product. The unsaturated polyether is a mixture of allyl alcohol polyether and allyl polyoxyethylene polyoxypropylene epoxy ether in a weight ratio of 2.5:

1.

2. The application of the fungicide composition containing pyraclostrobin and mancozeb as described in claim 1 in the prevention and control of scab, downy mildew and blight in vegetables and fruit trees.

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