A fungicidal composition for foliar spray

Abstract

This invention relates to the field of pesticides, specifically to a fungicide composition for foliar spraying, its preparation method, and application scheme. The active ingredients of the fungicide composition include quinoline copper and phosphite A. Phosphite A is selected from at least one of phosphorous acid, alkali metal salts or alkaline earth metal salts of phosphorous acid, alkylphosphonic acids containing C1-C6 groups of phosphorous acid or alkali metal salts of alkylphosphonic acids, alkaline earth metal salts, and aluminum salts. In the fungicide composition, the weight ratio of quinoline copper to phosphite A is 99:1 to 1:99. The fungicide composition of this invention has high activity against bacterial and fungal diseases occurring in various crops, such as canker and downy mildew, and also exhibits significant synergistic effects. It not only improves the antibacterial or bacteriostatic effect but also broadens the control spectrum. Simultaneously, it can reduce the number of applications and alleviate environmental pressure, thereby achieving the effect of prevention-oriented and integrated pest management.

Description

Technical Field

[0001] This invention relates to pesticide fungicide compositions and their applications, specifically a fungicide composition for foliar spraying, its preparation method, and application scheme. The fungicide composition includes quinoline copper and phosphite, and can be used to control bacterial and fungal diseases in crops. Background Technology

[0002] Quinoline copper, CAS No.: 10380-28-6, English name: oxine-copper; Chemical name: 8-hydroxyquinoline copper; Molecular formula: C 18 H 12 CuN2O2; relative molecular weight 351.8.

[0003] Quinoline copper is a quinoline-based protective low-toxicity fungicide, belonging to the organic copper chelate family. It is broad-spectrum, highly effective, and leaves minimal residue, making it safe to use. It has good preventive and curative effects against both fungal and bacterial diseases. Studies by Huang Yajun et al. ["Pesticide Science and Management," 2016, Issue 08] and ["Agricultural Disaster Research," 2019, Issue 03] found that quinoline copper can control brown spot and canker disease in bayberries. Studies by Liang Bo et al. ["World Pesticides," 2008, Issue S1] found that quinoline copper can control bacterial black spot in peaches, bacterial black spot in walnuts, and angular leaf spot in persimmons.

[0004] Phosphites refer to phosphorous acid, alkali metal or alkaline earth metal salts of phosphorous acid, alkylphosphonic acids containing C1-C6 groups or alkali metal salts, alkaline earth metal salts, and aluminum salts of phosphorous acid, and possess bactericidal properties. Wang Shikui et al. [Superstar Journal, 2018, Issue 09] explained that phosphorous acid (H3PO3) and phosphite fertilizers contain higher concentrations of phosphorus than traditional phosphoric acid (H3PO4) and phosphate fertilizers, and are less easily fixed by calcium, magnesium, and zinc ions in the soil, thus improving fertilizer utilization, especially the utilization of micronutrients, making crops less prone to nutrient deficiency symptoms. The synergistic effect of various nutrients promotes healthy crop growth. Research has found that phosphites achieve their disease control effects through direct antibacterial action and inducing immune responses in plants.

[0005] Patent CN1051907C discloses a method for treating seeds with a fungicide composition containing phosphite active substances; the patent mentions a fungicide composition of quinoline copper and phosphite active substances, relating to plant seeds protected from fungal diseases, to a fungicide composition required to obtain such protected seeds, and to a method for treating seeds to obtain such protected seeds. This technology discloses the use of quinoline copper and phosphite active substances to treat monocotyledonous seeds and prevent them from contracting the following fungal diseases: *Pythium arrhenomanes* (a common species on gramineous crops such as corn and sugarcane, causing root rot), *Pythium graminicola* (one of the main pathogens causing bacterial wilt in maize), *Pythium torulosum* (known to infect wheat, beans, corn, alfalfa, weeds, lettuce, cabbage, ryegrass, fescue, pineapple, pine seedlings, etc.), *Pythium vanterpoolii* (mostly affecting leaves, flowers, and fruits of plants), *Pythium myriotylum* (causing root rot in various plants), and *Pythium periilum* (possibly a weak parasite that infects through wounds). Aristosporum (which causes brown lesions or rot on roots) and Pythium aphanidermatum (which damages seedlings and fruits of cucurbits, legumes, solanaceae, tobacco, corn, cotton, beets, etc., causing seedling damping-off and root and fruit rot) provide protection for cereal seeds, especially wheat, barley, rye, winter barley, oats, black wheat, corn, or rice. However, no specific cases or data on their protective effects have been published, nor have the disease resistance and treatment effects of combining the two on fungal diseases been disclosed, and the treatment method is singular.

[0006] This invention primarily targets bacterial and fungal diseases of crops. The bacterial diseases it controls include bacterial leaf streak of rice, bacterial leaf blight of cucumber, black rot of cabbage, citrus canker, bacterial shot-hole disease of peach, bacterial angular leaf spot of cucumber, bacterial wilt of solanaceous plants, bacterial leaf blight of melon, bacterial wilt of tomato, bacterial wilt of potato, and bacterial wilt of strawberry. The pathogens include *Xanthomonas orientalis* (rice leaf streak pathogen), *Xanthomonas brassicae* (cucumber pathogen), *Xanthomonas brassicae* (rapeseed pathogen), *Xanthomonas carpetii*, and *Xanthomonas caudatus* (cabbage black rot pathogen). The fungal pathogens include *Ralstonia solanacearum* (a type of *Pseudomonas syringae*), *Ralstonia solanacearum*, *Alternaria cucumeri*, and *Pseudomonas*. It controls fungal diseases such as rice bacterial blight, cucumber powdery mildew, zucchini powdery mildew, grape downy mildew, cucumber downy mildew, melon downy mildew, and cucumber gray mold. The pathogens include the rice bacterial blight pathogen, *P. cucumeris* and *P. cucumeris*, *P. cucumeris*, *P. cucumeris*, *P. cucumeris*, and *Botrytis cinerea*. Furthermore, it can control diseases in grain crops, cash crops, fruits and vegetables, and turf and garden crops.

[0007] Compared to patent CN1051907C, this invention differs significantly in the following ways: 1) The application methods are different. The composition disclosed in the patent is used for treating monocotyledonous plant seeds by film coating, which simply involves mixing the treated seeds with the fungicidal composition. In contrast, the application method of this invention is foliar spraying, typically applied at an agronomically effective and essentially non-phytotoxic level via foliar or stem application. This method offers diverse modes of action and a wider range of application periods. Compared to the single-period seed treatment, foliar spraying can act on plants throughout their entire growth cycle. 2) The targets of control are different. The fungal diseases disclosed in the patent are all caused by Pythium spp. In contrast, the composition of this invention targets both bacterial and fungal diseases, including Xanthomonas spp., Pseudomonas spp., Ascomycetes spp., Oomycetes, Peronosporales, and Apocytozoa spp. These pathogens are completely different from those disclosed in the patent, and their modes of infection are also drastically different, resulting in a broader spectrum of control. Furthermore, the combination of quinoline copper and phosphite has unexpected control effects on various bacterial or fungal diseases such as ulcer and downy mildew, with significant synergistic effects.

[0008] Patent CN1305347A reports a biocidal composition containing phosphite ions. This patent describes how phosphite combined with quinoline copper provides antifungal or antibacterial protection to the substrate, suitable for trees used in wood and lignocellulose products, providing relative immunity or self-protection against fungal attacks during growth, and applicable to wood preservation in the timber industry. Lü Jun [Journal of Mountain Agriculture and Biology, 2023, Vol. 43, No. 3] found that wood rot is a common plant disease, usually caused by wood-decaying fungi. Based on the harmful characteristics of wood-decaying fungi, they can be divided into three categories: white rot fungi, brown rot fungi, and soft rot fungi. The composition of this invention is mainly applied in the agrochemical industry, suitable for the prevention and control of bacterial and fungal diseases in food crops, cash crops, fruits and vegetables, and turf and garden crops. The application industries and target pests / diseases are completely different.

[0009] Patent CN106172497B reports a fungicide composition containing thiazolium zinc and phosphite, and its uses, disclosing the combination of the active compound thiazolium zinc and phosphite. Thiazolium zinc primarily controls bacterial diseases, but it has no inhibitory effect on bacteria outside the plant and its protective effect is inferior to quinoline copper. Furthermore, copper formulations are more widely used than zinc formulations in the pesticide fungicide industry, as they can quickly form a film, are resistant to rain washout, and have a long-lasting effect. Patent CN111466393A discloses a fungicide combination containing thiamethoxam and phosphite, disclosing the combination of the active compound thiamethoxam and phosphite. Thiamethoxam has preventive and curative effects against fungal diseases, but its protective effect is inferior to quinoline copper. Patent CN111848295A reports a fungicide composition containing potassium phosphite and its applications. The active ingredients of the fungicide composition include at least one of potassium phosphite and kasugamycin, kasugamycin salts, kasugamycin, jinggangmycin, tetracycline, and polyoxin. Patent CN112056319B discloses a bactericidal composition containing benzylthiamethoxam and phosphite, and its application.

[0010] Therefore, the active ingredients and mechanisms of action described in the above reports are fundamentally different from those of this invention. To date, there are no reports on the effectiveness of bactericidal compositions of quinoline copper and phosphites in controlling bacterial and fungal diseases.

[0011] Agricultural bacterial and fungal diseases refer to plant diseases caused by bacterial and fungal infections, such as bacterial canker, bacterial wilt, downy mildew, and powdery mildew. Bacterial and fungal diseases are important factors affecting agricultural production value. This invention uses citrus canker and grape downy mildew as examples to illustrate the application value of this invention in the treatment of bacterial and fungal diseases.

[0012] Citrus canker is a global disease and one of the major diseases in citrus-producing areas. The pathogen is Xanthomonas Campestris pv. citri [TropicalPlant Pathology. 2012, 37(1)]. It mainly affects leaves, branches, fruits, and sepals. When the disease is severe, it can cause leaf drop, fruit drop, or branch dieback, affecting the normal growth of the plant. When the fruit is infected, it will rot and lose its commercial value. Citrus is the world's largest fruit, and it is grown in 138 countries and regions, including Brazil, China, and the United States, with a total area of ​​about 8 million hectares and a total output of more than 120 million tons. China is the most important origin center of citrus. At present, the citrus cultivation area is about 1.9 million hectares, and the annual output is about 20 million tons, ranking first and second in the world, respectively. Citrus canker has had a significant impact on my country's citrus industry, and the disease has been prevalent in coastal areas such as Guangdong, Guangxi, Fujian, Zhejiang, and Hainan. In Jiangxi Province, with a citrus planting area of ​​approximately 150,000 hectares, citrus canker has affected about 25,000 hectares; in Hunan Province, with a citrus planting area of ​​over 280,000 hectares, citrus canker has affected over 10,000 hectares. 2 In Guizhou Province, the affected area of ​​citrus canker exceeds 3,000 hectares. It is evident that citrus canker directly impacts the yield and value of citrus.

[0013] Grape downy mildew was first recorded in China in 1899, and has a history of over 100 years. Its causative agent is *Plasmopara viticola* (Berk. & Curt.), an obligate parasite belonging to the phylum Oomycetes, order Peronomales, family Peronomycetes, genus *Plasmopara*. It primarily affects leaves, impairing their nutrient synthesis capacity, affecting flower bud differentiation, leading to premature leaf drop, and in severe cases, causing vine death. It can also infect inflorescences, fruit stalks, and berries, resulting in deteriorated fruit quality and significantly impacting vine vigor and yield. This disease spreads rapidly and occurs quickly, making it the most prevalent grape disease in my country, particularly severe during the rainy season in southern regions, significantly affecting both grape yield and quality.

[0014] In summary, this invention creatively proposes a fungicidal composition of quinoline copper and phosphite for foliar spraying to control bacterial and fungal diseases in crops. It exhibits a significant synergistic effect, enhancing control efficacy while delaying resistance accumulation, thus contributing positively to the "reduced dosage, increased efficiency" approach to pesticides. This invention, applied through foliar spraying and other methods, is suitable for controlling fungal and bacterial diseases, with a wide range of application methods, applicable periods, and control scope, providing a new solution for disease control in agricultural production. Summary of the Invention

[0015] The purpose of this invention is to provide a composition for foliar spraying that has a synergistic effect in controlling bacterial and fungal diseases of crops.

[0016] Another object of the present invention is to apply the bactericidal composition to the prevention and control of bacterial and fungal diseases caused by crop monotypic bacteria, bacilli, or parasitic oomycetes.

[0017] The above-mentioned objective of the present invention is achieved through the following technical solution:

[0018] This invention provides a bactericidal composition for foliar spraying, wherein the active ingredients of the bactericidal composition include quinoline copper and phosphite A, wherein phosphite A is selected from one or more of phosphorous acid, alkali metal salts or alkaline earth metal salts of phosphorous acid, alkylphosphonic acids containing C1-C6 groups or alkali metal salts of alkylphosphonic acids, alkaline earth metal salts and aluminum salts, wherein the weight ratio of quinoline copper to phosphite A is 99:1 to 1:99, and the total weight percentage of quinoline copper and phosphite A in the total bactericidal composition is 1% to 70%.

[0019] Furthermore, the phosphite A is selected from at least one of potassium phosphite, sodium phosphite, and ethylphosphine aluminum. The weight ratio of quinoline copper to phosphite A is 70:1 to 1:60, and the total weight percentage of quinoline copper and phosphite A in the total bactericidal composition is 1%-60%.

[0020] The bactericidal composition of the present invention can be formulated into solid dosage forms: powders, wettable powders, water-dispersible granules, dry suspensions, or effervescent tablets; and liquid dosage forms: suspensions, dispersible oil suspensions, microcapsule suspensions, or suspension-microcapsule suspensions. The definitions, development methods, application technologies, quality indicators, and testing methods of the above dosage forms are referenced in Xu Yan, Liu Guangwen et al. ["Pesticide Liquid Formulations," (2018, Chemical Industry Press)], and Liu Guangwen et al. ["Pesticide Solid Formulations," (2018, Chemical Industry Press)].

[0021] The bactericidal composition of the present invention also contains commonly used adjuvants required for the formulation of pesticide formulations, wherein solid formulations include wetting agents, dispersants, defoamers, complexing agents, pH adjusters and fillers, etc., and liquid formulations include dispersants, emulsifiers, wetting agents, stabilizers, thickeners, pH adjusters, defoamers, antifreeze agents and encapsulating agents, etc.

[0022] The wetting agent is selected from one or more of EO / PO block polyether, fatty alcohol polyoxyethylene ether, fatty alcohol ethoxy compound, tallow ethoxy ammonium salt, alkyl naphthalene sulfonate, fatty alcohol polyoxyethylene ether sulfate, and acyl glutamate.

[0023] The dispersant is selected from one or more of the following: EO / PO block polyether, condensed naphthalene sulfonate, sodium salt of phenol sulfonic acid condensate, sodium formaldehyde condensate of methyl naphthalene sulfonate, sodium lignin sulfonate, sodium methylene dinaphthalene sulfonate, sodium salt of acrylic acid homopolymer, high molecular weight polycarboxylate, sodium dioctyl sulfosuccinate, and sodium salt of maleic acid-acrylic acid copolymer.

[0024] The emulsifier is selected from one or more of the following: alkylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, fatty amine polyoxyethylene ether, castor oil ethylene oxide adduct and its derivatives, alkyl sulfonates, alkyl biphenyl ether sulfonates, naphthalene sulfonic acid formaldehyde condensates, alkylphenol polyoxyethylene ether formaldehyde condensates, polyoxyethylene polyoxypropylene block copolymers, alkyl naphthalene sulfonic acid formaldehyde condensates, quaternary ammonium salts, tallow ethoxy ammonium salts, amino acids, amine oxides, betaine, and acylglutamates.

[0025] The bactericidal composition of the present invention can be used to prevent and control bacterial and fungal diseases of crops. The crops are selected from food crops, cash crops, fruits and vegetables and turf and garden crops. Food crops include corn, rice and wheat, cash crops include peanuts, cotton and rapeseed, fruits and vegetables include citrus, apples, grapefruits, pears, bayberries, tomatoes, eggplants and peppers, and turf and garden crops include flowers, grasses planted on lawns and trees.

[0026] The bactericidal composition of the present invention can be used to prevent and control bacterial and fungal diseases of crops. The bacterial diseases prevented and controlled include bacterial leaf streak of rice, bacterial leaf blight of cucumber, black rot of cabbage, citrus canker, bacterial shot-hole disease of peach, bacterial angular leaf spot of cucumber, bacterial wilt of solanaceous plants, bacterial leaf blight of melon, bacterial wilt of tomato, bacterial wilt of potato, and bacterial wilt of strawberry, etc. The fungal diseases prevented and controlled include bacterial leaf blight of rice, powdery mildew of cucumber, powdery mildew of zucchini, downy mildew of grape, downy mildew of cucumber, downy mildew of melon, and gray mold of cucumber, etc.

[0027] On the other hand, the bactericidal composition of the present invention can act on crop pathogens or their environment, or on plants, plant parts, plant propagation material and subsequently grown plant organs, soil or cultivation medium, material or space.

[0028] On the other hand, the bactericidal composition of the present invention is generally used by spraying, but may also be used by other agricultural application techniques as needed, usually by foliar application, stem application, etc., at an agronomically effective and substantially non-phytotoxic dosage.

[0029] Compared with the prior art, the advantages of the present invention are as follows:

[0030] 1. Diverse control targets: The composition of this invention has control effects on both bacterial and fungal diseases, with a variety of targets and a wide range of control.

[0031] 2. Increased bactericidal activity: The bactericidal composition of the present invention is composed of effective ingredients with different mechanisms of action, which enhances bactericidal activity and delays the development of resistance.

[0032] 3. It combines antibacterial, bactericidal, and growth-promoting effects: The bactericidal composition of this invention synergistically increases the antibacterial and bactericidal effects, supplements crops with copper and phosphorus elements, and promotes crop growth, stress resistance, and disease resistance.

[0033] 4. Aerial spraying: The composition of this invention has excellent stability and is more suitable for aerial spraying. Detailed Implementation

[0034] To better understand the essence of this invention, the following embodiments further illustrate the content of this invention, but these should not be considered as limitations on the invention. The content mentioned in the embodiments is not intended to limit the invention, and the selection of material formulations can be adapted to local conditions without substantially affecting the results. In these embodiments, unless otherwise stated, all percentages are weight percentages.

[0035] Indoor activity assay method

[0036] This invention has undergone extensive target testing. Taking the virulence test of Xanthomonas Campestris pv. citri, the pathogen of citrus canker, and Plasmoparaviticola (Berk. & Curt.), the pathogen of grape downy mildew, as examples, the invention demonstrates its indoor activity determination.

[0037] Xanthomonas campestris pv. citri, a citrus-pathogenic strain of *Xanthomonas campestris*.

[0038] The experiment was conducted in accordance with the People's Republic of China Agricultural Industry Standard NY / T 1156.16-2008 "Guidelines for Indoor Bioassay of Pesticides - Fungicides Part 16: Test for Inhibition of Bacterial Growth - Turbidity Method".

[0039] 1. Experimental objective: To screen the indoor toxicity of different compound combinations to pathogenic bacterial bacteria;

[0040] 2. Experimental conditions

[0041] 2.1 Test Target: Xanthomonas Campestris pv. citri

[0042] 2.2 Culture conditions: LB liquid medium, temperature 28.0-30.0℃;

[0043] 2.3 Experimental apparatus: electronic balance, shaking incubator, petri dishes, conical flasks, pipettes, spreaders, constant temperature incubator;

[0044] 3. Test methods

[0045] 3.1 Prepare the stock solution and adjust it to the treatment concentration according to each treatment, then set it aside for use;

[0046] 3.2. According to the experimental design, add 3.00 mL of drug solution sequentially from low to high concentration to 27.0 mL of LB liquid medium, with 3 replicates for each treatment; and ensure that the final concentration of each treatment is the required concentration.

[0047] 3.3. Take 100.0 μL of the activated fresh bacterial solution and add it to LB liquid medium;

[0048] 3.4 Before starting the culture, take 3.00 mL from one replicate of each treatment and measure its OD. 600 The value serves as a control for the drug in each treatment;

[0049] 3.5. Incubate at 28.0℃ with constant temperature shaking (180 rpm) for 24 hours.

[0050] 4. Experimental investigation and calculation methods:

[0051] Before starting the culture, the turbidity of each treatment was measured. When the control treatment reached the logarithmic growth phase, the turbidity of each treatment was measured and recorded.

[0052]

[0053]

[0054] Theoretical toxicity index of mixture

[0055] = Toxicity index of drug A × Percentage content of drug A in the mixture

[0056] +B agent toxicity index × B agent percentage in the mixture

[0057]

[0058] The theoretical toxicity index of a mixture is equal to the sum of the products of the toxicity indices of each individual agent and their content in the mixture. A co-toxicity coefficient greater than 120 indicates a synergistic effect, a co-toxicity coefficient greater than or equal to 80 and less than or equal to 120 indicates an additive effect, and a coefficient less than 80 indicates an antagonistic effect.

[0059] Plasmopara viticola (Berk. & Curt.) is a grape-borne monocoid fungus.

[0060] The experiment was conducted in accordance with the People's Republic of China Agricultural Industry Standard NY / T 1156.3-2006 "Guidelines for Indoor Bioassay of Pesticides - Fungicides Part 3: Test for Inhibition of Cucumber Downy Mildew - Plate Leaf Method".

[0061] 1. Experimental objective: To screen the indoor toxicity of different compound combinations against *Pseudomonas pseudoperonocrinoides*;

[0062] 2. Experimental conditions

[0063] 2.1 Test target: Plasmopara viticola (Berk. & Curt.)

[0064] 2.2. Culture conditions: constant temperature incubator, temperature 17-22℃, light intensity L:D = 12:12h;

[0065] 2.3 Experimental apparatus: electronic balance, shaking incubator, petri dishes, conical flasks, pipettes, constant temperature incubator;

[0066] 3. Test methods

[0067] 3.1 Prepare the stock solution and adjust it to the treatment concentration according to each treatment, then set it aside for use;

[0068] 3.2 Select diseased leaves, wash off the sporangia of the pathogen from the underside of the leaves with distilled water at 4℃, prepare a suspension (concentration 1×10⁵~1×10⁷ sporangia / mL), and store at 4℃ for later use.

[0069] 3.3. Spray the pesticide solution evenly onto the underside of the leaves. After the solution has air-dried naturally, place the leaves of each treatment with the underside facing upwards in a petri dish according to the treatment label. A blank control was provided for a treatment containing the corresponding organic solvent but without the pesticide. Each treatment was repeated three times.

[0070] 3.4. Apply 10 μL of the prepared fresh sporangium suspension to the underside of each leaf. Inoculate 4 drops per leaf, with at least 5 leaves per treatment. Inoculate 24 hours after treatment and include a control treatment containing the appropriate organic solvent but without the pesticide. After inoculation, cover the dish and place it in a constant temperature incubator.

[0071] 4. Experimental investigation and calculation methods:

[0072] Based on the incidence of the blank control group, the diameter of the lesions was measured and recorded in millimeters (mm).

[0073]

[0074] Theoretical toxicity index of mixture

[0075] = Toxicity index of drug A × Percentage content of drug A in the mixture

[0076] +B agent toxicity index × B agent percentage in the mixture

[0077]

[0078] The theoretical toxicity index of a mixture is equal to the sum of the products of the toxicity indices of each individual agent and their content in the mixture. A co-toxicity coefficient greater than 120 indicates a synergistic effect, a co-toxicity coefficient greater than or equal to 80 and less than or equal to 120 indicates an additive effect, and a coefficient less than 80 indicates an antagonistic effect.

[0079] Indoor Activity Assay Example 1: Quinoline Copper and Potassium Phosphite

[0080] Based on extensive mixing experiments of this invention, five mixing ratios (1:10, 1:1, 10:1, 20:1, and 40:1) were used for toxicity testing and demonstration. The experimental dosage design after preliminary testing is shown in Table 1.

[0081] Table 1. Dosage design for the experiment involving quinoline copper and potassium phosphite.

[0082]

[0083] Turbidity tests were conducted using the drug dosages shown in Table 1, and the OD values ​​of each cell were statistically analyzed. 600 Values ​​were obtained through data analysis to determine the growth inhibition rate of each plot. The growth inhibition rates of single-agent quinoline copper and potassium phosphite were analyzed to infer the baseline toxicity and EC50 of quinoline copper and potassium phosphite. 50 The values ​​are shown in Table 2:

[0084] Table 2. Indoor toxicity determination of quinoline copper and potassium phosphate against pathogens of citrus canker.

[0085]

[0086] Table 2 shows that quinoline copper and potassium phosphate have antibacterial activity against the pathogen of citrus canker, with quinoline copper showing EC antibacterial activity against the pathogen of citrus canker. 50 The concentration of potassium phosphate was 47.64 mg / L, with an EC value of 47.64 mg / L, indicating its antibacterial activity against the pathogen causing citrus canker. 50 The concentration was 273.38 mg / L.

[0087] Turbidity tests were conducted using the drug dosages shown in Table 1 to obtain the growth inhibition rates of five dosages of quinoline copper and potassium phosphite at five different ratios against the pathogen of citrus canker. Analysis revealed the baseline toxicity and EC50 values ​​for each ratio. 50 The results are shown in Table 3:

[0088] Table 3. Toxicity determination of five compound formulations against citrus canker.

[0089]

[0090] Table 3 shows that all formulations of quinoline copper and potassium phosphite exhibited inhibitory activity against the pathogen causing citrus canker. The EC50 values ​​for each formulation are as follows: 50 The concentrations ranged from 42.53 to 202.82 mg / L, with the 20:1 ratio showing the highest activity. (EC) 50 The concentration was 35.34 mg / L.

[0091] The compound preparations EC in each group are shown in Table 3. 50 The combined effects of five compound ratios of quinoline copper and potassium phosphite on the pathogens causing citrus canker were evaluated by analyzing the data, as shown in Table 4.

[0092] Table 4. Evaluation of the combined effects of five compound ratios of quinoline copper and potassium phosphite on the pathogens causing citrus canker.

[0093]

[0094] As shown in Table 4, the co-toxicity coefficients of the five ratios of quinoline copper and potassium phosphite ranged from 93.19 to 140.32. The different ratios showed different modes of combined action against the pathogens of citrus canker. Among them, the co-toxicity index value of the quinoline copper:potassium phosphite ratio of 20:1 was 140.32.

[0095] The above experiments on the combination of potassium phosphite and quinoline copper showed that the two have a synergistic effect. The combined use can delay the development of drug resistance in citrus canker, improve the control effect, reduce environmental pollution, save resources, and reduce the agricultural cost of the product.

[0096] Example 2 of Indoor Activity Assay: Quinoline Copper and Sodium Phosphite

[0097] Based on extensive mixing experiments of this invention, five mixing ratios (1:1, 15:1, 30:1, 45:1, and 60:1) were used for toxicity testing and demonstration. The experimental dosage design after preliminary testing is shown in Table 5.

[0098] Table 5. Dosage design for the quinoline copper and sodium phosphite experiments.

[0099]

[0100] Turbidity tests were conducted using the drug dosages shown in Table 5, and the OD values ​​of each cell were statistically analyzed. 600 Values ​​were obtained through data analysis to determine the growth inhibition rate of each plot. The growth inhibition rates of single-agent quinoline copper and sodium phosphite were analyzed to infer the baseline toxicity and EC50 of quinoline copper and sodium phosphite. 50 The values ​​are shown in Table 6:

[0101] Table 6. Indoor toxicity determination of quinoline copper and sodium phosphite against pathogens causing citrus canker.

[0102]

[0103] Table 6 shows that quinoline copper and sodium phosphite have antibacterial activity against the pathogen of citrus canker, with quinoline copper exhibiting EC activity against the pathogen of citrus canker. 50 The concentration of sodium phosphite was 47.64 mg / L, with an EC value of 47.64 mg / L, indicating its antibacterial activity against the pathogen causing citrus canker. 50 The concentration was 338.08 mg / L.

[0104] Turbidity tests were conducted using the drug dosages shown in Table 5 to obtain the growth inhibition rates of five dosages of quinoline copper and sodium phosphite against the pathogen of citrus canker. Analysis revealed the baseline toxicity and EC50 values ​​for each dosage. 50 The results are shown in Table 7:

[0105] Table 7. Toxicity determination of five compound formulations against citrus canker.

[0106]

[0107] Table 7 shows that all formulations of quinoline copper and sodium phosphite exhibited antibacterial activity against the pathogen causing citrus canker. The EC50 values ​​for each formulation are as follows: 50 The concentrations ranged from 34.91 to 92.77 mg / L, with the 30:1 ratio showing the highest activity. (EC) 50 The concentration was 34.91 mg / L.

[0108] The compound preparations EC in each group are shown in Table 7. 50 The combined effects of five compound ratios of quinoline copper and sodium phosphite on the pathogenic bacteria of citrus canker were evaluated by analyzing the data, as shown in Table 8.

[0109] Table 8 Evaluation of the combined effects of five compound ratios of quinoline copper and sodium phosphite on the pathogens causing citrus canker.

[0110]

[0111] As shown in Table 8, the co-toxicity coefficients of the five ratios of quinoline copper and sodium phosphite ranged from 90.03 to 140.36. Different ratios showed different modes of combined action against the pathogens of citrus canker. Among them, the co-toxicity index value of the quinoline copper:sodium phosphite ratio of 30:1 was 140.36.

[0112] The above experiments on the combination of sodium phosphite and quinoline copper showed that the two have a synergistic effect. The combined use can delay the development of drug resistance in citrus canker, improve the control effect, reduce environmental pollution, save resources, and reduce the agricultural cost of the product.

[0113] Indoor Activity Assay Example 3: Quinoline Copper and Ethylphosphine Aluminum

[0114] Based on extensive mixing experiments of this invention, five mixing ratios (1:10, 1:1, 10:1, 20:1, and 40:1) were used for toxicity testing and demonstration. The experimental dosage design after preliminary testing is shown in Table 9.

[0115] Table 9. Dosage Design for Quinoline Copper and Ethylphosphine Aluminum Experiments

[0116]

[0117] Turbidity tests were conducted using the drug dosages shown in Table 9, and the OD values ​​of each cell were statistically analyzed. 600 Values ​​were obtained through data analysis to determine the growth inhibition rate of each plot. The growth inhibition rates of quinoline copper and fosetyl-aluminum single agents were analyzed to infer the baseline toxicity and EC50 of quinoline copper and fosetyl-aluminum. 50 The values ​​are shown in Table 10:

[0118] Table 10. Indoor toxicity determination of quinoline copper and ethionyl aluminum against pathogens causing citrus canker.

[0119]

[0120]

[0121] Table 10 shows that quinoline copper and fosetyl-aluminum have antibacterial activity against the pathogen of citrus canker. The EC50 of quinoline copper against the pathogen of citrus canker is 47.64 mg / L, and the EC50 of fosetyl-aluminum against the pathogen of citrus canker is 243.17 mg / L.

[0122] Turbidity tests were conducted using the drug dosages shown in Table 9 to obtain the growth inhibition rates of five dosages of quinoline copper and fosetyl-aluminum in five ratios against the pathogen of citrus canker. The baseline toxicity and EC50 values ​​for each ratio are shown in Table 11.

[0123] Table 11. Toxicity determination of five compound formulations against citrus canker.

[0124]

[0125] Table 11 shows that all the compound formulations of quinoline copper and fosetyl-aluminum exhibited antibacterial activity against the pathogen causing citrus canker. The EC50 values ​​of each formulation ranged from 40.39 to 208.22 mg / L, with the 40:1 formulation showing the highest activity and an EC50 of 40.39 mg / L.

[0126] The combined effects of five compound formulations of quinoline copper and fosetyl-aluminum against the pathogen of citrus canker were evaluated by analyzing the EC50 values ​​of each group in Table 11, as shown in Table 12.

[0127] Table 12 Evaluation of the combined effects of five compound ratios of quinoline copper and fosetyl-aluminum on the pathogens causing citrus canker.

[0128]

[0129] As shown in Table 12, the co-toxicity coefficients of the five ratios of quinoline copper and fosetyl-aluminum ranged from 80.98 to 125.04. The different ratios showed different modes of combined action against the pathogen of citrus canker. Among them, the co-toxicity index value of the quinoline copper:fosetyl-aluminum ratio of 20:1 was 125.04.

[0130] The above experiments on the combination of ethionyl aluminum and quinoline copper showed that the two have a synergistic effect. The combined use can delay the development of drug resistance in citrus canker, improve the control efficacy, reduce environmental pollution, save resources, and reduce the agricultural cost of the product.

[0131] Example 4 of Indoor Activity Assay: Quinoline Copper and Ethylphosphine Aluminum

[0132] Based on extensive mixing experiments of this invention, five mixing ratios (1:40, 1:20, 1:1, 20:1, and 40:1) were used for toxicity testing and demonstration. The experimental dosage design after preliminary testing is shown in Table 13.

[0133] Table 13 Dosage Design for Quinoline Copper and Ethylphosphine Aluminum Experiments

[0134]

[0135] The pesticides were sprayed according to the dosages shown in Table 13. The lesion situation in each plot was recorded. The control effect of each plot was obtained through data analysis. The control effects of quinoline copper and fosetyl-aluminum as single agents were analyzed. The baseline toxicity and EC50 values ​​of quinoline copper and fosetyl-aluminum are shown in Table 14.

[0136] Table 14. Indoor toxicity determination of quinoline copper and phosphoaluminum against the pathogen of grape downy mildew.

[0137]

[0138] Table 14 shows that quinoline copper and fosetyl-aluminum have antibacterial activity against the pathogen causing grape downy mildew, with quinoline copper showing the highest antibacterial activity against the pathogen, EC. 50 The concentration of fosetyl-aluminum was 47.64 mg / L, with an EC50 concentration of [missing value]. 50 The concentration was 273.38 mg / L.

[0139] The control effects of five different ratios and dosages of quinoline copper and fosetyl-aluminum against the pathogen causing grape downy mildew were obtained by spraying according to the dosages shown in Table 13. Analysis revealed the baseline toxicity and EC50 values ​​for each ratio. 50 The results are shown in Table 15:

[0140] Table 15. Virulence determination of five compound formulations against grape downy mildew.

[0141]

[0142] Table 15 shows that the combined formulations of quinoline copper and fosetyl-aluminum all exhibited inhibitory activity against the pathogen causing grape downy mildew. The EC50 values ​​for each formulation are as follows: 50 The concentrations ranged from 8.590 to 42.19 mg / L, with the 20:1 ratio showing the highest activity. (EC) 50 It is 8.590 mg / L.

[0143] The compound preparations EC in each group of Table 15 50 The combined effects of five compound ratios of quinoline copper and fosetyl-aluminum on the pathogens causing grape downy mildew were evaluated by analyzing the data, as shown in Table 16.

[0144] Table 16 Evaluation of the combined effects of five compound ratios of quinoline copper and fosetyl-aluminum on the pathogens causing grape downy mildew.

[0145]

[0146]

[0147] As shown in Table 16, the co-toxicity coefficients of the five ratios of quinoline copper and fosetyl-aluminum ranged from 93.52 to 133.5. Different ratios showed different modes of combined action against the pathogen of grape downy mildew. Among them, the co-toxicity index value of the quinoline copper:fosetyl-aluminum ratio of 20:1 was 133.58.

[0148] The above experiments on the combination of quinoline copper and ethion aluminum show that the two have a synergistic effect. The combined use can delay the development of resistance to grape downy mildew, improve the control effect, reduce environmental pollution, save resources, and reduce the agricultural cost of the product.

[0149] Formulation Excipient Example 1: 11% Quinoline Copper·Potassium Phosphite Suspension (10:1)

[0150] The composition of 11% quinoline copper·potassium phosphite suspension is shown in Table 17:

[0151] Table 17 Component Details of 11% Quinoline Copper·Potassium Phosphite Suspension

[0152]

[0153] According to the component details in Table 17, weigh out the active ingredient, wetting agent, dispersant, antifreeze, preservative, and a portion of the thickener, defoamer, and water in proportion, mix thoroughly, and grind. Stop grinding when the particle size reaches 5 μm. Add the remaining thickener and defoamer and adjust until homogeneous to obtain the suspension product. The product standard test results of the 11% quinoline copper·potassium phosphite suspension of this invention are shown in Table 18.

[0154] Table 18 Detailed Test Results of Various Indicators for 11% Quinoline Copper·Potassium Phosphite Suspension

[0155]

[0156]

[0157] As shown in Table 18, the bactericidal composition of the present invention, 11% quinoline copper·potassium phosphite suspension, meets all product standards and is a qualified product. Formulation Example 2: 42% quinoline copper·potassium phosphite water-dispersible granules (20:1)

[0158] The composition of 42% quinoline copper·potassium phosphite water-dispersible granules is shown in Table 19:

[0159] Table 19 Component Details of 42% Quinoline Copper·Potassium Phosphite Water Dispersible Granules

[0160]

[0161] According to the component details in Table 19, active ingredient 1, active ingredient 2, dispersant, wetting agent, and carrier are added to a mixing tank and mixed for 10 minutes. The above materials are then subjected to air jet milling until D90 ≤ 25 μm. The milled materials are then mixed with water using a mixer (125-135 kg of deionized water per ton of material) to make the material plastic. The uniformly mixed material is extruded into columnar particles with a diameter of 1.0 mm and dried with hot air at 105°C until the moisture content is less than 3%, thus obtaining the 42% quinoline copper·potassium phosphite water-dispersible granules of the present invention. The product standard test results of the 42% quinoline copper·potassium phosphite water-dispersible granules of the present invention are shown in Table 20.

[0162] Table 20 Detailed Test Results of Various Indicators for 42% Quinoline Copper·Potassium Phosphite Water Dispersible Granules

[0163]

[0164]

[0165] As shown in Table 20, the bactericidal composition of the present invention, 42% quinoline copper·potassium phosphite water-dispersible granules, meets all product standards and is a qualified product.

[0166] Formulation Excipient Example 3: 35% Quinoline Copper·Potassium Phosphite Wettable Powder (1:1)

[0167] The composition of 35% quinoline copper·potassium phosphite wettable powder is shown in Table 21:

[0168] Table 21 Component Details of 35% Quinoline Copper·Potassium Phosphite Wettable Powder

[0169]

[0170] According to the component details in Table 21, the carrier and active ingredient 2 were mixed in a mixer for 10 minutes. Active ingredient 1, wetting agent, dispersant, and filler were then added in sequence and mixed for 10 minutes. The mixture was then subjected to air jet milling until D90 ≤ 35 μm, thus obtaining the 35% quinoline copper·potassium phosphite wettable powder of the present invention. The product standard test results of the 35% quinoline copper·potassium phosphite wettable powder of the present invention are shown in Table 22.

[0171] Table 22 Detailed Test Results of Various Indicators for 35% Quinoline Copper·Potassium Phosphite Wettable Powder

[0172]

[0173]

[0174] As shown in Table 22, the bactericidal composition of the present invention, 35% quinoline copper·potassium phosphite wettable powder, meets all product standards and is a qualified product.

[0175] Formulation Excipient Example 4: 31% Quinoline Copper·Sodium Phosphite Suspension (30:1)

[0176] The composition of 31% quinoline copper·sodium phosphite suspension is shown in Table 23:

[0177] Table 23 Component Details of 31% Quinoline Copper·Sodium Phosphite Suspension

[0178]

[0179] According to the component details in Table 23, weigh out the active ingredient, wetting agent, dispersant, antifreeze, preservative, and a portion of the thickener, defoamer, and water according to the specified proportions, mix them evenly, and grind them. When the particle size reaches 5 μm, stop grinding, add the remaining thickener and defoamer, and adjust evenly to obtain the suspension product. The product standard test results of the 31% quinoline copper·sodium phosphite suspension of the bactericidal composition of this invention are shown in Table 24.

[0180] Table 24 Detailed Test Results of Various Indicators for 31% Quinoline Copper·Sodium Phosphite Suspension

[0181]

[0182]

[0183] As shown in Table 24, the bactericidal composition of the present invention, 31% quinoline copper·sodium phosphite suspension, meets all product standards and is a qualified product. Formulation Example 5: 57.6% quinoline copper·sodium phosphite wettable powder (15:1)

[0184] The composition of 57.6% quinoline copper·sodium phosphite wettable powder is shown in Table 25:

[0185] Table 25 Component Details of 57.6% Quinoline Copper·Sodium Phosphite Wettable Powder

[0186]

[0187] According to the component details in Table 25, the carrier and active ingredient 2 were mixed in a mixer for 10 minutes. Active ingredient 1, wetting agent, dispersant, and filler were then added in sequence and mixed for 10 minutes. The mixture was then subjected to air jet milling until D90 ≤ 35 μm, thus obtaining the 57.6% quinoline copper·sodium phosphite wettable powder of the present invention. The product standard test results of the 57.6% quinoline copper·sodium phosphite wettable powder of the present invention are shown in Table 26.

[0188] Table 26 Detailed Test Results of Various Indicators for 57.6% Quinoline Copper·Sodium Phosphite Wettable Powder

[0189]

[0190]

[0191] As shown in Table 26, the bactericidal composition of the present invention, 57.6% quinoline copper·sodium phosphite wettable powder, meets all product standards and is a qualified product.

[0192] Formulation Excipient Example 6: 31.5% Quinoline Copper·Sodium Phosphite Water Dispersible Granules (1:20)

[0193] The composition of 31.5% quinoline copper·sodium phosphite water-dispersible granules is shown in Table 27:

[0194] Table 27 Component Details of 31.5% Quinoline Copper·Sodium Phosphite Water Dispersible Granules

[0195]

[0196] According to the component details in Table 27, active ingredient 1, active ingredient 2, dispersant, wetting agent, and carrier are added to a mixing tank and mixed for 10 minutes. The above materials are then subjected to air jet milling until D90 ≤ 25 μm. The milled materials are then mixed with water using a mixer (175-185 kg of deionized water per ton of material) to make the material plastic. The uniformly mixed material is then extruded into columnar particles with a diameter of 1.0 mm and dried with hot air at 120°C until the moisture content is less than 3%, thus obtaining the 31.5% quinoline copper·sodium phosphite water-dispersible granules of the present invention. The product standard test results of the 31.5% quinoline copper·sodium phosphite water-dispersible granules of the present invention are shown in Table 28.

[0197] Table 28 Detailed Test Results of Various Indicators for 31.5% Quinoline Copper·Sodium Phosphite Water Dispersible Granules

[0198]

[0199]

[0200] As shown in Table 28, the bactericidal composition of the present invention, 31.5% quinoline copper·sodium phosphite water-dispersible granules, meets all product standards and is a qualified product.

[0201] Formulation Excipient Example 7: 21% Quinoline Copper·Aluminum Fosetyl-Al Suspension (20:1)

[0202] The composition of 21% quinoline copper·aluminum fosetyl-aluminum suspension is shown in Table 29:

[0203] Table 29 Component Details of 21% Quinoline Copper·Aluminum Fosetyl Phosphate Suspension

[0204]

[0205] According to the component details in Table 29, weigh out the active ingredient, wetting agent, dispersant, antifreeze, preservative, and a portion of the thickener, defoamer, and water according to the specified proportions, mix them evenly, and grind them. When the particle size reaches 5 μm, stop grinding, add the remaining thickener and defoamer, and adjust evenly to obtain the suspension product. The product standard test results of the bactericidal composition 21% quinoline copper·aluminum fosetyl-aluminum suspension of the present invention are shown in Table 30:

[0206] Table 30 Detailed Test Results of Various Indicators for 21% Quinoline Copper·Aluminum Fosinate Suspension

[0207]

[0208]

[0209] According to Table 30, the bactericidal composition of the present invention, 21% quinoline copper·aluminum fosetyl-aluminum suspension, meets all product standards and is a qualified product. Formulation Example 8: 41% quinoline copper·aluminum fosetyl-aluminum wettable powder (1:40)

[0210] The composition of 41% quinoline copper·aluminum fosetyl-aluminum wettable powder is shown in Table 31:

[0211] Table 31 Component Details of 41% Quinoline Copper·Aluminum Fosetyl-Al

[0212]

[0213] According to the component details in Table 31, the carrier and active ingredient 2 were mixed in a mixer for 10 minutes. Active ingredient 1, wetting agent, dispersant, and filler were then added in sequence and mixed for 10 minutes. The mixture was then subjected to air jet milling until D90 ≤ 35 μm, thus obtaining the 41% quinoline copper·aluminum fosetyl-aluminum wettable powder of the present invention. The product standard test results of the 41% quinoline copper·aluminum fosetyl-aluminum wettable powder of the present invention are shown in Table 32.

[0214] Table 32 Detailed Test Results of Various Indicators for 41% Quinoline Copper·Aluminum Fosetyl-Al Wettable Powder

[0215]

[0216] According to Table 32, the bactericidal composition of the present invention, 41% quinoline copper·aluminum fosetyl-aluminum wettable powder, meets all product standards and is a qualified product.

[0217] Field efficacy methods for products:

[0218] According to the product formulation excipient examples, the present invention conducts field efficacy tests on the above formulations. The present invention uses *Pseudomonas syringae* pv. *actinidiae*, *Xanthomonas Campestris* pv. *citri*, *Clavibacter michiganense* subsp. *michiganense*, and *Plasmopara viticola* (Berk. & Curt.), the pathogen causing grape downy mildew, as examples to conduct field efficacy tests on the products. The standard description is as follows: Field test methods for kiwi fruit canker, citrus canker, and tomato canker.

[0219] The experiment was conducted in accordance with the People's Republic of China National Standard GB / T17980.103-2004 "Guidelines for Field Efficacy Tests of Pesticides (II) Part 103: Control of Citrus Canker by Fungicides":

[0220] 1. Experimental objective: To investigate the field control efficacy of different compound combinations against bacterial canker.

[0221] 2. Target pathogens for control: *Pseudomonas syringaepv. actinidiae*, *Xanthomonas campestris pv. citri*, and *Clavibacter michiganense subsp. michiganense*.

[0222] 3. Application method: Foliar spray at normal dosage

[0223] 4. Cell arrangement, area, and repetition:

[0224] The plots are arranged using a randomized block design, with the specific arrangement depending on the plant density. The plot area is approximately 30-100 square meters. 2 Repeat 3 times.

[0225] 5. Experimental investigation and calculation methods:

[0226] 5.1 Survey period: Surveys were conducted before spraying and 10 days after the first spraying, 10 days after the second spraying, and 10 days after the third spraying.

[0227] 5.2 Survey method: The number of disease spots on 5 leaves in each plot was randomly investigated using the "five-point sampling method", avoiding sampling at the edge of the plot.

[0228] Lesion grading criteria:

[0229]

[0230] 5.3 Method for Calculating Drug Efficacy

[0231]

[0232]

[0233] Field trial methods for grape downy mildew

[0234] The experiment was conducted in accordance with the People's Republic of China National Standard GB / T 17980.122-2004 "Field Efficacy Test Guidelines (II) Part 122: Efficacy Test of Fungicides for Controlling Grape Downy Mildew":

[0235] 1. Experimental objective: To investigate the field control efficacy of different compound combinations against grape downy mildew;

[0236] 2. Target pathogen for control: Plasmopara viticola (Berk. & Curt.) which causes grape downy mildew.

[0237] 3. Application method: Foliar spray at normal dosage

[0238] 4. Cell arrangement, area, and repetition:

[0239] The plots are arranged using a randomized block design, with the specific arrangement depending on the plant density. The plot area is approximately 30-100 square meters. 2 Repeat 3 times.

[0240] 5. Experimental investigation and calculation methods:

[0241] 5.1 Survey period: Surveys were conducted before spraying and 10 days after the first spraying, 10 days after the second spraying, and 10 days after the third spraying.

[0242] 5.2 Survey method: The number of disease spots on 5 leaves in each plot was randomly investigated using the "five-point sampling method", avoiding sampling at the edge of the plot.

[0243] Lesion grading criteria:

[0244]

[0245] 5.3 Method for Calculating Drug Efficacy

[0246]

[0247]

[0248] Example 1 of field efficacy of the product: Field trial of quinoline copper and potassium phosphite for the control of kiwifruit canker.

[0249] This experiment was conducted in Yichang City, Hubei Province. The experimental site comprised approximately 150 mu (about 10 hectares) of open-field kiwifruit (including Donghong and Jinyan varieties), with normal irrigation and drainage conditions and management. Kiwifruit canker was treated 5-8 times annually, but the incidence remained consistently low. The cultivation conditions (kiwifruit variety, soil type, water and fertilizer management, transplanting date, planting density, growth period, and water management) were relatively uniform across all experimental plots. The experimental design is shown in Table 29.

[0250] Based on the above conditions, according to Table 29, the present invention was sprayed once each on March 2, 2021, March 12, 2021, and March 22, 2021, for a total of three sprayings. The blank control was sprayed with an equal amount of water.

[0251] Table 29 Reagent Experimental Design

[0252]

[0253]

[0254] Based on the design in Table 29, on April 2, 2021, this invention statistically analyzed the disease index and prevention and control effects using the above-mentioned experimental survey and calculation methods. The results are shown in Table 30:

[0255] Table 30. Experimental results of various preparations for the prevention and treatment of kiwifruit canker.

[0256]

[0257] Table 30 shows that the field control efficacy of different ratios of quinoline copper and potassium phosphite formulations against kiwifruit canker was superior to that of quinoline copper and potassium phosphite alone. In Example 1 of the product formulation, the optimal control efficacy was achieved at a 1400-fold dilution and an active ingredient dosage of 150 mg / kg, with an average control efficacy of 76.14%.

[0258] Example 2 of product field efficacy: Field trial of quinoline copper and sodium phosphite for the control of citrus canker

[0259] This experiment was conducted in Taizhou City, Zhejiang Province. The experimental site comprised approximately 200 mu (about 33 acres) of open-field citrus trees (including Wogan and Meiren varieties), with normal irrigation and drainage conditions and management. The cultivation conditions (citrus variety, soil type, water and fertilizer management, transplanting date, planting density, growth stage, and water management) were relatively uniform across all experimental plots. Five-year-old Wogan trees were selected for pesticide application during the summer shoot growth stage. The experimental design is shown in Table 31.

[0260] Based on the above conditions, according to Table 31, the present invention was sprayed once each on July 4, 2021, July 14, 2021, and July 24, 2021, for a total of three sprayings. The blank control was sprayed with an equal amount of water.

[0261] Table 31 Reagent Experimental Design

[0262]

[0263] Based on the design in Table 31, on August 4, 2021, this invention statistically analyzed the disease index and prevention and control effects using the aforementioned experimental survey and calculation methods. The results are shown in Table 32:

[0264] Table 32. Experimental results of various formulations for the prevention and treatment of citrus canker.

[0265]

[0266] Table 32 shows that the field control efficacy of different ratios of quinoline copper and sodium phosphite formulations against citrus canker was superior to that of quinoline copper and sodium phosphite alone. In Example 3, the product formulation was best controlled at a 1400-fold dilution, with an effective ingredient dosage of 150 mg / kg, achieving an average control efficacy of 78.95%.

[0267] Example 3 of product field efficacy: Field trial of quinoline copper and ethionyl aluminum for the control of tomato bacterial canker

[0268] This experiment was conducted in Wenzhou City, Zhejiang Province. The experimental site comprised approximately 300 mu (about 20 hectares) of greenhouse-grown tomatoes (pink tomato variety), with normal irrigation and drainage conditions and management. The cultivation conditions (tomato variety, soil type, water and fertilizer management, transplanting date, planting density, growth period, and water management) were relatively uniform across all experimental plots. The experimental design is shown in Table 41.

[0269] Based on the above conditions, according to Table 33, the present invention was sprayed once each on December 8, 2020, December 18, 2020, and December 28, 2020, for a total of three sprayings. The blank control was sprayed with an equal amount of water.

[0270] Table 33 Reagent Experimental Design

[0271]

[0272] Based on the design in Table 33, on January 8, 2021, this invention statistically analyzed the disease index and prevention and control effects using the above-mentioned experimental survey and calculation methods. The results are shown in Table 34:

[0273] Table 34. Experimental results of various formulations for the prevention and control of tomato bacterial canker.

[0274]

[0275] Table 34 shows that the field control efficacy of different ratios of quinoline copper and fosetyl-aluminum formulations against tomato bacterial canker was superior to that of quinoline copper and fosetyl-aluminum alone. In Example 5, the product formulation was best controlled at a 1400-fold dilution, with an active ingredient concentration of 150 mg / kg, achieving an average control efficacy of 77.01%.

[0276] Example 4 of product field efficacy: Field trial of quinoline copper and fosetyl-aluminum for the control of grape downy mildew.

[0277] This experiment was conducted in Shaoxing City, Zhejiang Province. The experimental site comprised approximately 500 mu (about 33 hectares) of greenhouse-grown grapes (including varieties such as Xiahei and Jufeng), with normal irrigation and drainage conditions and management. The cultivation conditions (grape varieties, soil type, water and fertilizer management, transplanting time, planting density, growth period, and water management) were relatively uniform across all experimental plots. The experimental design is shown in Table 35.

[0278] Based on the above conditions, according to Table 35, the present invention was sprayed once each on May 20, 2021, May 30, 2021, and June 9, 2021, for a total of three sprayings. The blank control was sprayed with an equal amount of water.

[0279] Table 35 Reagent Experimental Design

[0280]

[0281] Based on the design in Table 35, on June 20, 2021, this invention statistically analyzed the disease index and prevention and control effects using the aforementioned experimental survey and calculation methods. The results are shown in Table 36:

[0282] Table 36. Test results of various formulations for controlling grape downy mildew.

[0283]

[0284]

[0285] Table 36 shows that the field control efficacy of different ratios of quinoline copper and fosetyl-aluminum formulations against grape downy mildew was superior to that of either quinoline copper or fosetyl-aluminum alone. In Example 7, the product formulation was best controlled at a 1400-fold dilution, with an active ingredient concentration of 150 mg / kg, achieving an average control efficacy of 81.29%.

[0286] In summary, the present invention employs a bactericidal composition for the prevention and control of bacterial and fungal diseases in crops. Compared with existing formulations, it not only has a significant synergistic effect but also exhibits excellent control efficacy, making it worthy of widespread application in agricultural production.

[0287] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. The use of a fungicide composition for foliar spraying in the prevention and control of citrus canker, characterized in that, The active ingredients of the bactericidal composition include quinoline copper and phosphite A, wherein phosphite A is selected from at least one of potassium phosphite, sodium phosphite, and ethylphosphite aluminum, wherein the weight ratio of quinoline copper to potassium phosphite is 10:1 to 20:1, the weight ratio of quinoline copper to sodium phosphite is 15:1 to 30:1, the weight ratio of quinoline copper to ethylphosphite aluminum is 20:1 to 40:1, and the total weight percentage of quinoline copper and phosphite A in the total bactericidal composition is 1% to 60%.

2. The use according to claim 1, characterized in that, The bactericidal composition can be formulated into one of the following: powder, wettable powder, granules, emulsifiable granules, water-dispersible granules, tablets, suspensions, emulsions, dispersible oil suspensions, and microcapsule suspensions.

3. The use according to claim 2, characterized in that, The bactericidal composition also contains commonly used adjuvants required for the formulation of pesticide formulations. These commonly used adjuvants are selected from one or a mixture of several of the following: solvents, wetting agents, stabilizers, dispersants, thickeners, pH adjusters, defoamers, antifreeze agents, and fillers.

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