Bactericidal suspending agent containing metalaxyl-M

Abstract

The invention relates to the technical field of pesticides, and discloses a sterilization suspending agent containing metalaxyl-M. 1000 parts by weight of the bactericidal suspending agent comprises the following raw materials: 30-150 parts by weight of metalaxyl-M, 90-450 parts by weight of oxine-copper, 10-200 parts by weight of a synergist, 50-400 parts by weight of an auxiliary agent and the balance of water, and the weight ratio of metalaxyl-M to oxine-copper is 1: 3. The synergist is a mixture of a microbial metabolite and a chemical synergist, and the weight ratio of the microbial metabolite to the chemical synergist is (2: 1)-(1: 2). The bactericidal suspending agent is used for preventing and treating grape downy mildew, the permeability of the agent can be obviously improved, the downy mildew can be rapidly controlled, photosynthesis of grape leaves can be promoted, fruit surfaces are purified, and fruit powder is not damaged.

Description

Technical Field

[0001] The present invention belongs to the technical field of pesticides, and particularly relates to a bactericidal suspension containing metalaxyl-M and its application. Background Art

[0002] Metalaxyl-M is a bactericide and soil disinfectant, which has a dual effect of protecting and treating crops. It has been widely used all the time. Generally, compound preparations are used. Using it alone easily induces the resistance of pathogenic bacteria.

[0003] Quinoline copper is an organic copper chelate, which has the characteristics of broad spectrum, high efficiency, low toxicity and low residue, and has good preventive and therapeutic effects on fungal and bacterial diseases.

[0004] Grape downy mildew occurs widely in grape-growing areas and is the largest grape disease in China. It causes different degrees of losses to fruit farmers every year. In some rainy years, it will cause the outbreak and epidemic of the disease, resulting in early leaf shedding or withering, poor growth of plants, and reduction of fruit yield and quality. The pathogen of grape downy mildew mainly overwinters in diseased tissues or in the soil with diseased tissues. As the main disease on grapes, due to the long latent period of the pathogen and easy generation of resistance, it is difficult to control once it occurs. And because of the large amount of pesticide use, multiple pests and diseases occur simultaneously, which is likely to cause the proliferation of pests such as spider mites. Most of the products on the market at present are for the purpose of prevention and protection, that is, applying medicine before the disease occurs. Therefore, how to provide a product with good bactericidal effect, less dosage and effective treatment of diseases is an urgent problem to be solved by those skilled in the art. Summary of the Invention

[0005] The purpose of the present invention is to provide a bactericidal suspension containing metalaxyl-M, which can effectively control grape downy mildew, can significantly increase the permeability of the medicament, can quickly control downy mildew, can also promote the photosynthesis of grape leaves, purify the fruit surface, does not damage the fruit powder, and avoids the problem of the proliferation of spider mites caused by diseases.

[0006] The technical solution of the present invention is as follows:

[0007] A bactericidal suspension containing metalaxyl-M, characterized in that: based on 1000 parts by weight of the bactericidal suspension, it comprises the following raw materials: 30-150 parts by weight of metalaxyl-M, 90-450 parts by weight of copper quinolate, 10-200 parts by weight of synergist, 50-400 parts by weight of auxiliary agent, and the balance is water, wherein the weight ratio of metalaxyl-M to copper quinolate is 1:3; the synergist is a mixture of microbial metabolites and chemical synergists, and the weight ratio of the two is 2:1 to 1:2, and the optional weight ratio is 1:1; the microbial metabolite is selected from one of erythritol, rhamnolipid, sophorolipid; the chemical synergist is selected from a mixture of polyethoxylated modified silane and polyethoxylated modified fatty alcohol or alkoxy modified polysiloxane.

[0008] Further, based on 1000 parts by weight of the bactericidal suspension, it comprises the following raw materials: 100 parts by weight of metalaxyl-M, 300 parts by weight of copper quinolate, 20-100 parts by weight of synergist, 70-300 parts by weight of auxiliary agent, and the balance is water.

[0009] Further, based on 1000 parts by weight of the bactericidal suspension, it is composed of the following components in the following contents: 100 parts by weight of metalaxyl-M, 300 parts by weight of copper quinolate, 50 parts by weight of synergist, 50 parts by weight of dispersant, 20 parts by weight of wetting agent, 50 parts by weight of antifreeze, 5 parts by weight of thickener, 1 part by weight of defoamer, 2 parts by weight of preservative, and the balance is water.

[0010] Further, the auxiliary agent is selected from one or more of a dispersant, a wetting agent, an antifreeze, a thickener, a defoamer, and a preservative.

[0011] The dispersant is selected from one or more of alkylnaphthalene sulfonates, alkylnaphthalene sulfonate formaldehyde polymers, lignin sulfonates, fatty alcohol polyoxyethylene ether phosphates, polycarboxylates, comb-shaped polycarboxylates, EO-PO block copolymers, and phenethylphenol polyoxyethylene ether phosphates;

[0012] The wetting agent is selected from one or more of alkyl sulfonates, alkylnaphthalene sulfonates, fatty alcohol polyoxyethylene ethers, alkyl glycosides, trisiloxane polyoxyethylene ethers, polyaryl phenol polyoxyethylene ethers, and castor oil polyoxyethylene ethers;

[0013] The antifreeze is selected from one or more of ethylene glycol, propylene glycol, glycerol, polyethylene glycol, allantoin, and sorbitol;

[0014] The preservative is benzoic acid and its sodium salt, isothiazolinone, sorbic acid and its sodium or potassium salt;

[0015] The defoamer is a silicone defoamer, a C10-20 saturated fatty acid compound, or a C8-10 fatty alcohol;

[0016] The thickener is selected from one or more of xanthan gum, polyvinyl alcohol, magnesium aluminum silicate, sodium carboxymethyl cellulose, sodium alginate and guar gum.

[0017] Furthermore, the fungicidal suspension is used in preventing and treating grape downy mildew.

[0018] Furthermore, when the fungicidal suspension is used to prevent and treat grape downy mildew, at the early larval stage of grape downy mildew, the dosage of the active ingredient is 100-400 mg / kg, and the optional dosage is 266.7 mg / kg.

[0019] Compared with the prior art, the composition of the present invention has the following beneficial effects: (1) compared with a single agent, the composition has a significant bactericidal effect on grape downy mildew, increases the permeability and surface tension of the agent, and significantly improves the control effect; (2) it is low in toxicity and high in efficiency, reduces the amount of pesticide used, reduces the amount of pesticide residue on crops, and has a short safety interval; (3) it has both rapid and long-lasting effects, and has a particularly good effect on resistant pests; (4) it improves the ability of crops to resist diseases and insects, and enhances crop photosynthesis; and (5) it has a certain promoting effect on increasing grape yield. DETAILED DESCRIPTION

[0020] The present invention is further described below in conjunction with embodiments, but the present invention is not limited thereto.

[0021] Application Example 1 The suspension composition disclosed in the following example contains the following components in 1000 parts by weight:

[0022]

[0023] Implementation application example 2:

[0024] Experiment on the combined toxicity test of metalaxyl, quinoline copper and their mixture against grape downy mildew in the laboratory 1. Experimental purpose

[0025] The toxicity of metalaxyl-M, quinoline copper and their different mixed combinations against downy mildew was determined indoors, and the fungicidal effects were evaluated to clarify the compatibility of the two, providing a scientific basis for the research and development of metalaxyl-M and quinoline copper mixtures.

[0026] 2 Experimental conditions

[0027] 2.1 Test targets

[0028] For downy mildew (Plasmopara viticola), grape leaves with more disease spots were collected from the field and brought back to the laboratory for use.

[0029] 2. Culture Conditions

[0030] Select the diseased leaves, wash the sporangia of downy mildew on the back of the leaves with distilled water at 4°C, and prepare a sporangia suspension with a concentration of 1x10 5 / mL. Store it in a refrigerator at 4°C for later use.

[0031] 3 Experimental design

[0032] 3.1 Experimental agents

[0033] Metalaxyl 92% technical, Oxine copper 98.5% technical.

[0034] 3.2 Agent preparation

[0035] Since the oxine copper technical is insoluble in many organic solvents, in the laboratory, oxine copper is processed into 33.5% oxine copper suspension by grinding with a sand mill.

[0036] Using DMF as a solvent, prepare a mother liquor of the experimental agent metalaxyl technical (A) at 1.0×10 4 mg / L and store it in a refrigerator for later use.

[0037] Prepare a mother liquor of oxine copper (B) at 1.0×10 4 mg / L with distilled water.

[0038] The effective ingredient ratios of the mixture of the two are Metalaxyl:Oxine copper at 3:1, 1:1, 1:3, 1:5, and 1:7 respectively, and they are also prepared into acetone mother liquors at 1.0×10 4 mg / L. The mixed mother liquor is prepared and used immediately.

[0039] Dilute and prepare with an aqueous solution containing 0.1% Tween 80. Design 5 concentrations for each ratio treatment, and use the treatment without the agent as the blank control. Each treatment is repeated 4 times.

[0040] Metalaxyl (A): 3.125, 6.25, 12.5, 25, 50 mg / L

[0041] Oxine copper (B): 10, 20, 40, 80, 160 mg / L

[0042] A:B (3:1): 3.125, 6.25, 12.5, 25, 50 mg / L

[0043] A:B (1:1): 3.75, 7.5, 15, 30, 60 mg / L

[0044] A:B (1:3): 5, 10, 20, 40, 80 mg / L

[0045] A:B (1:5): 5, 10, 20, 40, 80 mg / L

[0046] A:B(1:7): 7.5, 15, 30, 60, 120 mg / L

[0047] 4 Test methods

[0048] Refer to the "Pesticide Bioassay Guidelines for Indoor Fungicides - Inhibiting Pseudoperonospora cubensis Test - Petri Dish Leaf Method and Determination of the Combined Action of Fungicide Mixtures" (NY / T 1156.3 - 2006, NY / T 1156.6 - 2006).

[0049] 5 Data investigation and statistical analysis

[0050] 5.1 Investigation time and method

[0051] Measure and record the lesion diameter according to the disease incidence of the blank control, and calculate the control effect (%).

[0052]

[0053] Where: P - control effect; D0 - lesion diameter of the blank control; D1 - lesion diameter of the treatment.

[0054] 5.2 Evaluation method of bactericidal action

[0055] Refer to the bioassay standard method NY / T1156.6-2006, and evaluate the synergistic effect of the fungicide mixture 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.

[0056]

[0057] The theoretical toxicity index (TTI) of the mixture = toxicity index of agent A × percentage of agent A in the mixture (%) + toxicity index of agent B × percentage of agent B in the mixture (%)

[0058]

[0059] 6 Experimental results

[0060] Table 1 Toxicity determination results of metalaxyl - M and oxine - copper mixture against Plasmopara viticola

[0061]

[0062] It can be seen from the test results (see Table 1) that the test agents metalaxyl - M and oxine - copper both have high activity against Plasmopara viticola. The EC 50 value of metalaxyl - M is 11.7638 mg / L, and the EC 50The value is 38.4880 mg / L; the virulence (EC 50 ) of the two agents mixed in different ratios against Plasmopara viticola is 12.8665, 14.4956, 18.4402, 22.2080, and 29.8454 mg / L respectively, and the co-toxicity coefficient CTC values are 110.63, 124.31, 133.12, 125.71, and 100.44 respectively. It shows that within the range of the experimental design ratio of 1:1 to 1:5 for the two agents, the co-toxicity coefficient is greater than 120, indicating a synergistic effect. When the ratio is 1:3, the co-toxicity coefficient is the largest and the synergistic effect is significant.

[0063] Application Example 3: Field efficacy test of Examples 1 - 4 for controlling Plasmopara viticola 1 Test purpose

[0064] Verify the control effect of the 400 g / L metalaxyl-M · oxolinic copper suspension concentrate developed by the applicant against Plasmopara viticola and its safety to grapes, clarify the field application dosage and application technology, and provide a scientific basis for pesticide registration.

[0065] 2 Test basis

[0066] "Good Laboratory Practice for Pesticide Registration Tests", "GB / T17980.122 - 2004 Fungicides for Controlling Plasmopara viticola".

[0067] 3 Experimental location

[0068] This test is arranged in Xinjiang Uygur Autonomous Region and Sichuan Province.

[0069] 4 Selection of test object, crop and variety

[0070] Test object: Plasmopara viticola;

[0071] 5 Test design and arrangement

[0072] 5.1 Dosage and numbering of agents

[0073] Table 2 Experimental design of tested agents

[0074]

[0075]

[0076] 5.2 Application time and frequency

[0077] During the occurrence period of Plasmopara viticola, spraying is used for application, and it is applied once every 7 days for a total of 3 applications.

[0078] 5.3 Application volume

[0079] The liquid medicine dosage is 750 - 875 L / ha.

[0080] 5.4 Investigation Time and Frequency

[0081] Investigate the disease base number before applying the medicine, and investigate once every 7 days after each application of the medicine, for a total of 4 investigations.

[0082] 5.5 Investigation Method

[0083] Investigate 10 newly sprouted vines in the current year in each plot, and investigate all the leaves from top to bottom, record the number of diseased leaves and the disease severity of the investigated plants. The leaf grading method is as follows:

[0084] For 2 plants, take samples at 5 points in the east, west, south, north, and middle of each plant. Investigate 2 branches at each point, and investigate 4 leaves under the top leaf of each branch. The leaf (fruit) grading standard is as follows:

[0085] Grade 0: No disease spots;

[0086] Grade 1: The disease spot area accounts for less than 5% of the entire leaf area;

[0087] Grade 3: The disease spot area accounts for 6% - 25% of the entire leaf area;

[0088] Grade 5: The disease spot area accounts for 26% - 50% of the entire leaf area;

[0089] Grade 7: The disease spot area accounts for 51% - 75% of the entire leaf area;

[0090] Grade 9: The disease spot area accounts for more than 76% of the entire leaf area.

[0091] 5.6 Calculation Method of Drug Efficacy

[0092]

[0093]

[0094]

[0095]

[0096] Note: CK0 - Disease index of the control area (before applying the medicine);

[0097] CK1 - Disease index of the control area (after applying the medicine);

[0098] PT0 - Disease index of the prevention and control area (before applying the medicine);

[0099] PT1 - Disease index of the prevention and control area (after applying the medicine).

[0100] 6 Experimental Results

[0101] Table 3 Field Efficacy Test Results of Examples 1 - 3 for Controlling Grape Downy Mildew

[0102]

[0103] The experimental results show that the test substance 400 g / L of metalaxyl-quinoline copper suspension in the embodiment is applied to grape downy mildew at the early stage of grape downy mildew, and is sprayed at an effective ingredient dosage of 266.67 mg / kg. It can be seen from Table 3 that the test drug embodiments 1-4 of the present invention are used to prevent and control grape downy mildew. After 7 days of each application, the control effect is significantly better than that of the control agent. According to variance analysis, it is found that the test drug 400 g / L metalaxyl-quinoline copper suspension shows a very significant difference compared with the control single agent. With the increase in the number of times of application, the prevention effect is significantly increased, and it has a longer lasting effect. The yield is measured at the harvest time, and the yield increase rate of the test agent treatment is 5.82% to 7.40%. The entire experimental period is safe for crops and safe for applicators.

[0104] Application Example 4: Risk Assessment of (Examples 1 to 4) and Control Single Dose

[0105] Our company commissioned a third-party company to conduct residue determination on grapes for Examples 1 to 4 and a single control dose.

[0106] 1 Test basis

[0107] This test design refers to the "Guidelines for Testing for Pesticide Residues" and is determined by referring to the methods specified in GB23200.117 and GB23200.112.

[0108] 2 Experimental location

[0109] This experiment was conducted in Shaanxi Province.

[0110] 3. Selection of experimental subjects, crops and varieties

[0111] Test subject: Grapes.

[0112] 4 Experimental design and arrangement

[0113] 4.1 Dosage and number of medicines

[0114] Table 4 Experimental design of test drugs

[0115]

[0116] 5.2 Application and extraction.

[0117] The pesticide was applied three times, and 1 kg of fresh grape leaves were collected 1 day, 3 days, 7 days and 14 days after the last application of the pesticide. Random sampling was adopted, and the extraction was followed by detection and analysis using a chromatograph.

[0118] 6 Experimental results

[0119] Table 5 Results of the residual test of the tested drugs on grapes

[0120]

[0121] As can be seen from Table 5, compared with the pesticide residue experiments on grapes of Examples 1 to 4 and the control single agent, the residue amount of the Examples on the 1st day after application is equivalent to that of the control single agent, slightly better than the control single agent, and the residue amounts after 3 days, 7 days, and 14 days are significantly less than that of the control single agent, making the pesticide safety interval shorter and safer for consumers.

[0122] Application Example Five: Toxicological Determination Experiments of Examples 1 to 4

[0123] Our company entrusted a third-party testing agency to conduct acute toxicity determination tests on Examples 1 to 4, and the test results are as follows:

[0124] 1) Acute oral toxicity test. Experimental animals: rats; LD 50 Male / Female: 2350 / 2110 mg / kg body weight; the toxicity levels are all low toxicity.

[0125] 2) Acute percutaneous toxicity test. Experimental animals: rats; LD 50 Male / Female: >2000 mg / kg body weight; the toxicity level is low toxicity.

[0126] 3) Eye irritation test. Experimental animals: New Zealand white rabbits; irritation intensity: moderate irritation; recovery time: 48 h.

[0127] 4) Skin irritation test. Experimental animals: New Zealand white rabbits; irritation intensity: non-irritating.

[0128] 5) Skin sensitization test. Experimental animals: guinea pigs; sensitization intensity: weak.

[0129] The above content is a further detailed description of the present invention in combination with specific preferred embodiments, and it cannot be determined that the specific implementation of the present invention is only limited to these descriptions. For those of ordinary skill in the technical field to which the present invention belongs, without departing from the concept of the present invention, several simple deductions or substitutions can still be made, which should all be regarded as belonging to the protection scope of the present invention.

Claims

1. A bactericidal suspension containing metalaxyl-M, characterized in that: The bactericidal suspension, based on 1000 parts by weight, comprises the following raw materials: 30 - 150 parts by weight of metalaxyl - M, 90 - 450 parts by weight of oxine - copper, 10 - 200 parts by weight of synergist, 50 - 400 parts by weight of auxiliary agent, and the balance of water, wherein the weight ratio of metalaxyl - M to oxine - copper is 1:3; The synergist is a mixture composed of microbial metabolites and chemical synergists, and the weight ratio of the two is 2:1 - 1:2, and the optional weight ratio is 1:1; The microbial metabolite is selected from one of erythritol, rhamnolipid, sophorolipid; the chemical synergist is selected from the mixture of polyethoxylated modified silane and polyethoxylated modified fatty alcohol or alkoxy - modified polytri - siloxane.

2. The bactericidal suspending agent according to claim 1, wherein: The bactericidal suspension, based on 1000 parts by weight, comprises the following raw materials: 100 parts by weight of metalaxyl - M, 300 parts by weight of oxine - copper, 20 - 100 parts by weight of synergist, 70 - 300 parts by weight of auxiliary agent, and the balance of water.

3. The bactericidal suspension according to claim 1 or 2, characterized in that: The auxiliary agent is selected from one or more of dispersant, wetting agent, antifreeze, thickener, defoamer, preservative.

4. The bactericidal suspension according to claim 1 or 2, characterized in that: The bactericidal suspension, based on 1000 parts by weight, is composed of the following components in the following contents: 100 parts by weight of metalaxyl - M, 300 parts by weight of oxine - copper, 50 parts by weight of synergist, 50 parts by weight of dispersant, 20 parts by weight of wetting agent, 50 parts by weight of antifreeze, 5 parts by weight of thickener, 1 part by weight of defoamer, 2 parts by weight of preservative, and the balance of water.

5. The bactericidal suspension according to claim 3 or 4, characterized in that: The dispersant is selected from one or more of alkylnaphthalene sulfonates, alkylnaphthalene sulfonate formaldehyde polymers, lignosulfonates, fatty alcohol polyoxyethylene ether phosphates, polycarboxylates, comb - shaped polycarboxylates, EO - PO block copolymers, phenethylphenol polyoxyethylene ether phosphates; The wetting agent is selected from one or more of alkyl sulfonates, alkylnaphthalene sulfonates, fatty alcohol polyoxyethylene ethers, alkyl glycosides, trisiloxane polyoxyethylene ethers, polyaryl phenol polyoxyethylene ethers, castor oil polyoxyethylene ethers; The antifreeze is selected from one or more of ethylene glycol, propylene glycol, glycerol, polyethylene glycol, allantoin, sorbitol; The preservative is benzoic acid and its sodium salt, isothiazolinone, sorbic acid and its sodium salt or potassium salt; The defoamer is silicone defoamer, C10 - 20 saturated fatty acid compounds, C8 - 10 fatty alcohols; The thickener is selected from one or more of xanthan gum, polyvinyl alcohol, magnesium aluminum silicate, sodium carboxymethyl cellulose, sodium alginate, guar gum.

6. The bactericidal suspension according to claim 1, characterized in that: Application of the bactericidal suspension in preventing and treating grape downy mildew.

7. The bactericidal suspension according to claim 6, characterized in that: When the bactericidal suspension is used for preventing and treating grape downy mildew, at the low - instar larval stage of grape downy mildew, the dosage of the active ingredient is 100 - 400 mg / kg, and the optional dosage is 266.7 mg / kg.

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