Pesticide preparation containing benziothiazolinone

Abstract

The invention relates to a pesticide preparation containing benziothiazolinone, in particular to a pesticide preparation containing benziothiazolinone and copper calcium sulfate, which is mainly characterized in that the weight ratio of benziothiazolinone to copper calcium sulfate is 1: 1-1: 13, and the preparation is water dispersible granules. The pesticide composition has a very high control effect on bacterial diseases and can also avoid the problem of red spider outbreak caused by a copper preparation.

Description

Technical Field

[0001] The present invention belongs to the technical field of pesticides, and particularly relates to a pesticide preparation containing thiabendazole. The pesticide preparation is composed of thiabendazole, copper calcium sulfate, synergist, and adjuvant. Background Art

[0002] Thiabendazole is a new type of broad-spectrum fungicide, mainly used for preventing and treating various bacterial and fungal diseases such as cucumber downy mildew, pear scab, apple scab, citrus anthracnose, and grape black rot. Its bactericidal mechanism mainly includes two aspects: destroying the nuclear structure of the pathogen, causing it to lose its heart and die of exhaustion, and interfering with the metabolism of the pathogen's cells, causing its physiological disorder and ultimately leading to death.

[0003] Copper calcium sulfate, with the English name copper calcium sulphate, is mostly used in plants and has the effect of eliminating fungal diseases. It is slightly toxic, and direct contact with the human body should be avoided. However, due to the presence of Cu, its dosage and usage need to be cautious. It is a broad-spectrum protective fungicide and is widely used in fungal diseases on fruit trees and vegetables for preventing and treating canker, downy mildew, etc.

[0004] Cucumber bacterial angular leaf spot mainly occurs on cucumber leaves, petioles, stems, tendrils, and fruits. When the leaves are infected, small transparent spots the size of a needle tip appear initially, which expand into light yellow spots with a yellow halo. The center turns brown or grayish white and perforates and ruptures. When the humidity is high, a milky white bacterial ooze is produced at the diseased part. When the stems and fruits are infected, water-soaked lesions appear initially, and then white bacterial ooze also overflows. When it dries, it turns gray and often forms ulcers or cracks.

[0005] With the increasing scale of greenhouse vegetable and fruit cultivation, the occurrence of cucumber bacterial angular leaf spot is more serious. Warm and humid conditions, that is, the temperature is 21-28°C and the relative humidity is above 86%, are conducive to the disease. And the pathogenic bacteria overwinter on seeds or remain in the soil with diseased residues, becoming the primary infection source in the following year.

[0006] Currently, the agents commonly used in the market to prevent and treat cucumber bacterial angular leaf spot are mainly copper preparations. However, copper preparations are prone to phytotoxicity during use and are likely to cause a large number of red spiders to occur, polluting the fruit surface and leaf surface and affecting the commercial value of the melons.

[0007] The inventor found through experiments that by making thiabendazole and copper calcium sulfate with different action mechanisms into a water dispersible granule in a certain proportion and adopting a dry suspension process, it has a fast disintegration rate and high drug efficacy utilization rate. It can not only effectively improve the control effect on cucumber bacterial angular leaf spot and reduce the control cost, but also solve the problems that copper preparations are easy to corrode equipment and packaging materials, cause drug leakage and phytotoxicity, and avoid the problem of red spider outbreaks caused by copper preparations, and has high safety for crops. Summary of the Invention

[0008] The object of the present invention is to provide a pesticide preparation containing thiabendazole ketone, which solves the problems that copper preparations are easy to corrode equipment and packaging, are unsafe in production, transportation and use, and are prone to phytotoxicity, and effectively avoids the problem of the outbreak of spider mites caused by copper preparations.

[0009] The technical solution of the present invention is as follows:

[0010] A pesticide preparation containing thiabendazole ketone, characterized in that: the pesticide preparation is composed of an effective active ingredient, a synergist and an adjuvant, and the dosage form of the pesticide preparation is a water dispersible granule.

[0011] Further, the effective active ingredient is thiabendazole ketone and copper sulfate calcium, and the weight ratio of thiabendazole ketone to copper sulfate calcium is 1:1 to 1:13; the preferred weight ratio is 1:10 to 1:13, and the best weight ratio is 1:13.

[0012] Further, the synergist is selected from microbial metabolites or amino acids. The weight ratio of the effective active ingredient to the synergist in the pesticide preparation is 5:1 to 15:1.

[0013] Further, the total weight of thiabendazole ketone and copper sulfate calcium in the pesticide preparation is 42% to 80%, and the preferred total weight is 70%.

[0014] Further, the adjuvant is selected from one or more of a dispersant, a wetting agent, an antifoaming agent, a pH regulator, and a filler.

[0015] The dispersant is selected from one or more of alkylphenol polyoxyethylene ether formaldehyde condensate sulfate, alkylphenol polyoxyethylene ether formaldehyde condensate phosphate, sodium methylene bisnaphthalene sulfonate, sodium or calcium lignosulfonate, melamine formaldehyde resin, alkylnaphthalene sulfonate, EO-PO block polyether, styrene phenol polyoxyethylene ether phosphate, alkylnaphthalene formaldehyde condensate sulfonate, alkylphenol polyoxyethylene ether phosphate ester, alkylphenol polyoxyethylene ether sulfonate, phenethylphenol polyoxyethylene ether phosphate ester, alkyl polyoxyethylene ether sulfonate, polyoxyethylene polyoxypropylene block copolymer, dodecyl polyoxyethylene ether phosphate ester, fatty alcohol polyoxyethylene ether phosphate ester, nonylphenol polyoxyethylene ether phosphate ester, sodium naphthalene sulfonate formaldehyde condensate block copolymer, comb-shaped polycarboxylate, and sodium polycarboxylate;

[0016] The wetting agent(s) selected from one or more of sodium dodecylbenzenesulfonate, sodium diisobutylnaphthalenesulfonate, sorbitan fatty acid ester, sodium sulfosuccinate octyl ester, alkylsulfosuccinate, phenethylphenol polyoxyethylene ether phosphate, alkyl sulfate, alkyl sulfonate, alkylnaphthalenesulfonate, alkylphenol formaldehyde resin polyoxyethylene ether, tribenzylethylphenol polyoxypropylene polyoxyethylene block polymer, sodium dodecyl sulfate, styrylphenol formaldehyde resin propylene oxide block polyether, castor oil polyoxyethylene ether, fatty alcohol polyoxyethylene ether, alkyl glycoside, sodium fatty alcohol polyoxyethylene ether sulfonate;

[0017] The defoaming agent(s) selected from one or more of silicone, fatty alcohol, fatty acid;

[0018] The pH regulator(s) selected from one or more of citric acid, glacial acetic acid;

[0019] The filler(s) selected from one or more of silica white, calcined kaolin, ammonium sulfate, potassium sulfate, talc powder, diatomite, starch, urea, washed kaolin.

[0020] Furthermore, the application rate of the active ingredient of the pesticide formulation is 300 - 700 g / ha, and preferably the application rate of the active ingredient is 450 - 550 g / ha.

[0021] When the pesticide formulation is made into a water dispersible granule, it contains the following components and percentage contents: thiabendazole 3 - 7%, calcium hydroxide 7 - 16.4%, copper sulfate pentahydrate 31.5 - 73.7%, synergist 1 - 10%, dispersant 1 - 10%, wetting agent 1 - 6%, pH regulator 0.01 - 1%, defoaming agent 0 - 3%, filler up to 100%.

[0022] The reaction formula of calcium copper sulfate technical in the pesticide formulation of the present invention is:

[0023] 3Ca(OH)2 + 4Cu(SO4)2·5H2O → CuSO4·3Cu(OH)2·3CaSO4·nH2O

[0024] A certain amount of copper sulfate is made into an aqueous solution for standby. Calcium hydroxide is added to the reaction kettle to make a calcium hydroxide slurry, heated to 50°C - 80°C, stirred for 0.5 - 1 hour, and the prepared copper sulfate aqueous solution is added to the calcium hydroxide slurry, followed by stirring reaction for 1 hour and heat preservation reaction for 4 hours. After the reaction is completed, calcium copper sulfate technical is obtained. Start stirring, then successively add thiabendazole technical, synergist, dispersant, wetting agent, pH regulator, defoaming agent, filler, and perform high-speed shearing for 20 minutes, followed by three-stage sand grinding to obtain an intermediate of calcium copper sulfate·thiabendazole water dispersible granule. Take a small sample for testing. After passing the test, perform spray granulation and then secondary drying to obtain the finished product of thiabendazole·calcium copper sulfate water dispersible granule.

[0025] Compared with the prior art, the pesticide preparation for preventing and controlling cucumber bacterial angular leaf spot of the present invention has the following beneficial effects: (1) Compared with single agents, the pesticide preparation has a more significant synergistic effect on preventing and controlling cucumber bacterial angular leaf spot; (2) The mixing of two compounds with different action mechanisms can effectively delay the generation of disease resistance; (3) It is safe for producers, users and crops, solves the technical problems that common copper preparations are easy to corrode equipment and packaging materials and are not safe for crops and prone to phytotoxicity during use, and can also be mixed with various types of pesticide products, reducing the pesticide application cost for farmers. Detailed implementation modes

[0026] The present invention will be further described below in conjunction with embodiments. The percentages in the embodiments are all weight percentages, but the present invention is not limited thereto.

[0027] Application Example 1

[0028] Example 1 70% thiabendazole·copper calcium sulfate water dispersible granules

[0029] 5% thiabendazole technical, 15.2% calcium hydroxide, 68.5% copper sulfate pentahydrate, 5% lysine, 4% alkyl naphthalene formaldehyde condensate sulfonate, 2% comb-shaped polycarboxylate, 2% sodium dodecylbenzenesulfonate, 0.1% citric acid, 0.2% fatty alcohol, 2% white carbon black, calcined kaolin added to 100%, to obtain 70% thiabendazole·copper calcium sulfate water dispersible granules.

[0030] Example 2 70% thiabendazole·copper calcium sulfate water dispersible granules

[0031] 5% thiabendazole technical, 15.2% calcium hydroxide, 68.5% copper sulfate pentahydrate, 5% threonine, 3% sodium lignosulfonate, 2% block copolymer of naphthalene sulfonic acid formaldehyde condensate sodium salt, 1% sodium diisobutylnaphthalenesulfonate, 0.1% citric acid, 0.1% fatty alcohol, calcined kaolin added to 1000 g, to obtain 70% thiabendazole·copper calcium sulfate water dispersible granules.

[0032] Example 3 70% thiabendazole·copper calcium sulfate water dispersible granules

[0033] 5% thiabendazole technical, 15.2% calcium hydroxide, 68.5% copper sulfate pentahydrate, 6% alanine, 4% alkyl polyoxyethylene ether sulfonate, 1.5% sodium sulfosuccinate octyl ester, 0.2% fatty acid, 0.2% glacial acetic acid, 1% white carbon black, washed kaolin added to 100%, to obtain 70% thiabendazole·copper calcium sulfate water dispersible granules.

[0034] Example 4 42% thiabendazole·copper calcium sulfate water dispersible granules

[0035] 3% of thiabendazole technical, 9.2% of calcium hydroxide, 41.1% of copper sulfate pentahydrate, 3% of glutamic acid, 5% of sodium methylene dinaphthalene sulfonate, 2% of alkylphenol formaldehyde resin polyoxyethylene ether, 0.3% of fatty alcohol, 0.1% of citric acid, potassium sulfate added to 100%, to obtain 42% thiabendazole·copper calcium sulfate water dispersible granules.

[0036] Example 5: 56% thiabendazole·copper calcium sulfate water dispersible granules

[0037] 4% of thiabendazole technical, 12.2% of calcium hydroxide, 54.8% of copper sulfate pentahydrate, 7% of proline, 3% of polyoxyethylene polyoxypropylene block copolymer, 3% of comb-shaped polycarboxylate, 1% of sodium dodecyl sulfate, 1% of alkyl sulfate, 0.1% of fatty acid, 0.1% of glacial acetic acid, calcined kaolin added to 100%, to obtain 56% thiabendazole·copper calcium sulfate water dispersible granules.

[0038] Example of application 2:

[0039] Virulence determination of the mixture of thiabendazole and copper calcium sulfate against cucumber bacterial angular leaf spot

[0040] According to the standards of NY / T1156.16 - 2008 and NY / T1156.6 - 2006, the virulence of thiabendazole, copper calcium sulfate and their mixtures in the ratios of 1:13, 1:10, 1:7, 1:3 and 1:1 against Pseudomonas syringae pv lacKrymans was determined by the turbidity method. The results showed that the mixtures of thiabendazole and copper calcium sulfate in the above 5 ratios showed additive or synergistic effects against Pseudomonas syringae pv lacKrymans, and their EC 50 values were 9.05, 9.62, 9.94, 10.30 and 9.55 mg / L respectively, and the co-toxicity coefficients were 155.55, 145.35, 138.84, 127.99 and 126.66 respectively. Among them, the synergistic effect was most obvious when the two were mixed in a ratio of 1:13. The experimental process is as follows: 1 Test purpose

[0041] The virulence of the mixtures of thiabendazole and copper calcium sulfate and their different ratios was determined indoors against Pseudomonas syringae pv lacKrymans, and the synergistic effect was evaluated to clarify their compatibility, providing a scientific basis for the research and development of the mixture of thiabendazole and copper calcium sulfate.

[0042] 2 Test conditions

[0043] 2.1 Test target

[0044] Pseudomonas syringae pv lacKrymans, preserved and provided by the experimental unit.

[0045] 2.2 Culture conditions

[0046] The culture conditions for the test targets and the targets after the test are a temperature of 25 ± 5°C and a relative humidity of 65 ± 5% or more.

[0047] 2.3 Instruments and equipment

[0048] Beakers, pipettes, Erlenmeyer flasks, autoclaves, constant temperature shaking incubators, ultraviolet spectrophotometers, etc.

[0049] 3 Experimental design

[0050] 3.1 Test agents

[0051] Benziothiazolinone 98% technical; Copper calcium sulphate 98% technical.

[0052] 3.2 Design of agent concentrations and preparation of solutions

[0053] Benziothiazolinone solution: Weigh 0.0500 g of benziothiazolinone 98% technical, dissolve it in 0.5 mL of DMF, add 97.5 mL of clear water containing 0.1% Tween 80 emulsifier, stir evenly, prepare a 500 mg / L mother liquor, and then dilute it with sterile water to concentrations of 250, 125, 62.5, 31.25, 15.625 mg / L for standby;

[0054] Copper calcium sulphate solution: Weigh 0.1500 g of copper calcium sulphate 98% technical, dissolve it in 1 mL of DMF, add 293 mL of clear water containing 0.1% Tween 80 emulsifier, stir evenly, prepare a 500 mg / L mother liquor, and then dilute it with sterile water containing 0.1% Tween 80 emulsifier to concentrations of 250, 125, 62.5, 31.25, 15.625 mg / L for standby;

[0055] Each mixed solution: Take 3, 4, 6, 11, 25 mL of 500 mg / L benziothiazolinone solution and add them to 39, 40, 42, 33, 25 mL of 500 mg / L copper calcium sulphate solution respectively to prepare 500 mg / L benziothiazolinone·copper calcium sulphate 1:13, 1:10, 1:7, 1:3 and 1:1 solutions, and then dilute them with sterile water containing 0.1% Tween 80 emulsifier to concentrations of 250, 125, 62.5, 31.25, 15.625 mg / L for standby;

[0056] Control solution: 1 mL of DMF plus 99 mL of sterile water containing 0.1% Tween 80 emulsifier.

[0057] 4 Test methods

[0058] Refer to the standard bioassay method NY / T 1156.16 - 2008 and adopt the turbidity method. Take 5 mL of the liquid medicine with a series of concentrations of each single agent, add it to 45 mL of NB medium cooled to 45 °C, and prepare a medicated medium with the required final concentration. Dilute the bacterial strain growing on the slant of NA medium with sterilized water to a suspension with a concentration of 1×10 7 spores / mL, and inoculate 100 μL of the bacterial solution into each treatment medium, with 4 replicates for each treatment. After the treatment is completed, place it in a shaking incubator at 28 °C - 30 °C (120 r / min), measure the absorbance value after 12 h, and calculate the growth inhibition rate.

[0059] 5 Data investigation and statistical analysis

[0060] 5.1 Investigation method

[0061] Measure the absorbance value of each treatment before starting the culture. When the control treatment reaches the logarithmic growth phase, measure and record the absorbance value of each treatment. The measurement wavelength is 660 nm. Calculate the growth inhibition rate (%).

[0062]

[0063] In the formula: P - growth inhibition rate; A0 - absorbance value increase of the blank control; At - absorbance value increase of the medicament treatment.

[0064] 5.2 Evaluation method for synergistic effect

[0065] Refer to the bioassay test guideline NY / T 1156.6-2006, and evaluate the synergistic effect of the mixed use of medicaments 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.

[0066]

[0067] The theoretical toxicity index (TTI) of the mixture = toxicity index of medicament A × percentage of medicament A in the mixture (%) + toxicity index of medicament B × percentage of medicament B in the mixture (%)

[0068]

[0069] 5.3 Data statistical analysis

[0070] All experimental data are analyzed using the SAS6.12 statistical software. Calculate the mycelial growth inhibition rate (%) based on the experimental data, and obtain the toxicity regression equation, correlation coefficient (r), and EC50 (95% confidence limit).

[0071] 6 Result analysis and discussion

[0072] 6.1 Efficacy evaluation

[0073] The results of the virulence determination of the mixture combinations of thiabendazole and calcium copper sulfate at different ratios against Pseudomonas syringae pv. lachrymans are shown in Table 1. As can be seen from Table 1, among the 1:13, 1:10, 1:7, 1:3, and 1:1 mixture combinations of thiabendazole and calcium copper sulfate, the five ratios showed additive or synergistic effects against Pseudomonas syringae pv. lachrymans, and their EC 50 values were 9.05, 9.62, 9.94, 10.30, and 9.55 mg / L, respectively, and the co-toxicity coefficients were 155.55, 145.35, 138.84, 127.99, and 126.66. Among them, the synergistic effect was most obvious when the two were mixed at a ratio of 1:13.

[0074] Table 1 Results of the virulence determination of the mixture of thiabendazole and calcium copper sulfate against Pseudomonas syringae pv. lachrymans

[0075]

[0076] 6.2 Discussion and conclusion

[0077] The results of the in-door bioassay showed that when thiabendazole and calcium copper sulfate were mixed at ratios of 1:13, 1:10, 1:7, 1:3, and 1:1, they all showed synergistic effects against Pseudomonas syringae pv. lachrymans, and the best synergistic effect was obtained at a ratio of 1∶13.

[0078] Application Example 3: Field efficacy experiment of 70% thiabendazole·calcium copper sulfate water dispersible granules against Pseudomonas syringae pv. lachrymans

[0079] The test was carried out in accordance with "Pesticide field efficacy test guidelines (part 2) GB / T 17980.110-2004: Fungicides for controlling Pseudomonas syringae pv. lachrymans".

[0080] Test crop: Cucumber

[0081] Control object: Pseudomonas syringae pv. lachrymans

[0082] 1 Basic information of the test

[0083] 1.1 Test name

[0084] Field efficacy test of 70% thiabendazole·calcium copper sulfate water dispersible granules against Pseudomonas syringae pv. lachrymans.

[0085] 1.2 Test purpose

[0086] To clarify the control effect, applicable dosage and safety of the 70% thiabendazole·calcium copper sulfate water dispersible granules provided by the applicant against Pseudomonas syringae pv. lachrymans, and to provide a basis for the registration and promotion of the test agent.

[0087] 2 Environmental and Facility Cultivation Conditions

[0088] 2.1 Test Location

[0089] Jiangxi, Shanxi.

[0090] 2.2 Test Target Situation

[0091] Cucumber Bacterial Angular Leaf Spot (Pseudomonas syringae).

[0092] 2.3 Test Crops, Varieties and Growth Conditions

[0093] The experimental crop is cucumber, and it grows well after transplanting.

[0094] 3 Test Design and Arrangement

[0095] 3.1 Test Dosage and Numbering

[0096] Table 2 Test Design of Test Agents

[0097]

[0098] 3.2 Application Method

[0099] 3.2.1 Application Period and Method

[0100] Apply the first dose at the early flowering stage of cucumber, before the onset or at the initial stage of bacterial angular leaf spot, and apply the dose again after 7 days, for a total of 3 applications.

[0101] 3.2.2 Application Volume

[0102] Spray, and the water consumption for application is 600 - 900 liters / ha.

[0103] 3.3 Investigation Method, Time and Frequency

[0104] 3.3.1 Investigation Time and Frequency

[0105] This test was investigated 3 times in total. The disease index was investigated before application, and investigated again 7 days or 10 days after the last application, for a total of 2 investigations.

[0106] 3.3.2 Investigation Method

[0107] Take 5 samples at 5 points along the diagonal of each plot, 3 plants at each point, investigate the disease occurrence of all leaves, and grade according to the percentage of the disease spot area on each leaf.

[0108] Grading Method (per leaf):

[0109] Grade 0: No disease spots;

[0110] Grade 1: The disease spot area accounts for less than 5% of the entire leaf area;

[0111] Level 3: The lesion area accounts for 6% - 10% of the entire leaf area;

[0112] Level 5: The lesion area accounts for 11% - 20% of the entire leaf area;

[0113] Level 7: The lesion area accounts for 21% - 50% of the entire leaf area;

[0114] Level 9: The lesion area accounts for more than 51% of the entire leaf area.

[0115] 3.3.3 Efficacy calculation method

[0116]

[0117]

[0118] 4 Results and analysis

[0119] Table 3 Test results of 70% thiabendazole·calcium copper sulfate water dispersible granule against bacterial angular leaf spot of cucumber

[0120]

[0121]

[0122] The test results show that: The test agent, 70% thiabendazole·calcium copper sulfate water dispersible granule, has a good control effect on bacterial angular leaf spot of cucumber. When the application rate of its active ingredient is 420 - 525 g / ha, the control effect is significantly better than that of the control single agent. Variance analysis shows that the test agent shows a highly significant level compared with the control single agent.

[0123] Through field systematic observation, it is known that: When the experimental agent is applied before the occurrence or at the initial stage of bacterial angular leaf spot of cucumber, with a spraying interval of 7 - 10 days each time and continuous spraying for 3 times, and the water consumption per hectare is 600 - 900 liters, when the application rate of the active ingredient is 420 - 525 g / ha, it can not only effectively control bacterial angular leaf spot of cucumber, but also be safe for cucumber during the entire application period, and the cucumber shape is regular.

Claims

1. A pesticide preparation containing thiabendazole ketone, characterized in that: The pesticide preparation consists of an active ingredient, a synergist and adjuvants; The active ingredient is thiabendazole and copper calcium sulfate, and the weight ratio of thiabendazole to copper calcium sulfate is 1:1 to 1:13; The dosage form of the pesticide preparation is a water dispersible granule.

2. The pesticide preparation according to claim 1, wherein: The synergist is selected from microbial metabolites or amino acids.

3. The pesticide preparation according to claim 1, characterized in that: The weight ratio of the active ingredient to the synergist is 5:1 to 15:

1.

4. The pesticide formulation according to any one of claims 1-3, characterized in that: The weight ratio of thiabendazole to copper calcium sulfate is 1:10 to 1:

13.

5. The pesticide formulation according to claim 4, characterized in that: The weight ratio of thiabendazole to copper calcium sulfate is 1:

13.

6. The pesticide preparation according to claim 4, characterized in that: The total weight of thiabendazole and copper calcium sulfate in the pesticide preparation is 42% to 80%.

7. The pesticide formulation according to claim 6, characterized in that: The total weight of thiabendazole and copper calcium sulfate in the pesticide preparation is 70%.

8. The pesticide preparation according to claim 1, characterized in that: The adjuvants are selected from one or more of a dispersant, a wetting agent, an antifoaming agent, a pH regulator, and a filler.

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