Sterilization combined preparation containing stabilizer and application thereof

Abstract

The invention relates to a sterilizing composite preparation containing a stabilizer and application thereof. The invention belongs to the field of pesticide formulation processing, and relates to an epoxiconazole-containing suspending agent formula. According to the formula, a composition of an epoxiconazole-containing effective component and a stabilizer is mainly combined with a wetting agent, a dispersing agent, a thickening rheological agent, an antifreeze agent, a preservative, a defoaming agent and deionized water for use. After the suspending agent is prepared, a sample is subjected to a heating storage experiment (54 + / -2 DEG C, 14 days; the temperature is 54 + / -2 DEG C for 28 days; after 14 days at the temperature of 70 + / -2 DEG C, compared with a normal-temperature storage sample, the particle size (D50 / D90) increase range is within 100%, and the viscosity increase range is within 100 cP. The suspension rate and the dumping property of the sample both meet the national standard requirements (the suspension rate is greater than or equal to 90%; the dumping property is less than or equal to 5.0% after dumping and less than or equal to 0.5% after washing).

Description

Technical Field

[0001] The present invention belongs to the field of pesticide formulation processing, and specifically relates to a bactericidal combination preparation containing a stabilizer and its application. Background Art

[0002] Epoxiconazole, with the English name epoxiconazole, is a systemic triazole fungicide. Its active ingredient, epoxiconazole, inhibits the synthesis of ergosterol in pathogens, hinders the formation of the pathogen cell wall, and the epoxiconazole molecule has a strong affinity for a fungal enzyme (14-dencthylase), which can effectively inhibit the original fungi of the pathogen. Epoxiconazole can increase the chitinase activity of crops, cause the contraction of fungal haustoria, and inhibit the invasion of pathogens, which is a unique property of epoxiconazole among all triazole products. It has good control effects on diseases such as leaf spot, powdery mildew, rust on crops such as bananas, onions, garlic, celery, kidney beans, melons, asparagus, peanuts, and beets, as well as anthracnose and white rot on grapes.

[0003] In practical applications, some suspension concentrate products are transported and stored in areas with relatively high temperatures according to the usage requirements. Due to the too high temperature, it is easy to occur particle size growth, viscosity increase, and even pasting phenomenon, seriously affecting the product quality. In order to make the suspension concentrate meet the requirements of transportation and storage in areas with relatively high temperatures, higher heating storage experiments than the national standard requirements are needed, such as: storing at 54 ± 2 °C for 28 days, storing at 70 ± 2 °C for 14 days. When the inventor developed the suspension concentrate product containing epoxiconazole, it was found that the particle size and viscosity of the sample would increase significantly after high-temperature storage (storing at 54 ± 2 °C for 28 days, storing at 70 ± 2 °C for 14 days), resulting in the suspension rate and pourability exceeding the qualified range. Through the combined action of the composition of the active ingredient and the stabilizer with the auxiliary agent and water, the present invention controls the growth amplitude of the particle size and viscosity of the sample after heat storage, so that after the sample undergoes the heating storage experiment (54 ± 2 °C, 14 days; 54 ± 2 °C, 28 days; 70 ± 2 °C, 14 days), the suspension rate and pourability of the sample both meet the national standard requirements (suspension rate ≥ 90%; pourability: ≤ 5.0% after pouring, ≤ 0.5% after washing). The stability of the suspension concentrate containing epoxiconazole during transportation and storage in areas with relatively high temperatures is improved.

[0004] Patent CN107535488 reported a pesticide suspension concentrate of jinggangmycin and epoxiconazole and its preparation method. This invention utilizes the synergistic effect of sucrose fatty acid ester and sodium bis(tridecyl) sulfosuccinate to prevent the aggregation of the original drug particles, making the compound pesticide suspension concentrate have a relatively high suspension rate, but it does not mention that this method can control the growth amplitude of the viscosity of the suspension concentrate, and thus the effect is unknown. Summary of the Invention

[0005] The purpose of the present invention is to provide a bactericidal combination preparation containing a stabilizer and its application.

[0006] To achieve the above object, the technical solution adopted by the present invention is as follows:

[0007] A bactericidal combined preparation containing a stabilizer, the preparation containing an active ingredient and an agriculturally acceptable adjuvant, characterized in that: the bactericidal combined preparation containing a stabilizer contains, by weight percentage, 5-50% of the active ingredient, 0.5-5% of the stabilizer, 6.2-39% of the agriculturally acceptable adjuvant, and the balance is water; the active ingredient contains epoxiconazole or a mixture of epoxiconazole and compound A.

[0008] The stabilizer is selected from sodium gluconate and / or potassium gluconate.

[0009] The active ingredient is epoxiconazole or a mixture of epoxiconazole and compound A respectively; wherein, compound A is selected from one or more of flumorph, chlorothalonil, kresoxim-methyl, pyraclostrobin, tebuconazole, azoxystrobin, fluopicolide, difenoconazole.

[0010] The preparation is a water suspension agent.

[0011] The bactericidal combined preparation containing a stabilizer contains, by weight percentage, 5-50% of the active ingredient, 0.5-5% of the stabilizer, 1-5% of the wetting agent, 3-15% of the dispersant, 1-5% of the thickening rheology modifier, 1-10% of the antifreeze, 0.1-1% of the preservative, 0.1-3% of the defoamer, and the balance is water.

[0012] The dispersant is selected from one or more of sodium lignosulfonate, calcium lignosulfonate, sodium methylene bisnaphthalenesulfonate, polycarboxylate, acrylic acid copolymer, phosphate ester; the wetting agent is selected from one of alkyl sulfates, alkyl sulfonates, naphthalenesulfonates; the thickening rheology modifier is selected from one or more of xanthan gum, magnesium aluminum silicate and silica white; the antifreeze is selected from one of ethylene glycol, propylene glycol, glycerol; the preservative is selected from one of sodium benzoate, carbendazim; the defoamer is selected from one of silicone-based, polyether-based, polyhydric alcohol-based.

[0013] The application of the preparation in agricultural sterilization.

[0014] A preparation process of a bactericidal combined preparation containing a stabilizer is: feeding all materials according to the formula ratio, then carrying out rough grinding and pulping by using a high-shear disperser and then carrying out sand grinding.

[0015] The advantages of the present invention:

[0016] By adding a certain amount of sodium / potassium gluconate, when used together with epoxiconazole, the hydroxyl groups in its molecular structure can interact with the epoxy groups in the epoxiconazole molecule and generate a certain steric hindrance, avoiding the decrease in suspension rate caused by the agglomeration of epoxiconazole particles under the action of their own electronegativity. At the same time, due to the steric hindrance effect, the dispersibility of epoxiconazole particles is enhanced, thereby reducing the formation of flocs caused by particle agglomeration, and further enhancing the fluidity of the system, so that the viscosity of the system will not increase significantly. After the preparation of the present invention undergoes a heat storage experiment (54±2°C, 14d; 54±2°C, 28d; 70±2°C, 14d), compared with the sample stored at room temperature, the growth rate of particle size (D50 / D90) is within 100%, and the growth rate of viscosity is within 100 cP. The suspension rate and pourability of the sample meet the national standard requirements (suspension rate ≥ 90%; pourability: ≤ 5.0% after pouring, ≤ 0.5% after washing). Detailed implementation mode

[0017] The present invention will be further described below in conjunction with specific embodiments, but the present invention is not limited to these specific implementation modes. Those skilled in the art should recognize that the present invention covers all alternative solutions, improvement solutions and equivalent solutions that may be included within the scope of the claims. The technical materials and other materials in the examples are all commercially available.

[0018] By adding a stabilizer, the present invention can not only keep the suspension rate of the epoxiconazole suspension agent good after heat storage, but also control the growth rate of the viscosity of the epoxiconazole suspension agent after heat storage.

[0019] The preparation process adopted in the present invention is as follows: all materials are fed in proportion, and then coarsely ground and slurried by a high-shear emulsifier and then sanded.

[0020] 1. Preparation example of the preparation

[0021] Experimental method: Samples are prepared according to the formula ratio and process for each example and control example, and a heat storage stability experiment is carried out. They are placed in a constant temperature oven at 54±2°C for 14d and 28d, and in a constant temperature oven at 70±2°C for 14d. After heat storage, the suspension rate of the sample is measured according to GB / T14825-2006 "Determination Method for Suspension Rate of Pesticides", the pourability of the sample is measured according to GB / T 31737-2015 "Determination Method for Pourability of Pesticides", and the particle size and viscosity of the sample are measured. The percentage content in the formulation ratio of all examples is by weight percentage, specifically as follows.

[0022] Table 1. Formulation of 5% epoxiconazole suspension concentrate (SC) examples and control examples

[0023]

[0024] Table 2. Formulations of 12.5% difenoconazole SC, examples and control examples

[0025]

[0026] Table 3. Formulations of 20% difenoconazole SC, examples and control examples

[0027]

[0028] Table 4. Formulations of 12% difenoconazole · flumorph SC, examples and control examples

[0029]

[0030] Table 5. Formulations of 20% difenoconazole · flumorph SC, examples and control examples

[0031]

[0032]

[0033] Table 6. Formulations of 15% difenoconazole · flumorph SC, examples and control examples

[0034]

[0035] Table 7. Formulations of 6% difenoconazole · chlorothalonil SC, examples and control examples

[0036]

[0037]

[0038] Table 8. Formulations of 11% difenoconazole · chlorothalonil SC, examples and control examples

[0039]

[0040] Table 9. Formulations of 17% difenoconazole · chlorothalonil SC, examples and control examples

[0041]

[0042]

[0043] Table 10. Formulations of 22% difenoconazole · chlorothalonil SC, examples and control examples

[0044]

[0045] Table 11. Formulations of 15% difenoconazole · kresoxim-methyl SC, examples and control examples

[0046]

[0047]

[0048] Table 12. Formulations of 20% difenoconazole·kresoxim-methyl SC, Examples and Control Examples

[0049]

[0050] Table 13. Formulations of 15% difenoconazole·kresoxim-methyl SC, Examples and Control Examples

[0051]

[0052] Table 14. Formulations of 6% difenoconazole·pyraclostrobin SC, Examples and Control Examples

[0053]

[0054] Table 15. Formulations of 12% difenoconazole·pyraclostrobin SC, Examples and Control Examples

[0055]

[0056] Table 16. Formulations of 22% difenoconazole·pyraclostrobin SC, Examples and Control Examples

[0057]

[0058] Table 17. Formulations of 10% difenoconazole·tebuconazole SC, Examples and Control Examples

[0059]

[0060] Table 18. Formulations of 15% difenoconazole·tebuconazole SC, Examples and Control Examples

[0061]

[0062] Table 19. Formulations of 30% difenoconazole·tebuconazole SC, Examples and Control Examples

[0063]

[0064] Table 20. Formulations of 20% difenoconazole·azoxystrobin SC, Examples and Control Examples

[0065]

[0066] Table 21. Formulations of 30% difenoconazole·azoxystrobin SC, Examples and Control Examples

[0067]

[0068] Table 22. Formulations of 30% difenoconazole·azoxystrobin SC, Examples and Control Examples

[0069]

[0070] Table 23. Formulations of 35% difenoconazole·azoxystrobin SC in Examples and Control Examples

[0071]

[0072] Table 24. Formulations of 15% difenoconazole·fluopicolide SC in Examples and Control Examples

[0073]

[0074] Table 25. Formulations of 25% difenoconazole·fluopicolide SC in Examples and Control Examples

[0075]

[0076] Table 26. Formulations of 40% difenoconazole·fluopicolide SC in Examples and Control Examples

[0077]

[0078] Table 27. Formulations of 11% difenoconazole·difenoconazole SC in Examples and Control Examples

[0079]

[0080] Table 28. Formulations of 17% difenoconazole·difenoconazole SC in Examples and Control Examples

[0081]

[0082] Table 29. Formulations of 22% difenoconazole·difenoconazole SC in Examples and Control Examples

[0083]

[0084] Table 30. Formulations of 33% difenoconazole·difenoconazole SC in Examples and Control Examples

[0085]

[0086] Table 31. Detection Results of Particle Size and Suspension Rate of Each Example and Control Example before and after Thermal Storage

[0087]

[0088]

[0089] As can be seen from the data in Table 31, without adding the stabilizer defined in the present invention, although the particle size (D50 / D90) growth rate of some samples after storage at 54 ± 2°C for 14 days is less than 100%, and the suspension rate is ≥ 90%. However, after storage at 54 ± 2°C for 28 days and at 70 ± 2°C for 14 days, the particle size (D50 / D90) growth rate is greater than 100% in both cases, and the suspension rate is less than 90% in both cases. While for the samples with the added stabilizer, the particle size (D50 / D90) growth rate is not large under the three storage conditions, and the suspension rate is ≥ 90% in all cases. This shows that adding the stabilizer can control the particle size growth rate of the fludioxonil suspension agent sample after heat storage and ensure that the suspension rate of the sample is within the qualified range after heat storage.

[0090] Table 32. Detection results of viscosity and pourability of each example and control example before and after heat storage

[0091]

[0092]

[0093] As can be seen from the data in Table 32, without adding the stabilizer defined in the present invention, although the viscosity growth rate of some samples after storage at 54 ± 2°C for 14 days is less than 100 cP and the pourability is qualified. However, after storage at 54 ± 2°C for 28 days and at 70 ± 2°C for 14 days, the viscosity growth rate is greater than 100 cP in both cases, and the pourability is unqualified in both cases. While for the samples with the added stabilizer, the viscosity growth rate is less than 100 cP under the three storage conditions, and the pourability is qualified in all cases. This shows that adding the stabilizer can control the viscosity growth rate of the fludioxonil suspension agent sample after heat storage and ensure that the pourability of the sample is within the qualified range after heat storage.

[0094] 2. Indoor bioassay examples

[0095] Test method: The pot seedling determination method was adopted in the test. Wheat seedlings (at the one-leaf and one-heart stage) with uniform growth in the greenhouse were taken for standby. According to the concentration design of the medicament, a three-dimensional crop sprayer was used to spray the stems and leaves of each treatment, and then it was naturally air-dried. For the safety test, after air-drying, it was transferred to the greenhouse for normal management; for the activity comparison test, after air-drying, the spores of wheat powdery mildew were inoculated 24 hours later, and then it was transferred to the greenhouse for normal management. Greenhouse conditions: temperature 22 - 30°C, humidity 40 - 60%, and the results were investigated after 7 days.

[0096] Test medicaments: 12.5% fludioxonil SC samples were prepared according to the formulations of Example 2 and Control Example 2 in Table 2. After heating and storing the two samples at 70 ± 2°C for 14 days, indoor bioassay tests were carried out to investigate the control efficacy of the test medicaments against wheat powdery mildew and the safety to wheat. The results are shown in Table 33 and Table 34 respectively.

[0097] Table 33. Indoor bioassay results of 12.5% fludioxonil SC against wheat powdery mildew

[0098]

[0099] The test results show that after heating and storing at 70±2°C for 14 days, Example 2 of 12.5% epoxiconazole SC with a stabilizer has better indoor activity against wheat powdery mildew than Control Example 2. From the results of the formulation examples, it can be seen that the particle size of the sample after heat storage with a stabilizer is smaller than that of the sample without a stabilizer, and the suspension rate is higher than that of the sample without a stabilizer. A higher suspension rate ensures that more effective ingredient particles are dispersed and suspended in water after the agent is dispersed in water. Compared with the sample with a lower suspension rate, more effective ingredient particles will be sprayed onto the target crop after application, so the efficacy is better than that of the sample with a lower suspension rate. Compared with the sample without a stabilizer, after heating and storage, the sample with a stabilizer can still maintain a higher suspension rate and better efficacy.

[0100] Table 34. Indoor bioassay results of 12.5% epoxiconazole SC on wheat safety

[0101]

[0102] The test results show that 12.5% epoxiconazole SC with a stabilizer is safe for wheat.

Claims

1. A bactericidal combination preparation containing a stabilizer, the preparation containing an active ingredient and an agriculturally acceptable adjuvant, characterized in that: The bactericidal combination preparation containing a stabilizer comprises, by weight percentage, 5-50% of active ingredients, 0.5-5% of stabilizers, 6.2-39% of agriculturally acceptable adjuvants, and the balance is water; the active ingredient contains epoxiconazole or a mixture of epoxiconazole and compound A.

2. The bactericidal combination preparation containing a stabilizer according to claim 1, characterized in that: The stabilizer is selected from sodium gluconate and / or potassium gluconate.

3. The bactericidal combination preparation containing a stabilizer according to claim 1, characterized in that: The active ingredient is fluopicolide or a mixture of fluopicolide and compound A; wherein compound A is selected from one or more of flumorph, thiophanate-methyl, kresoxim-methyl, pyraclostrobin, tebuconazole, myclobutanil, fluopicolide, and difenoconazole.

4. The bactericidal combination preparation containing a stabilizer according to any one of claims 1 to 3, characterized in that: The preparation is an aqueous suspension.

5. The bactericidal combination preparation containing a stabilizer according to claim 4, characterized in that: The bactericidal combination preparation containing a stabilizer comprises, by weight percentage, 5-50% of active ingredients, 0.5-5% of a stabilizer, 1-5% of a wetting agent, 3-15% of a dispersant, 1-5% of a thickening rheological agent, 1-10% of an antifreeze agent, 0.1-1% of a preservative, 0.1-3% of a defoaming agent, and the balance is water.

6. The bactericidal combination preparation containing a stabilizer according to claim 5, characterized in that: The dispersant is selected from one of sodium lignin sulfonate, calcium lignin sulfonate, sodium methylene bisnaphthalene sulfonate, polycarboxylates, acrylic copolymers, and phosphates, or a combination of several of them; the wetting agent is selected from one of alkyl sulfates, alkyl sulfonates, and naphthalene sulfonates; the thickening rheological agent is selected from one of xanthan gum, magnesium aluminum silicate, and white carbon black, or a combination of several of them; the antifreeze agent is selected from one of ethylene glycol, propylene glycol, and glycerol; the preservative is selected from one of sodium benzoate and kason; the defoaming agent is selected from one of silicones, polyethers, and polyols.

7. An application of the bactericidal combination preparation containing a stabilizer according to claim 1, characterized in that: The preparation is used for sterilization in agriculture.

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