A suspension agent containing cyenopyrafen and bifenazate and its application

Abstract

The present invention provides a fenpyroximate·bifenazate suspension concentrate, which comprises the following components in weight percentage: 10-20% of fenpyroximate, 25-35% of bifenazate, 1-8% of Agrilan 755, 0.5-8% of MORWET-D500, 1-5% of ethylene glycol, 0.1-1% of magnesium aluminum silicate, 0.05-0.5% of xanthan gum, 0.1-0.3% of fungicide BIT200, 0.01-1% of defoamer, and the balance is made up to 100% with water. The suspension concentrate provided by the present invention has excellent formulation properties and biological activity.

Description

Technical Field

[0001] The present invention relates to the technical field of pesticides, and particularly relates to a suspension agent containing cyenopyrafen and bifenazate and its application. Background Art

[0002] The hydrolyzate formed by the metabolism of cyenopyrafen in organisms can act on Complex II of the mitochondrial electron transport system, hindering the electron flow from succinic acid to coenzyme Q, thereby disrupting the intracellular respiration of spider mites. It can be used to control Panonychus ulmi, Tetranychus urticae, and Tetranychus bimaculatus on apple trees, strawberry plants.

[0003] Bifenazate is a new type of selective foliar spray acaricide that is effective against all life stages of mites, has ovicidal activity and knockdown activity against adult mites, and has a long residual period. This product can be used on apples and grapes to control Panonychus ulmi, Tetranychus urticae, and McDaniel mites, as well as Tetranychus urticae and Lewis mites on ornamental plants.

[0004] CN104522010A discloses a synergistic acaricidal composition containing cyenopyrafen and bifenazate. The weight ratio of cyenopyrafen to bifenazate is 20:1 to 1:20, and the total weight percentage of cyenopyrafen and bifenazate in the acaricidal composition is 5%-85%. The two active ingredients in the present invention have an obvious synergistic effect and have excellent control effects on various mite pests on crops such as fruit trees, vegetables, cotton, tea trees, and flowers. There is no record of a suspension agent in this patent. In addition, there are no registered products of cyenopyrafen and bifenazate suspension agents in pesticide enterprises.

[0005] The research on pesticide formulations is an important aspect of pesticide development. A good formulation can give full play to the functions of active ingredients as much as possible, cover the target to the greatest extent, reduce the amount of pesticides used, facilitate the use of pesticides, and reduce the impact on the environment. The company has developed a suspension agent formulation for the composition of cyenopyrafen and bifenazate with excellent formulation performance and biological activity. Summary of the Invention

[0006] The present invention provides the following technical solutions:

[0007] A cyenopyrafen·bifenazate suspension agent, comprising the following components in weight percentage: cyenopyrafen 10-20%, bifenazate 25-35%, Agrilan 755 1-8%, MORWET-D500 0.5-8%, ethylene glycol 1-5%, magnesium aluminum silicate 0.1-1%, xanthan gum 0.05-0.5%, fungicide BIT20 0.1-0.3%, defoamer 0.01-1%, and water is added to make up 100%.

[0008] A fenpyroximate·bifenazate suspension concentrate, comprising the following components in weight percentage: fenpyroximate 15%, bifenazate 30%, Agrilan 755 1 - 8%, MORWET-D500 0.5 - 8%, ethylene glycol 1 - 5%, magnesium aluminum silicate 0.1 - 1%, xanthan gum 0.05 - 0.5%, fungicide BIT20 0.1 - 0.3%, defoamer 0.01 - 1%, and water to make up 100%.

[0009] A fenpyroximate·bifenazate suspension concentrate, comprising the following components in weight percentage: fenpyroximate 15%, bifenazate 30%, Agrilan 755 2.5%, MORWET-D500 4.5%, ethylene glycol 4%, magnesium aluminum silicate 0.5%, xanthan gum 0.12%, fungicide BIT20 0.15%, defoamer 0.05%, and water to make up 100%.

[0010] The preparation method of the fenpyroximate·bifenazate suspension concentrate is as follows: the technical materials and auxiliaries are mixed in a certain proportion with water as the dispersion medium and subjected to wet ultrafine grinding. When grinding, zirconia beads need to be added to the mixture, and it is ground at a high speed at a rate of 1500 - 2000 r / min at room temperature to reduce the average particle size of the suspension concentrate to less than 3 μm, and the pesticide suspension concentrate is obtained after separating the zirconia beads.

[0011] The use of the fenpyroximate·bifenazate suspension concentrate for controlling crop pests. Preferably, the pests are spider mites.

[0012] Adopting the above technical solution, the present invention has the following beneficial effects:

[0013] Bifenazate and fenpyroximate both have high toxicity to citrus nymphs, and there is a significant synergistic effect on the combined toxicity after mixing.

[0014] When Agrilan 755 and MORWET-D500 are combined in the suspension formulation, the pourability of the suspension concentrate is excellent, and there is basically no wall-hanging phenomenon. The 45% bifenazate·fenpyroximate suspension concentrate has excellent control effects on citrus tree spider mites and apple spider mites. It is recommended to dilute 6000 - 10000 times for citrus tree spider mites; it is recommended to dilute the formulation 2500 - 3500 times for apple spider mites. Specific embodiments

[0015] Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts fall within the scope of protection of the present invention.

[0016] The present invention will be further explained and illustrated below in conjunction with specific embodiments. Example 1: Determination of the combined toxicity of bifenazate and pyridaben mixture against Panonychus citri and formulation screening

[0017] 1. Test purpose

[0018] To determine the toxicity of bifenazate and pyridaben single agents against Panonychus citri by the leaf disc spraying method and the combined toxicity of their mixtures in different ratios, and to determine the optimal formulation of the mixture.

[0019] 2. Materials and methods

[0020] 2.1 Test targets

[0021] Test mites: Panonychus citri were collected from the green orange base in Wanling Town, Qiongzhong County, Hainan Province in mid-January 2021, and reared indoors in a citrus seedling cage. Newly hatched female adult mites of Panonychus citri were selected as test mites for indoor toxicity determination of acaricides.

[0022] 2.2 Instrument and equipment

[0023] BURKARD type automatic control spray tower, precision pipette, electronic balance (0.1 mg), pipettor, beaker, graduated cylinder, incubator, etc.

[0024] 2.3 Chemical agents

[0025] 98% bifenazate technical, 97.3% pyridaben technical.

[0026] 2.4 Dose setting

[0027] Table 1 Test dose setting of bifenazate, pyridaben and their mixtures against Panonychus citri

[0028]

[0029]

[0030] 2.5 Test time

[0031] The test time was from July 15th to July 19th, 2021, and the test mites were the nymphs of Panonychus citri.

[0032] 2.6 Test method

[0033] The leaf disc spraying method was used for the test, referring to the indoor bioassay guidelines for acaricides NY / T 1154.13-2008 and 1154.7 - 2006.

[0034] The test agents were diluted with clear water according to a geometric progression to prepare 5 gradient concentrations, and indoor toxicity determination was carried out by the leaf disc spraying method. Citrus leaves with consistent growth were selected, made into leaf discs with a puncher, a wet sponge block was placed in a petri dish, a filter paper was placed on it, and the leaf discs were placed on the filter paper. There were 2 leaf discs in each dish, and 20 female adult mites were inoculated on each leaf disc. The petri dishes were placed on the chassis of the Potter spraying tower for stem and leaf spraying treatment. The spraying volume was 1 mL. After the liquid medicine settled for 1 min, it was taken out, and then placed in an insect rearing room at (25±1)°C, relative humidity of 70% - 80%, and light cycle L∶D = 16∶8. The treatment with 0.01% Triton-80 solution was used as a control. One petri dish was used for each treatment, with 4 replicates. After 48 h of treatment, the mortality rate was checked, and the death standard of Panonychus citri was that the body color of the mite turned black and it was immobile.

[0035] 3 Data processing and statistical methods

[0036] 3.1 Calculation methods for mortality rate and corrected mortality rate

[0037] Based on the number of dead mites and the total number of mites in the treatment group and the control group, the mortality rate and the corrected mortality rate were calculated, with the unit of percentage (%).

[0038]

[0039] In the formula:

[0040] P1—Mortality rate;

[0041] K—Represents the number of dead mites;

[0042] N—Represents the total number of mites in the treatment.

[0043]

[0044] In the formula:

[0045] P2—Corrected mortality rate;

[0046] Pt—Mortality rate of the treatment;

[0047] P0—Mortality rate of the blank control.

[0048] 3.2 Calculation method for LC50

[0049] The probit analysis method was adopted, and the data was analyzed using the DPS processing system.

[0050] 3.3 Calculation method for co-toxicity coefficient

[0051] Referring to the co-toxicity coefficient method of Sun Yunpei, the single agent bifenazate was used as the standard control agent, and its toxicity index was 100.

[0052] Toxicity index of standard acaricide A (bifenazate): 100

[0053] Toxicity index of standard acaricide B (cyenopyrafen).

[0054]

[0055] The theoretical toxicity index TTI of the mixture = Toxicity index of agent A × Content of A in the mixture (%) + Toxicity index of agent B × Content of B in the mixture (%).

[0056]

[0057] If the co-toxicity coefficient CTC of the mixture is greater than 120, it indicates a synergistic effect; if CTC is lower than 80, it indicates an antagonistic effect; if CTC is between 80 - 120, it shows an additive effect.

[0058] 4 Results and evaluation

[0059] Table 2 Indoor toxicity determination results of the mixture of bifenazate and cyenopyrafen against Panonychus citri

[0060]

[0061] The results show that both bifenazate and cyenopyrafen have high toxicity to adult female Panonychus citri. The LC50 of bifenazate is 8.83 mg / L, and the LC50 of the original cyenopyrafen is 2.19 mg / L. The LC50 of the mixed agents of bifenazate:cyenopyrafen (mass ratio after content conversion) at ratios of 8:1, 4:1, 2:1, 1:1, and 1:2 against Panonychus citri are 4.80, 2.95, 2.59, 2.28, and 2.08 mg / L respectively, and the co-toxicity coefficients CTC are 137.61, 186.34, 169.56, 153.93, and 128.18 respectively.

[0062] Conclusion: Both bifenazate and cyenopyrafen have high toxicity to young Panonychus citri. After mixing, there is a significant synergistic effect on the combined toxicity. Among the five ratios, the co-toxicity coefficients of bifenazate:cyenopyrafen at 4:1 and 2:1 are relatively high. The mixture of bifenazate and cyenopyrafen is expected to be an effective agent for field control of citrus red spider mites.

[0063] Example 2: Suspension formulation of bifenazate and cyenopyrafen

[0064] Table 3 Composition of the suspension formulation

[0065]

[0066] Remarks:

[0067] Agrilan 788: A hydrophobic group-modified carboxylic acid copolymer, from Nanjing Jierun;

[0068] Agrilan 755: A hydrophilic single comb-shaped polymer; from Nanjing Jierun;

[0069] Morwet-D500: A mixture of alkyl naphthalene sulfonate formaldehyde condensate and block copolymer; from Nanjing Jierun.

[0070] Preparation method of suspending agent:

[0071] The technical material and auxiliary materials are mixed in a certain proportion with water as the dispersion medium and subjected to wet ultrafine grinding. When grinding, zirconia beads need to be added to the mixture, and it is ground at a high speed at a rate of 1500 - 2000 r / min at room temperature to reduce the average particle size of the suspending agent to less than 3 μm. After separating the zirconia beads, the pesticide suspending agent is obtained.

[0072] Testing of formulation performance indicators:

[0073] When Agrilan 788 is used alone or in combination with MORWET-D500, the pourability of the suspending agent is poor and it is prone to wall sticking. When Agrilan 755 and MORWET-D500 are combined, the pourability of the suspending agent is excellent and there is basically no wall sticking phenomenon. Formulations 1 - 4 meet the control indicators of the suspending agent, and formulation 5 is a non-conforming preparation. Formulations 1 - 4 are used for field efficacy tests in field testing.

[0074] Table 4 Performance indicators of suspending agent formulation

[0075]

[0076] Example 3: Test report on the control of Panonychus citri on citrus trees with 45% bifenazate·cyenopyrafen suspending agent

[0077] Test purpose: To verify the control effect of the tested pesticide on Panonychus citri on citrus trees and its safety to crops, and to provide field efficacy basis for the registration of this pesticide.

[0078] 1. Test conditions

[0079] Crop and target: Crop / citrus tree / Jin Kuai; Target / Panonychus citri.

[0080] Test conditions: The test was conducted in Wenshu Village 7, Fengming Town, Pengshan District, Meishan City, Sichuan Province from April 24, 2020 to May 24, 2020. Citrus tree varieties: gold nuggets, 4×4m open boxes, 4 years old, fertilized 2-3 times a year, compound fertilizer about 100 grams / plant / time, citrus flowering period, red spider occurrence period. The field is sandy loam, pH 6.8, organic matter content 1.70%, and medium fertility level.

[0081] 2. Experimental design and arrangement

[0082] Test agent: 45% bifenazate-pyraclostrobin suspension (Shanghai Yuelian Biotechnology Co., Ltd.).

[0083]

[0084] Plot size and replication: 4 replications, 2 trees per plot, with guard rows between plots.

[0085] Application time and frequency: On April 24, 2020, spray once during the flowering period of citrus trees and the period when red spider mites occur.

[0086] Equipment and application method: The solution is prepared by the secondary dilution method. The main preparation tools are: balance, measuring cylinder, pipette, glass rod, etc. Use Linong HD400 sprayer for spraying, spray pressure 0.2-0.4Mpa, spray hole diameter 1mm. Spray the whole plant evenly, and make sure the leaves of the whole citrus tree are fully moistened. The water consumption per tree is about 2 liters.

[0087] Meteorological data: On April 24, 2020, it rained in the early morning, but it was sunny when the pesticide was applied, which did not affect the test.

[0088] Soil information: sandy loam, pH 6.8, organic matter content 1.70%, medium fertility level.

[0089] Control of non-target organisms: On May 8, 2020, 20% gibberellic acid soluble powder was applied at 7000 times the concentration to protect fruit.

[0090] 3 Investigation and Results

[0091] 3.1 Survey method: In each plot, young shoots were marked at the east, west, south, north and center of the tree. The number of insects on 5 leaves of each shoot was surveyed, and the number of active mites on 25 leaves was surveyed in total. The leaf surface was directly observed with a handheld magnifying glass to count the number of mites.

[0092] 3.2 Survey time and frequency: Survey once before medication and once 1, 10, 15, 20, and 30 days after medication, for a total of 6 times. Specific time: April 24, 2020, April 25, 2020, May 4, 2020, May 9, 2020, May 14, 2020, and May 24, 2020.

[0093] 3.3 This test complies with the "Good Laboratory Practice for Pesticide Registration Tests", the "Guidelines for Field Efficacy Trials of Pesticides" GB / T 17980.11 - 2000, and SOP - TM - 074a "Test on Panonychus citri". The calculation formula is as follows:

[0094]

[0095] In the formula: PT 0 -- The number of live insects before treatment in the medicament - treated area;

[0096] PT 1 - The number of live insects after treatment in the medicament - treated area;

[0097] CK 0 - The number of live insects before treatment in the blank control area;

[0098] CK 1 - The number of live insects after treatment in the blank control area.

[0099] 3.4 Effects on other organisms:

[0100] No obvious effects of the tested pesticides on other organisms were observed during the test.

[0101] 3.5 Test results

[0102] The 45% bifenazate·cyenopyrafen suspension concentrate is used to control Panonychus citri on citrus trees. It is recommended to dilute it 6000 - 10000 times and spray once during the occurrence period of Panonychus citri on citrus trees.

[0103] Table 5: Test on the control of Panonychus citri on citrus trees with 45% bifenazate·cyenopyrafen suspension concentrate

[0104]

[0105] Example 4: Field efficacy test on the control of Panonychus ulmi on apple trees with 45% bifenazate·cyenopyrafen suspension concentrate Test objective: To verify the efficacy of the tested pesticide in controlling Panonychus ulmi on apple trees and its safety to crops, and to provide field efficacy basis for the registration of this pesticide.

[0106] 1. Test conditions

[0107] The test was conducted in the apple demonstration garden of the Tianjin Modern Agricultural Science and Technology Innovation Base in Dongpuwa Street, Wuqing District, Tianjin. Apples, pears, cherries, peaches, etc. are planted in the garden, which is concentrated and contiguous.

[0108] Test target situation:

[0109] Red spider, Tetranychus viennensis Zacher, active mites. During the test, 6.5 - 8.5 active mites of various stages such as larvae, nymphs and adults could be seen on the mite - infested leaves.

[0110] Test crops, growth periods and growth conditions:

[0111] The test apple trees are about 8 - 10 years old adult trees, with a plant spacing of 2.5m × 3m, a plant height of over 2.5m, and a canopy diameter of about 1.8m.

[0112] Soil type of the test plot:

[0113] Slightly alkaline clay loam, with a pH value of about 7.8; the organic matter content is 1.2%.

[0114] Water and fertilizer management of the test plot:

[0115] The water and fertilizer management is conventional, and there are irrigation and drainage channels in the orchard.

[0116] Meteorological data:

[0117] On the day of pesticide application (June 23, 2022), it was overcast with scattered light rain, with a southerly wind, wind force 1 - 2, the highest temperature of 35.9℃, the lowest temperature of 22.7℃, and an average temperature of 28.6℃; during the mid - term of the test (there were short - term showers on the 5th and 6th days after spraying, with rainfall of 3.3mm and 6.5mm), the overall weather was fine.

[0118] Pesticide data for controlling other pests and diseases:

[0119] Fifteen days before and during the test, no other insecticides, acaricides, etc. were sprayed on the apple trees in each treatment area.

[0120] 2. Test design and arrangement

[0121] Test pesticides

[0122] 45% Bifenazate·Cyenopyrafen Suspension Concentrate (Shanghai Yuelian Biotechnology Co., Ltd.).

[0123]

[0124] Plot area and replicates:

[0125] Plot area: 4 plants; another 2 protection trees or isolation trees are set between plots to prevent the drift and interference of liquid medicine. Number of replicates: Four times, arranged in a randomized block design between plots.

[0126] Pesticide application time and method:

[0127] On June 23, 2022, a knapsack manual sprayer was used for spraying pesticides, and the blank control area was sprayed with an equal amount of clear water.

[0128] Pesticide application equipment: Chaolv Meidebi 16 - type manual sprayer.

[0129] Usage capacity: 800-1000ml of liquid medicine for a single plant. The amount of liquid medicine used should be adjusted according to the size of the tree crown. In principle, it is best to use a method that water drips from the leaves.

[0130] 3. Investigation and Results

[0131] Survey time and frequency: The number of active mites on apple trees in each treatment area was investigated before application and on the 2nd, 7th and 14th days after application. A total of 4 surveys were conducted.

[0132] Survey method: Select 2 test trees in the middle of each plot, and hang signs on the branches in the five directions of east, west, south, north and center. Investigate the number of active mites on 10 leaves. Use a handheld magnifying glass to check and record the number of active mites on the leaves.

[0133] Efficacy calculation method: The control effect data of each plot were analyzed by variance analysis using the DMRT method, and the SSR method was used to compare the significance of the difference between the average control effects of each drug treatment. The control effect (%) was calculated according to the formula of Example 3.

[0134] 4. Direct impact on crops

[0135] No adverse effects of the test agent on the growth, branches and fruit surface of apple trees were found.

[0136] 5. Impact on other organisms

[0137] No adverse effects of the test agents on non-target organisms were observed during the investigation.

[0138] Test results

[0139] At the beginning of the peak period of active red spider mites in apple trees, dilute 45% bifenazate·pyraclostrobin suspension preparation 2500-3500 times, and spray evenly inside and outside the tree trunk and up and down the canopy of the apple tree once. The front and back of the leaves should be evenly sprayed with the medicine. The amount of liquid used should be enough to drip water from the leaves. This can effectively control the damage of red spider mites in apple trees.

[0140] Table 6: Field efficacy test of 45% bifenazate·pyraclostrobin suspension in controlling red spider mites in apple trees

[0141]

[0142] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention, rather than to limit it.

Claims

1. A fenpyroximate·bifenazate suspension concentrate, characterized in that, it contains the following components in weight percentage: fenpyroximate 15%, bifenazate 30%, Agrilan 755 2.5%, MORWET-D500 4.5%, ethylene glycol 4%, magnesium aluminum silicate 0.5%, xanthan gum 0.12%, fungicide BIT20 0.15%, defoamer 0.05%, and water is added to make up 100%.

2. The fenpyroximate·bifenazate suspension concentrate according to claim 1, characterized in that, the preparation method is: the technical material and the auxiliary agents are mixed in a certain proportion with water as the dispersion medium and subjected to wet ultrafine grinding. When grinding, zirconia beads need to be added to the mixture, and it is ground at a high speed at a rate of 1500 - 2000 r / min at room temperature to reduce the average particle size of the suspension concentrate to less than 3 μm, and the pesticide suspension concentrate is obtained after separating the zirconia beads.

3. Use of the fenpyroximate·bifenazate suspension concentrate according to any one of claims 1 - 2 for controlling crop pests.

4. The use according to claim 3, characterized in that, the pest is spider mite.

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