Pesticide composition and application thereof

Abstract

The invention belongs to the technical field of pesticide mite killing, and discloses a pesticide composition and application thereof.The pesticide composition comprises a compound shown in the formula I, imgabs0 # and mineral oil, and the mass ratio of the compound shown in the formula I to the mineral oil is 1: 35-36: 1. The invention also provides a pesticide preparation prepared from the compound as shown in the formula I, mineral oil and auxiliary components acceptable in pesticide. The pesticide composition disclosed by the invention is used for preventing and treating various plant mites, has a remarkable synergistic effect, and can effectively delay the generation and development of drug resistance of the mites and reduce the use amount of pesticides.

Description

Technical Field

[0001] The present invention belongs to the technical field of pesticidal acaricides, and discloses a pesticidal composition and its use. Background Art

[0002] Harmful mites belong to Arachnida of the class Arachnida, and are mainly distributed in temperate regions. They are important pest groups that harm fruit trees such as citrus and lemon. Usually, they cause direct harm by damaging the plant epidermis with their mouthparts and sucking the plant sap. They can also act as vectors for viruses to spread virus diseases, causing indirect harm and resulting in huge economic losses. Harmful mites have the characteristics of large population, short growth cycle, strong adaptability and great difficulty in control. In agricultural production, the control of harmful mites mainly relies on chemical control, but the long-term use of chemical control has led to the resistance of harmful mites to some acaricides. Therefore, the development of highly efficient, low-toxic, safe and non-resistant acaricides has become a new direction for the control of harmful mites.

[0003] Mineral oil belongs to organic pesticides and has the advantages of being environmentally friendly, non-resistant, residue-free and less toxic to beneficial organisms. It is an ideal agent for integrated pest management.

[0004] At present, there is no relevant report on the compounding of mineral oil with the compound of formula I and its reasonable compounding for the control of mites. Studying the control effect of the reasonable compounding of mineral oil and insecticidal and acaricidal agents on mites, and finally finding a control method that is highly efficient and low-toxic to mites and low-toxic or non-toxic to the environment, so as to significantly reduce the impact of mites on agricultural production, which is of great significance for reducing and replacing the application of conventional chemical pesticides and protecting the agricultural ecological environment. Summary of the Invention

[0005] In order to solve the above problems existing in the prior art, the present invention provides a pesticidal composition. The pesticidal composition is prepared into a suitable preparation dosage form by reasonably compounding mineral oil with the compound of formula I. The pesticidal composition has excellent control effects on harmful mites in agriculture, horticulture and forestry, reduces the dosage of pesticides, and slows down the generation of mite resistance.

[0006] In order to achieve the above object, the present invention adopts the following technical solution: A pesticidal composition, characterized in that the pesticidal composition is composed of a compound of formula I and mineral oil, and the compound of formula I: The mass ratio with mineral oil is 1:35 to 36:1, or any value within the above numerical range.

[0007] Further, the mass ratio of the compound of formula I to mineral oil is 1:35 to 22:1, or any value within the above numerical range.

[0008] Furthermore, the mass ratio of the compound of Formula I to the mineral oil is 1:26 to 18:1, or any value within the above numerical range.

[0009] Furthermore, the mass ratio of the compound of Formula I to the mineral oil is 1:15 to 12:1, or any value within the above numerical range.

[0010] Furthermore, in addition to the active ingredient, the pesticide composition further comprises agriculturally acceptable auxiliary ingredients, and the auxiliary ingredients are fillers and / or surfactants.

[0011] The auxiliary ingredients are selected from one or more of wetting agents, dispersants, emulsifiers, thickeners, disintegrants, antifreezing agents, defoaming agents, solvents, preservatives, stabilizers, synergists or carriers;

[0012] Furthermore, the wetting agent is selected from one or more of alkyl benzene sulfonates, alkyl naphthalene sulfonates, lignin sulfonates, sodium dodecyl sulfate, sodium dioctyl sulfosuccinate, α-olefin sulfonates, alkylphenol polyoxyethylene ethers, castor oil polyoxyethylene ethers, alkylphenol ethoxylates, fatty alcohol ethoxylates, sodium fatty alcohol polyoxyethylene ether sulfate, silkworm excrement, saponin powder, sapindus powder, SOPA, detergent, emulsifier series 2000 and wetting penetrant F; and / or

[0013] Furthermore, the dispersant is selected from one or more of lignin sulfonates, alkyl naphthalene sulfonate formaldehyde condensates, naphthalene sulfonates, triphenylvinylphenol ethoxylate phosphates, fatty alcohol ethoxylates, alkylphenol polyoxyethylene ethers, alkylphenol polyoxyethylene ether methyl ether condensate sulfates, fatty amine polyoxyethylene ethers, glycerol fatty acid ester polyoxyethylene ethers, polycarboxylates, polyacrylates, phosphates, EO-PO block copolymers and EO-PO graft copolymers; and / or

[0014] Furthermore, the emulsifier is selected from one or more of calcium dodecylbenzenesulfonate, alkylphenol formaldehyde resin polyoxyethylene ether, phenethylphenol polyoxyethylene polyoxypropylene ether, fatty alcohol ethylene oxide-propylene oxide copolymer, styrylphenol polyoxyethylene ether, castor oil polyoxyethylene ether and alkylphenol ether phosphate; and / or

[0015] Furthermore, the thickener is selected from one or more of xanthan gum, organobentonite, gum arabic, sodium alginate, magnesium aluminum silicate, carboxymethyl cellulose and white carbon black; and / or

[0016] Furthermore, the disintegrant is selected from one or more of sodium sulfate, ammonium sulfate, aluminum chloride, sodium chloride, ammonium chloride, bentonite, glucose, sucrose, starch, cellulose, urea, sodium carbonate, sodium bicarbonate, citric acid and tartaric acid; and / or

[0017] Further, the antifreeze is selected from one or more of alcohols, alcohol ethers, chlorinated hydrocarbons, and inorganic salts; and / or

[0018] Further, the defoamer is selected from one or more of C 10 -C 20 saturated fatty acid compounds, silicone oils, silicone compounds, C 8 -C 10 fatty alcohols; and / or

[0019] Further, the solvent is selected from one or more of benzene, toluene, xylene, 1,2,4,5-tetramethylbenzene, methanol, ethanol, isopropanol, n-butanol, dimethyl sulfoxide, dimethylformamide, cyclohexanone, alkylene carbonate, diesel oil, solvent naphtha, vegetable oil, vegetable oil derivatives, and water; and / or

[0020] Further, the preservative is selected from one or more of propionic acid, sodium propionate, sorbic acid, sodium sorbate, potassium sorbate, benzoic acid, sodium benzoate, sodium p-hydroxybenzoate, methyl p-hydroxybenzoate, Kathon, and 1,2-benzisothiazolin-3-one; and / or

[0021] Further, the stabilizer is selected from one or more of disodium hydrogen phosphate, oxalic acid, succinic acid, adipic acid, borax, 2,6-di-tert-butyl-p-cresol, triethanolamine oleate, epoxidized vegetable oil, kaolin, bentonite, attapulgite, silica white, talc powder, montmorillonite, and starch; and / or

[0022] Further, the synergist is selected from synergistic phosphorus and synergistic ether; and / or

[0023] Further, the carrier is selected from one or more of ammonium salts, ground natural minerals, ground artificial minerals, silicates, resins, waxes, solid fertilizers, water, organic solvents, mineral oils, vegetable oils, and vegetable oil derivatives.

[0024] Further, the preparation dosage form that the composition can prepare is a liquid preparation.

[0025] Further, the preparation dosage form is an emulsifiable concentrate, an emulsion in water, or a dispersible oil suspension.

[0026] Further, the total weight of the compound of formula I and the mineral oil accounts for 1% to 80% of the total weight of the pesticide composition.

[0027] The present invention also discloses the use of the pesticide composition as described above for controlling phytophagous mites.

[0028] Further, the phytophagous mites are phytophagous mites of the family Tetranychidae and phytophagous mites of the family Eriophyidae;

[0029] Further, the tetranychid mites are Panonychus citri, Panonychus ulmi, Tetranychus cinnabarinus or Tetranychus urticae, and the eriophyid mites are Phyllocoptruta oleivora.

[0030] Advantages of the present invention:

[0031] The pesticide composition of the present invention rationally combines the organic pesticide mineral oil with the compound of formula I. The components are reasonable, the acaricidal effect is good, the drug use cost is low, and its acaricidal activity is not a simple superposition of active ingredients, but has a significant synergistic effect, which can delay the generation of mite resistance, is safe for crops, and meets the safety requirements of pesticide formulations. Specific embodiments

[0032] To make the technical solutions, objectives and advantages of the present invention clearer, the present invention is described by the following specific embodiments, but the present invention can be implemented in various forms and should not be limited by the embodiments described herein.

[0033] Formulation preparation examples:

[0034] Preparation method of emulsifiable concentrate: Weigh the compound of formula I, mineral oil, solvent and cosolvent, add them to a mixing kettle and stir to dissolve. Then add an emulsifier, make up the balance with the remaining solvent, stir evenly in the stirring kettle, and filter to obtain the emulsifiable concentrate required by the present invention.

[0035] Preparation method of emulsion in water: Dissolve the weighed compound of formula I in a solvent, add it and mineral oil to an emulsifier to form a uniform oil phase. Mix deionized water, antifreeze, etc. together to form a uniform aqueous phase. Under high-speed shearing, add the oil phase to the aqueous phase, shear until the particle size is qualified, and then add an antifoaming agent, thickener and preservative and stir evenly to form a well-dispersed emulsion in water product.

[0036] Preparation example 1: 27% compound of formula I · mineral oil emulsifiable concentrate (1:26)

[0037] Formulation composition: 1% compound of formula I, 26% mineral oil, 18% cyclohexanone, 12% polyoxyethylene glycerol fatty acid ester, 2% calcium dodecylbenzenesulfonate, 22% propylene carbonate, and make up the balance with xylene.

[0038] Preparation example 2: 22% compound of formula I · mineral oil emulsifiable concentrate (2:9)

[0039] Formulation composition: 4% compound of formula I, 18% mineral oil, 20% cyclohexanone, 15% polyoxyethylene sorbitan oleate, 2% calcium dodecylbenzenesulfonate, and make up the balance with methyl oleate.

[0040] Preparation example 3: 38.5% compound of formula I · mineral oil emulsifiable concentrate (1:10)

[0041] Formulation composition: 3.5% of Compound of Formula I, 35% mineral oil, 13% EO / PO block copolymer, 16% acetophenone, 10% cyclohexanone, 2% calcium dodecylbenzenesulfonate, and the balance is made up with pseudocumene.

[0042] Preparation Example 4: 34% Compound of Formula I·Mineral Oil EC (15:2)

[0043] Formulation composition: 30% of Compound of Formula I, 4% mineral oil, 25% propylene glycol methyl ether, 12% phenethylphenol polyoxyethylene polyoxypropylene ether, 2% calcium dodecylbenzenesulfonate, 12% cyclohexanone, and the balance is made up with methyl oleate.

[0044] Preparation Example 5: 10% Compound of Formula I·Mineral Oil EW (1:9)

[0045] Formulation composition: 1% of Compound of Formula I, 9% mineral oil, 5% xylene, 15% cyclohexanone, 2% BHT, 2% polyoxyethylene sorbitan monooleate, 5% ethylene oxide - propylene oxide copolymer, 5% propylene glycol, 0.05% silicone defoamer, 0.25% xanthan gum, 0.1% sodium benzoate, and the balance is made up with deionized water.

[0046] Preparation Example 6: 12% Compound of Formula I·Mineral Oil EW (1:15)

[0047] Formulation composition: 0.75% of Compound of Formula I, 11.25% mineral oil, 3% EO / PO block copolymer, 2% alkylphenol formaldehyde resin polyoxyethylene ether sulfate, 20% cyclohexanone, 0.25% xanthan gum, 5% ethylene glycol, 0.1% potassium benzoate, 0.05% silicone oil, and the balance is made up with deionized water.

[0048] Preparation Example 7: 13% Compound of Formula I·Mineral Oil EW (12:1)

[0049] Formulation composition: 12% of Compound of Formula I, 1% mineral oil, 8% triphenylethylene phenol polyoxyethylene polyoxypropylene ether, 1% alkyl polyoxyethylene ether sulfonate, 20% cyclohexanone, 0.25% xanthan gum, 5% glycerol, 0.1% sodium benzoate, 0.04% silicone oil, and the balance is made up with deionized water.

[0050] Preparation Example 8: 9% Compound of Formula I·Mineral Oil EW (2:1)

[0051] Formulation composition: 6% of Compound of Formula I, 3% mineral oil, 8% alkylphenylethylphenol polyoxyethylene polyoxypropylene ether, 2% styrylphenol polyoxyethylene ether sulfate, 20% cyclohexanone, 0.25% xanthan gum, 5% glycerol, 0.1% sodium sorbate, 0.05% silicone oil, and the balance is made up with deionized water.

[0052] Example 1: Indoor Toxicity Test on Panonychus citri

[0053] Basis for the test: The test was carried out with reference to NY / T 1154.12-2008 Guidelines for Indoor Bioactivity Tests of Pesticides - Part 12: Slide Immersion Method for Tetranychidae.

[0054] Test targets: Nymphs of Panonychus citri and nymphs of Phyllocoptruta oleivora.

[0055] Test agents: Technical compound of Formula I (provided by the R & D Center of Hailir Pesticides & Chemicals Group Co., Ltd.) and 99% mineral oil (provided by Hailir Pesticides & Chemicals Group Co., Ltd., PD20121278).

[0056] Test method: The test agents were diluted to 5 concentrations based on preliminary tests, with 4 replicates for each concentration.

[0057] Select test mites that are reared indoors and in the same physiological state. Cut a 2-cm long double-sided tape and stick it to one end of a glass slide. Pick healthy test mites and stick them to the double-sided tape, with 30 mites on each slide. After treatment, place the pest mites in a container lined with a wet sponge, cover it with a lid, and place it under the condition of (25 ± 1)°C. After 2 hours, conduct microscopic examination, remove the dead, injured, and inactive individuals, and make up to 30 mites per slide.

[0058] Immerse the glass slide in the above agents, gently shake for 5 s, then take it out, blot the excess liquid with absorbent paper, place it in a white porcelain dish lined with a wet sponge, cover it with a plastic film with good light transmittance, and set up a treatment containing no agent (containing all organic solvents and emulsifiers) as the blank control.

[0059] Rearing and observation: Place the treated pest mites in an artificial climate chamber under the conditions of (25 ± 1)°C, relative humidity of 75% - 85%, and a light cycle of L:D = (16:8) h for rearing and observation. Check after 48 hours of treatment, check the mortality of the pest mites, and record the total number of mites and the number of dead mites.

[0060] Data statistics and analysis:

[0061] According to the investigated data, calculate the corrected mortality of each treatment, and calculate according to the following formula. The calculation results are all rounded to two decimal places.

[0062]

[0063] In the formula:

[0064] P - Mortality rate, in percentage (%);

[0065] K - Number of dead insects, in number;

[0066] N —— represents the total number of insects processed, with the unit of head.

[0067]

[0068] In the formula:

[0069] P 1 —— corrected mortality rate, with the unit of percentage (%)

[0070] P t —— treatment mortality rate, with the unit of percentage (%)

[0071] P 0 —— mortality rate of the blank control, with the unit of percentage (%).

[0072] If the mortality rate of the control < 5%, no correction is required; if the mortality rate of the control is between 5% and 20%, the correction should be made according to the formula of the corrected mortality rate; if the mortality rate of the control > 20%, the test needs to be redone.

[0073] Use the DPS statistical analysis system for analysis to obtain the virulence regression equation, correlation coefficient, and LC 50 value to evaluate the activity of the test agent against the biological test material.

[0074] The co-toxicity coefficient (CTC value) of the mixture is calculated as follows:

[0075]

[0076] In the formula:

[0077] ATI—— actual measured virulence index of the mixture;

[0078] S—— LC 50 of the standard acaricide, with the unit of milligram per liter (mg / L);

[0079] M—— LC 50 of the mixture, with the unit of milligram per liter (mg / L).

[0080] TTI = TI A × P A + TI B × P B

[0081] In the formula:

[0082] TTI—— theoretical virulence index of the mixture;

[0083] TI A —— virulence index of agent A;

[0084] P A——Percentage content of Agent A in the mixture, in percentage (%)

[0085] TI B ——Toxicity index of Agent B

[0086] P B ——Percentage content of Agent B in the mixture, in percentage (%)

[0087]

[0088] Wherein:

[0089] CTC - Co-toxicity coefficient

[0090] ATI - Measured toxicity index of the mixture

[0091] TTI - Theoretical toxicity index of the mixture

[0092] When the co-toxicity coefficient CTC of the compounding is ≥ 120, it shows a synergistic effect; when CTC ≤ 80, it shows an antagonistic effect; when 80 < CTC < 120, it shows an additive effect

[0093] The results of the indoor activity test are shown in the following table

[0094] Table 1 Results of the indoor bioactivity test of the compound of Formula I and mineral oil against Panonychus citri

[0095]

[0096] The indoor test results show that the compound of Formula I and mineral oil have good bioactivity against Panonychus citri. When the mass ratio of the compound of Formula I to mineral oil is 1:35 - 20:1, the co-toxicity coefficient against Panonychus citri is greater than 120, showing a synergistic effect; when the mass ratio of the compound of Formula I to mineral oil is 1:26 - 18:1, the synergistic effect is obvious; when the mass ratio of the compound of Formula I to mineral oil is 1:15 - 12:1, the synergistic effect is significant

[0097] Table 2 Results of the indoor bioactivity test of the compound of Formula I and mineral oil against Phyllocoptruta oleivora

[0098]

[0099]

[0100] Indoor test results show that the compound of formula I has good biological activity when compounded with mineral oil. The mass ratio of the compound of formula I to mineral oil is 1:35 to 22:1, and the co-toxicity coefficient against Phyllocoptruta oleivora is greater than 120, showing a synergistic effect; when the mass ratio of the compound of formula I to mineral oil is 1:16 to 15:1, the synergistic effect is obvious; when the mass ratio of the compound of formula I to mineral oil is 1:9 to 15:2, the synergistic effect is significant.

[0101] Example 2: Field efficacy test against Panonychus citri

[0102] Test site: A citrus orchard in Gaoqiao Town, Lianjiang City, Zhanjiang City, Guangdong Province. The citrus variety in the test plot is Hongjiang orange, with a tree age of 4 years and strong growth. The soil fertility of the test plot is medium to high, and the fertilizer and water management of all test plots is the same.

[0103] Test design: There are 9 treatments in the test, and each treatment is repeated 4 times. The test is arranged in a randomized block design, with 3 citrus trees in each plot, and a protection row is set.

[0104] Application time: The test was applied on April 20, 2024, and only one application was made during the entire application period. The conventional spraying method was used for application, and the application equipment was a MATABI super green 16 backpack hand-press sprayer with a double nozzle, so that all the leaves inside and outside the tree crown were evenly covered with the medicine, and the blank control was sprayed with an equal amount of clear water.

[0105] Investigation method: Before the test, two fruit trees were randomly selected in each plot, and for each tree, the young shoots were investigated and marked according to the east, south, west, north, and middle directions, and the number of active mites on 25 leaves was investigated. A total of 50 leaves were investigated in each plot. The leaf surface was directly observed with a hand-held magnifying glass to count the number of mites. The mite population base was investigated before application, and the number of active mites was investigated 3 days, 10 days, and 15 days after application.

[0106] Method for calculating efficacy:

[0107]

[0108] Results and analysis of the field efficacy test:

[0109] Table 3 Results of the field efficacy test against Panonychus citri

[0110]

[0111]

[0112] The results of the field efficacy experiment showed that the compound of formula I and mineral oil were compounded in a suitable mass ratio, and the control effect on Panonychus citri was significant. The compounding still showed a high control effect 15 days after application, and the long-lasting period was long. Within the above reasonable application concentration range of the test agents, there was no toxic effect or adverse impact on citrus trees, and there was no obvious killing effect on natural enemies such as Stethorus punctillum and predatory mites in citrus orchards.

[0113] Example 3: Field Efficacy Test for Controlling Phyllocoptruta oleivora

[0114] Test site: Dongchong Town, Nansha District, Guangzhou City, Guangdong Province. The plot is flat, with convenient drainage and irrigation, medium fertility, good management conditions, the citrus tree age is about 4 years, growing vigorously and in good growth. The cultivation and management conditions (soil type, water and fertilizer management, planting density, growth period, water layer management, etc.) of all test plots are consistent with the local area. The test period is the fruit swelling period.

[0115] Test crop: Zhengyuehong tangerine.

[0116] Test design: The test was set with 7 treatments, 4 replicates for each treatment, a total of 28 plots, and 2 trees in each plot. Randomized block arrangement, with protective plants set between plots. The application was carried out on a sunny and windless day. Using the spraying method, the actual dosage of each plot was dissolved and diluted with clear water, and then applied with a Gongnong-16 type knapsack sprayer. The application rate was such that the leaves and fruits were moist and a little liquid medicine dripped from the leaves, and it was applied once in total.

[0117] Test investigation time and method: 2 trees were fixed for investigation in each plot. For each tree, 2 damaged leaves of the same shoot stage were fixed and marked at 5 positions: east, south, west, north, and the middle top, and 2 visual fields were investigated to record the number of live insects. The pest population base was investigated before application, and the remaining mite numbers were investigated 1, 7, 14, and 21 days after application respectively. Calculate the mite population reduction rate and control effect.

[0118] Safety investigation: During the whole efficacy test process, the test agents were observed irregularly for any phytotoxicity to citrus plants and any phenomena of promoting or inhibiting growth.

[0119] Efficacy calculation method:

[0120]

[0121] Results and analysis of the field efficacy test:

[0122] Table 4 Results of the Field Efficacy Test for Controlling Phyllocoptruta oleivora

[0123]

[0124]

[0125] The control effect of the compound preparation composed of the compound of formula I and mineral oil can reach 85.77% - 92.23% 7 days after application, indicating that the compound preparation has good quick-acting property. 21 days after application, the control effects of each compound preparation are 86.31% - 93.71%, indicating that the residual efficacy period of the pesticide composition after compounding can reach more than 21 days, and the damage can be controlled by applying the pesticide once per generation. During the whole efficacy test process, the tested pesticides had no phytotoxicity to citrus plants and no inhibition of citrus growth was observed.

[0126] In summary, through indoor bioactivity tests and field trials, the pesticide composition of the present invention has significant control effect on target mites, good quick-acting property, long residual efficacy period, and has no phytotoxicity to target crops and is safe for crops.

[0127] Although the present invention has been described in detail with general descriptions and specific embodiments above, based on the present invention, some modifications or improvements can be made, which are obvious to those skilled in the art. Therefore, these modifications or improvements made without departing from the spirit of the present invention all fall within the scope of protection of the present invention.

Claims

1. A pesticide composition, characterized in that: The pesticide composition comprises a compound of formula I and mineral oil, wherein the compound of formula I is: The mass ratio to mineral oil is 1:35~36:

1.

2. The pesticide composition according to claim 1, characterized in that The mass ratio of the compound of formula I to the mineral oil is 1:35 to 22:

1.

3. The pesticide composition according to claim 2, characterized in that The mass ratio of the compound of formula I to the mineral oil is 1:26 to 18:

1.

4. The pesticide composition according to claim 3, characterized in that The mass ratio of the compound of formula I to the mineral oil is 1:15 to 12:

1.

5. The pesticide composition according to claim 1, characterized in that The pesticide composition includes, in addition to the active ingredients, auxiliary ingredients acceptable to pesticides, and the auxiliary ingredients are fillers and / or surfactants.

6. The pesticide composition according to claim 1, characterized in that The composition can be prepared in the form of a liquid preparation.

7. The pesticide composition according to claim 6, characterized in that The preparation dosage form is emulsifiable concentrate, aqueous emulsion, and dispersible oil suspension.

8. The pesticide composition according to claim 1, characterized in that The total weight of the compound of formula I and the mineral oil accounts for 1% to 80% of the total weight of the pesticide composition.

9. Use of the pesticide composition according to any one of claims 1 to 8 for controlling plant pests mites.

10. The use according to claim 9, characterized in that The harmful mites are the pests of Tetranychus mites and Tetranychus mites.

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