A composition, formulation and application of emamectin benzoate and spinosad.

Abstract

This invention discloses a composition, formulation, and application of abamectin and ethyl spinosad. The microemulsion comprises the active ingredient, conventional adjuvants, and a key functional systemic absorption enhancer. A specific ratio of organosilicon surfactant (such as Silwet L-77) and methylated vegetable oil (such as Pro-MSO) is used as the functional systemic absorption enhancer; this combination produces a synergistic effect, significantly improving the systemic conductivity of the active ingredient within the plant. Indoor bioassay results show that the LC50 of this formulation... 50 The dosage is reduced by more than 50% compared to traditional formulations; field efficacy trials have confirmed that, at the same effective ingredient dosage, its control efficacy against eggplant thrips is as high as 95% or more, with excellent residual effect. This invention, through innovative optimization of the adjuvant system, achieves simultaneous improvement in pesticide utilization and control efficacy, providing an effective solution for developing new pesticide formulations that are highly efficient, require low dosage, and delay resistance.

Description

Technical Field

[0001] This invention belongs to the field of pesticide formulations and relates to a composition, formulation and application of abamectin and spinosad. Background Technology

[0002] Emamectin benzoate (BAB) primarily acts as a stomach poison with some contact toxicity. It exhibits high activity against cotton bollworms, lepidopteran, mites, coleopteran, and homopteran pests. It does not cross-contaminate with other crops, degrades easily in soil and water without residue, and does not pollute the environment. Within conventional dosage ranges, it is safe for beneficial insects and humans and livestock, and can be mixed with most pesticides. BAB can rapidly penetrate plant tissues through leaves or epidermis, providing good contact toxicity against pests hidden on the underside of leaves or in rolled leaves (such as lepidopteran larvae). BAB has lateral translocation capabilities, spreading locally with plant sap, but it cannot be systemically translocated throughout the plant via the vascular bundles; for example, root application will not allow it to reach the leaves.

[0003] Ethyl spinosad, commonly known as spinosad, has both stomach poison and contact action. It acts on the nervous system of insects and is effective against diamondback moth, beet armyworm, leaf miner, thrips, cotton bollworm, and bean pod borer. However, ethyl spinosad suffers from insufficient systemic activity.

[0004] Existing research mainly focuses on the development of compound formulations, achieving synergistic control effects by combining abamectin with ethyl spinosad. For example, reference 1: CN102396471A discloses a composition containing ethyl spinosad and abamectin or emamectin benzoate. The weight ratio of the two is in the range of 50:1 to 1:50. The composition can be formulated into various formulations such as wettable powder, water-dispersible granules, and suspension concentrates. The resulting compound composition has a synergistic effect and can control a variety of pests (such as diamondback moth, beet armyworm, and thrips), reducing pesticide dosage, reducing pesticide resistance, and reducing environmental pollution; reference 2: CN102396474A discloses an insecticidal composition containing ethyl spinosad and a bio-based insecticide, with the weight ratio of ethyl spinosad to the bio-based insecticide ranging from 1:60 to 60:1. The resulting composition can be used to control rice stem borers, diamondback moths, beet armyworms, and cotton bollworms. The composition expands the application range of insecticides, achieves synergistic effects, reduces pesticide usage, and lowers costs and environmental hazards. Reference 3: CN102578115A focuses on the formulation and preparation method of a suspension concentrate containing ethyl spinosad and abamectin. This formulation is environmentally friendly (water-based), has a broad spectrum of control, and is less likely to induce resistance. Reference 4: CN119867062A discloses a suspension concentrate containing ethyl spinosad and abamectin and its application. This reference relates to an improved suspension concentrate containing ethyl spinosad, abamectin, and a specific synergist (a combination of silwet 618 and GY-Tmax, with a mass ratio of 1:1 to 1:7). By adding specific synergists (such as Silwet 618 and GY-Tmax), the efficacy and persistence of compound suspension concentrates are enhanced, claiming that the synergists can significantly improve field control efficacy against pests (such as diamondback moth and fall armyworm). However, existing combinations or formulations of abamectin and spinosad do not overcome the deficiency of insufficient systemic activity in these two components.

[0005] While maintaining the stomach and contact toxicity of abamectin and spinosad, how to improve the systemic conductivity of the agent in plants, thereby further enhancing efficacy and correspondingly reducing the dosage, is an urgent problem to be solved in this field. Summary of the Invention

[0006] To address the technical problem of improving the systemic conductivity of emamectin benzoate and spinosad in plants, this invention provides a pesticide composition comprising emamectin benzoate and spinosad. The active ingredients in the composition include emamectin benzoate and spinosad, and the adjuvants include solubilizers, emulsifiers, surfactants, functional systemic absorption enhancers, antifreeze agents, preservatives, defoamers, buffers, and dispersion media. This invention, through the adjuvants, alters the adhesion and penetration of the active ingredients on the plant surface and improves their conduction within the vascular bundles (xylem and phloem), thereby enhancing their mobility and distribution within the plant.

[0007] Therefore, the present invention provides the following technical solution:

[0008] A composition comprising abamectin and spinosad, the composition comprising active ingredients and adjuvants, the active ingredients comprising abamectin and spinosad, and the adjuvants comprising solubilizers, emulsifiers, surfactants, functional systemic accelerators, antifreeze agents, preservatives, defoamers, buffers, and dispersion media.

[0009] The emamectin benzoate is emamectin benzoate or emamectin.

[0010] The co-solvent is selected from aromatic hydrocarbon solvents (Solvesso™ 150 / 200), methylated soybean oil, methylated rapeseed oil, methylated palm oil, methylated corn oil, N,N-dimethyldecylamide, N-methylpyrrolidone and / or methyl oleate.

[0011] The emulsifier is selected from fatty alcohol polyoxyethylene ether (AEO-7 or AEO-9), castor oil polyoxyethylene ether (EL-20 or EL-40), polyether block copolymer (PE-6400 or PE-6800), sodium lauryl polyoxyethylene ether sulfate (AES), or calcium dodecylbenzenesulfonate.

[0012] The co-surfactant is selected from short-chain alcohols (n-butanol, n-pentanol or n-hexanol), diols or ether alcohols (ethylene glycol, propylene glycol or ethylene glycol monobutyl ether), and polyethylene glycol (PEG-200 or PEG-400).

[0013] The functional systemic accelerator is selected from organosilicon surfactants (Silwet L-77), methylated vegetable oils, fatty alcohol polyoxyethylene ether phosphates, compound of alkyl ethoxylates and vegetable oils, polylactic acid-glycolic acid copolymer (PLGA), or chitosan.

[0014] The antifreeze is selected from ethylene glycol, propylene glycol, urea, or glycerin.

[0015] The preservative is selected from sodium benzoate, potassium sorbate, Kathon or formaldehyde.

[0016] The defoamer is selected from silicone defoamer emulsions or mineral oil-based defoamers.

[0017] The buffer is selected from the citric acid-sodium citrate buffer system (effective pH range 3.0-6.2) or the potassium dihydrogen phosphate-dipoxat phosphate buffer system (effective pH range 5.8-8.0).

[0018] The dispersion medium is selected from deionized water, tap water, or ultrapure water.

[0019] Furthermore, the present invention provides a composition comprising emamectin benzoate and ethyl spinosad, comprising:

[0020] abamectin 2-5%,

[0021] Ethyl spinosad 3-10%,

[0022] Cosolvent 8-20%,

[0023] Emulsifier 10-25%,

[0024] 5-10% co-surfactant

[0025] Functional systemic agonists 1-6%

[0026] Antifreeze 3-5%,

[0027] Preservative 0.1-0.5%,

[0028] Defoamer 0.1-0.5%,

[0029] Buffer 0.1-0.5%,

[0030] Add deionized water to make up the remaining amount.

[0031] Preferably, the present invention provides a composition of abamectin and ethyl spinosad, the specific composition of which is as follows:

[0032]

[0033] The preparation method of the composition includes the following steps:

[0034] Oil phase preparation: Under stirring, abamectin and spinosad technical grade were dissolved in a composite cosolvent of methylated palm oil and N-methylpyrrolidone. After complete dissolution, AEO-9, EL-40, PEG-400, Silwet L-77, and Pro-MSO were added and stirred until homogeneous and transparent oil phase was formed.

[0035] Aqueous phase preparation: In another container, mix deionized water, propylene glycol, sodium benzoate, buffer, and defoamer, and stir until completely dissolved.

[0036] Emulsion formation: Under high-speed shearing (3000 rpm), the aqueous phase is slowly added to the oil phase. After the addition is complete, shearing continues for 10-15 minutes until a transparent or translucent, homogeneous, and stable liquid is formed. This process may form a viscous liquid crystal phase, which can be converted into a low-viscosity microemulsion by continued shearing or slight heating.

[0037] Filtration and filling: After the sample passes the test, it is filtered and filled. The composition prepared according to the above preparation method is a microemulsion.

[0038] Compared with the prior art, the advantages of the present invention are as follows:

[0039] Superior control of piercing-sucking pests (thrips, aphids, whiteflies): The pesticide is systemically absorbed into the sap, causing poisoning upon ingestion. Improved control of leaf-mining and leaf-rolling pests (leaf miners, leaf rollers): The pesticide penetrates deep into leaf tissue. Better control of newly hatched larvae of boring pests (cattle borers, fruit borers): Systemic pesticides allow larvae to come into contact with or ingest the poison before they bore into the soil. Extended residual effect: Systemic pesticides are less likely to be washed away by rain. Reduced dosage: Due to improved absorption efficiency, the amount of active ingredient per unit area can be reduced to achieve the same control efficacy. Detailed Implementation

[0040] The present invention will be further described below with reference to the embodiments. The percentages in the embodiments are all weight percentages, but the present invention is not limited thereto.

[0041] I. Formulation Preparation

[0042] Formulation Example 1: 10% Abamectin·Ethyl Sponsauce Microemulsion

[0043] Emamectin benzoate (95%) 3.16% (3% by weight),

[0044] Ethyl spinosad (95%) 7.37% (7% by weight),

[0045] Methylated palm oil 7.0%,

[0046] N-methylpyrrolidone 3.0%,

[0047] EL-40 and AEO-9 (1:1 blend) 16.7%,

[0048] PEG-400 8.3%,

[0049] Silwet L-770.2%

[0050] Methylated vegetable oil (Pro-MSO) 1.5%,

[0051] Propylene glycol 4.0%,

[0052] Sodium benzoate 0.2%,

[0053] Citric acid-sodium citrate buffer system 0.4%,

[0054] 0.3% silicone defoamer emulsion

[0055] Add deionized water to bring the total to 100%.

[0056] A 10% abamectin·ethyl spinosad microemulsion was prepared according to the microemulsion preparation method described in the invention content section.

[0057] Formulation Example 2, 12% abamectin·spinosadine microemulsion, differs from Formulation Example 1 in that the amount of abamectin is 2% and the amount of spinosadine is 10%.

[0058] Formulation Example 3, 8% abamectin·spinosadine microemulsion, differs from Formulation Example 1 in that the amount of abamectin is 5% and the amount of spinosadine is 3%.

[0059] Comparative Example 1, 10% abamectin·ethyl spinosad microemulsion, differs from Formulation Example 1 in that it does not contain a functional systemic absorption enhancer.

[0060] Comparative Example 2, 10% abamectin·ethyl spinosad microemulsion, differs from Formulation Example 1 in that the functional systemic absorption promoter is Silwet L-77, and the dosage is 1.7%.

[0061] Comparative Example 3, 10% abamectin·ethyl spinosad microemulsion, differs from Formulation Example 1 in that the functional systemic absorption promoter is methylated vegetable oil (Pro-MSO), and the dosage is 1.7%.

[0062] Comparative Example 4: 15% Abamectin·Ethyl Sponsauce Microemulsion

[0063] 10% abamectin, 5% spinosad, 12.0% N,N-dimethyldecylamide, 10.0% alkylphenol polyoxyethylene ether (OP-10), 8% castor oil polyoxyethylene ether (EL-40), 2% ethylene glycol, 0.5% sodium benzoate, 0.3% citric acid-sodium citrate buffer, 0.6% polyether-siloxane defoamer, and deionized water to make up the balance.

[0064] Comparative Example 5: 10% spinosad·emamectin benzoate suspension prepared according to formulation 1 of Example 1 in reference 4: CN119867062A.

[0065] II. Formulation Performance Evaluation

[0066] 2.1 Physicochemical stability assessment

[0067] Test methods: The mass fraction of active ingredients was determined by HPLC; composition and appearance (transparent homogeneous liquid, free of suspended matter and sediment), emulsion stability, active ingredient content, emulsification and dispersibility, persistent foaming, pH value, and thermal and cold storage stability were all determined according to the relevant national standards.

[0068] Table 1. Results of stability tests for each formulation

[0069]

[0070] Both the formulation examples and the comparative examples prepared according to this invention meet the national standards for formulation stability and are qualified. The pH value of the formulation examples prepared according to this invention is lower than that of the comparative examples.

[0071] 2.2 Systemic conductivity bioassay

[0072] Crop: Potted cabbage;

[0073] Test insect: 3rd instar larvae of the diamondback moth;

[0074] Test reagents: Based on the preliminary test, a series of concentration gradients of 0.1 mg ai / L, 0.2 mg ai / L, 0.4 mg ai / L, 0.8 mg ai / L, 1.6 mg ai / L and 3.2 mg ai / L were set up for each example formulation and comparative formulation; a water control was set up.

[0075] Test material preparation:

[0076] Leaf preparation: Gently rinse the surface of the cabbage leaves with clean water and pat dry with soft paper. Use a hole punch to create leaf discs of uniform diameter.

[0077] Preparation of test insects: Use a soft brush to gently pick out healthy and active third instar larvae of the diamondback moth for later use.

[0078] Chemical impregnation:

[0079] Completely immerse the leaf discs in solutions of varying concentrations, ensuring both sides are evenly wetted. Immersion time should be controlled to 5 seconds. After removal, use filter paper to absorb excess solution from the leaf edges and allow to air dry naturally, avoiding direct sunlight or high temperatures.

[0080] Inward conduction processing:

[0081] Place the treated leaf discs, leaf back side up, in a petri dish lined with moistened filter paper to retain moisture and prevent wilting. Cover the petri dish and place it under suitable light and temperature conditions (25±1℃, photoperiod L:D=16:8) to allow sufficient time (24 hours) for the agent to penetrate and conduct locally within the leaf tissue.

[0082] Inoculation and observation:

[0083] Using a paintbrush, gently transfer the prepared test insects to the culture dishes, ensuring each dish contains the same number of insects (30). Observe and record the number of dead insects or symptoms of poisoning (paralysis, refusal to feed) under a microscope periodically after 24, 48, and 72 hours. The criterion for determining death is that the insects show no reaction when gently touched with the paintbrush.

[0084] Results Survey and Data Analysis:

[0085] Data recording: Detailed records of the total number of test insects and the number of deaths for each treatment and each replicate.

[0086] Mortality rate calculation: Calculate the adjusted mortality rate to eliminate the impact of natural deaths on the outcome. The calculation formula is as follows:

[0087] Corrected mortality rate (%) = (treatment group mortality rate - control group mortality rate) / (1 - control group mortality rate) × 100%.

[0088] If the mortality rate in the blank control exceeds 10%, the trial results are considered unreliable and must be repeated. Data were processed using DPS statistical analysis software to obtain the toxicity regression equation and LC. 50 The value is used to evaluate the biological activity of the test reagent.

[0089] Table 2 Results of bioassays on systemic conductivity of each formulation

[0090]

[0091] The above experimental results show that the formulation of the present invention significantly enhances the systemic activity of the active ingredient: LC-L of formulations 1-3 (using a "low-dose organosilicon + methylated vegetable oil" compounded with a functional systemic absorption enhancer system) 50 The values ​​(0.654-0.717 mg / L) were significantly lower than those of all comparative samples, indicating that the formulation of the present invention can greatly enhance the systemic conductivity of abamectin and spinosad in cabbage leaves, thereby achieving the same insecticidal effect at a lower concentration, and the bioactivity is increased by about 2.5-3 times.

[0092] The combination of functional systemic adsorption promoters has a key synergistic effect: Comparative Example 1 (without functional systemic adsorption promoter) has poor activity (LC). 50 =1.619), confirming the indispensability of functional systemic agonists. LC-100 of Comparative Examples 2 and 3 (using either organosilicon or vegetable oil alone, respectively, with the total amount equal to the sum of both in Example 1) 50 (1.077, 1.031) were both significantly higher than those in Example 1 (LC). 50 =0.654). This strongly demonstrates that the effect of a single adjuvant is limited, and increasing the dosage of any single functional systemic adsorption promoter alone cannot achieve the same systemic adsorption effect as the combination of the two at low doses. The combined use of organosilicon (Silwet L-77) and methylated vegetable oil (Pro-MSO) has achieved a synergistic effect of "1+1>2".

[0093] The formulation system of this invention is superior to conventional microemulsion and suspension systems: LC of Comparative Example 4 (using OP-10 and other adjuvants) 50Highest (LC) 50 =1.960), indicating that the traditional formulation has a significant shortcoming in promoting systemic conduction. Comparative Example 5 LC 50 (LC) 50 =1.899) is also much higher than that of the embodiments of the present invention, proving that the adjuvant combination scheme of the present invention has significant advantages in improving systemic activity.

[0094] 2.3 Field efficacy

[0095] Experimental location: Anzhou District, Mianyang City, with moderate to high soil fertility and basically the same cultivation and management conditions in each plot.

[0096] Test target: Palm thrips ( Thrips palmi Karny );

[0097] Experimental crop: Eggplant (Black Eggplant King) Solanummelongena L );

[0098] Test reagents: Formulation Examples 1-3, Comparative Examples 1-5, and water control;

[0099] This experiment was conducted in accordance with the People's Republic of China agricultural industry standards "Good Manufacturing Practice for Field Efficacy Trials of Pesticides" (NY / T2885-2016) and "Guidelines for Field Efficacy Trials of Pesticides (I)" (GB / T17980.13-2000). The treatment plots for the test pesticide, control pesticide, and blank control were randomly arranged, with a plot area of ​​50 m². 2 The experiment used a 3WBD-20 backpack electric sprayer to spray the pesticide evenly. Each treatment was sprayed evenly with 30 kg of water per acre. No other pesticides were used during the experiment. Each treatment was repeated 4 times.

[0100] Survey and statistical methods: Ten eggplant plants were selected from each plot, and three leaves were selected from the upper part of each plant, for a total of 30 leaves. A baseline survey was conducted before the application of pesticides; surveys were conducted three times after the application, on days 3, 7, and 14. The pest reduction rate and control effect were calculated using the following formula.

[0101] Insect population reduction rate (%) = {(number of insects before application - number of insects after application) / number of insects before application} × 100;

[0102] Control efficacy (%) = {(Pest population reduction rate in the treated area - Pest population reduction rate in the blank control area) / (100 - Pest population reduction rate in the blank control area)} × 100

[0103] Safety investigation and effects on other organisms: The effects of each pesticide treatment on cabbage growth and other organisms were observed on the first day after each spraying and several days after the spraying.

[0104] Table 3. Field efficacy test results of various formulations for controlling eggplant thrips.

[0105]

[0106] Field efficacy trials showed that the formulations of this invention (Examples 1-3) exhibited excellent field efficacy. At the same effective ingredient dosage (1.5 g ai / mu), the efficacy of Examples 1-3 remained stable above 94% at 3, 7, and 14 days after application, with excellent persistence (still above 94% after 14 days), far superior to all comparative examples (whose efficacy was generally below 90%). While the efficacy (86%-89%) of Comparative Example 1 (without functional systemic growth promoter), Comparative Example 2 (using only organosilicon), and Comparative Example 3 (using only vegetable oil) was better than the traditional formulations (Comparative Examples 4 and 5), it was significantly lower than that of Examples 1-3. This further confirms that the functional systemic growth promoters of this invention have a synergistic effect.

[0107] Observing the data 14 days after application, the efficacy of Examples 1-3 decreased by less than 2%, while Comparative Example 4 decreased by nearly 10% and Comparative Example 5 decreased by about 4%. This indicates that the adjuvant system of the present invention can not only promote rapid absorption, but also prolong the duration of efficacy and improve the retention and translocation of the agent in the plant.

[0108] In summary, the microemulsion system of this invention significantly enhances the systemic conductivity of abamectin and spinosad through the synergistic effect of the adjuvants. This compound formulation not only improves efficacy but also reduces dosage and cost, making it an ideal agent for controlling agricultural pests.

Claims

1. A microemulsion comprising emamectin benzoate and spinetoram, characterized in that: The composition of the microemulsion is as follows: emamectin 2-5%, spinosad 3-10%, co-solvent 8-20%, emulsifier 10-25%, co-surfactant 5-10%, functional systemic enhancer 1-6%, antifreeze 3-5%, preservative 0.1-0.5%, antifoaming agent 0.1-0.5%, buffer 0.1-0.5%, deionized water to make up the balance; the weight ratio of emamectin to spinosad is 1:10-10:1; the co-solvent is selected from methyl esterified palm oil and N-methyl pyrrolidone; the emulsifier is selected from EL-40 and AEO-9; the co-surfactant is selected from PEG-400; the antifreeze is selected from ethylene glycol, propylene glycol, urea or glycerol; the preservative is selected from sodium benzoate, potassium sorbate, kathon or formaldehyde; the antifoaming agent is selected from silicone antifoaming agent emulsion or mineral oil-based antifoaming agent; the buffer is selected from a citric acid-sodium citrate buffer system; the functional systemic enhancer is Silwet L-77 and methylated vegetable oil Pro-MSO, with a weight ratio of 2:

15.

2. A microemulsion comprising emamectin benzoate and spinetoram according to claim 1, characterized by: The composition of the microemulsion is as follows: emamectin 3%, spinosad 7%, methyl esterified palm oil 7.0%, N-methyl pyrrolidone 3.0%, EL-40 and AEO-9 compounded at a ratio of 1:1 16.7%, PEG-400 8.3%, Silwet L-770.2%, methylated vegetable oil Pro-MSO 1.5%, propylene glycol 4.0%, sodium benzoate 0.2%, citric acid-sodium citrate buffer system 0.4%, silicone antifoaming agent emulsion 0.3%, deionized water to make up to 100%.

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