CN101406192A - Compositional acaricide and uses thereof - Google Patents

Abstract

The invention relates to an acaricide composition and application thereof. The active ingredients in the composition are spirodiclofen and fenpyroximate or the spirodiclofen and tebufenpyrad; the mass percentage of the active ingredients is between 10 to 1 and 1 to 10 and between 5 to 1 and 1 to 50; and the active ingredients are processed into any of dosage forms in pesticide application, and the preferable dosage forms are wettable powder, water emulsion, emulsifiable solution, micro-emulsion, a water dispersible granule or tablet, and a suspending agent. The acaricide composition has significant synergism on pest mites for controlling pest mites on plants, and is helpful to reduce the pesticide dosage, reduce the cost, and delay the drug resistance of the pest mites.

Description

A kind of compound acaricide and its application

technical field

The invention relates to a pesticide composition and its application, in particular to an acaricidal composition with spirodiclofen, fenpyroxifen or tebufenpyrad as active ingredients, which is used to prevent and control harmful mites in agriculture.

Background technique

There are many kinds of harmful mites in my country's agriculture, with mixed feeding habits, wide host range, short life cycle, and strong fecundity. They can occur all year round under greenhouse conditions, and the generations overlap seriously. Pest mites are highly concealed. Once the number of pest mites increases explosively, it will cause great harm to crops. The harm of pest mites leads to stagnation of plant growth, premature senescence of plants, deformed fruits, and seriously reduces yield and quality.

At present, in the control of agricultural pest mites, due to the many generations of pest mites and rapid reproduction, resistance to acaricides is easy to occur. After many years of long-term use, the acaricidal effect has dropped significantly or the effective control time of one application is very short, and organophosphorus and pyrethroid pesticides are almost ineffective against harmful mites. Blindly increasing the frequency of use of pesticides and increasing the concentration of pesticides used will not achieve the desired control effect, and will also increase the poisonous pollution to people and the environment. With the improvement of the production level of agricultural products in our country and the technical barriers to the export of agricultural products in importing countries, it is even more necessary to select high-quality and efficient pesticides and use them scientifically and rationally in the prevention and control of pest mites, so as to reduce pesticide residues and improve the quality of agricultural products.

Spirodiclofen is a low-toxic tetronic acid acaricide, and its common name in English is spirodiclofen. Spirodifen has a wide spectrum of killing mites, excellent ovicidal effect, and good contact killing effect on young nymphs. The mechanism of action of spirodiclofen is to inhibit fat synthesis in mites, and there is no cross-resistance with existing acaricides. It is safe for humans, animals and crops when used at the recommended dose, and is suitable for use in pollution-free crop production. Spirodiclofen has a good effect on mite eggs, but its effect on adult mites is poor and its action is slow, and it cannot quickly control the damage of harmful mites when they occur in large numbers.

Fenpyroximate is a fenoxypyrazole acaricide, and its common name in English is fenpyroximate. High doses can directly kill mites, and low doses can inhibit mites shedding or laying eggs. Fenpyroxime is suitable for controlling pest mites on various plants, but after several years of use, the pest mites have developed severe resistance. At present, the control effect on harmful mites is unstable, and the duration of effect is not ideal.

Tebufenpyrad is an acaricide with pyrazole carboxamide structure, and its common name in English is tebufenpyrad. Tebuzafen has quick-acting and high-efficiency effects on all growth stages of mites, and has a long-lasting effect. It is used at the recommended dose (25-200mg(a.i.)/L), and has no phytotoxicity to most crops. However, in some orchards with severe resistance, the control effect is often unsatisfactory.

Contents of the invention

The object of the present invention is to provide an acaricidal composition, which has good quick-acting property and long-lasting effect, and has a good control effect on the pest mites that have developed drug resistance, and is helpful for overcoming and delaying the drug resistance of the pest mites.

Another object of the present invention is to provide the application of the acaricidal composition.

The purpose of the present invention is achieved through the following technical solutions:

When pesticides of different varieties are mixed, they usually show three types of effects: additive effect, synergistic effect and antagonistic effect. However, the specific role cannot be determined without a large number of experiments. The inventor unexpectedly found that the mixed use of spirodiclofen and pyrazafen or tebufenpyrad has obvious synergistic effect on pests through indoor biological activity measurement tests. After further research, the present invention has been completed.

The composition of the present invention uses spirodiclofen and fenpyrafen or tebufenpyrad as the main active ingredients, the ratio of the mass and number of spirofen to fenpyrafen is 10:1-1:10, and the ratio of spirofen to fenpyrafen is 10:1-1:10. The ratio of parts by mass is 5:1-1:50.

The acaricidal composition provided by the present invention can be made into any dosage form acceptable in pesticide application according to various factors such as the crops to be controlled, the environmental conditions, the control method, and the cost of control. Wet powder, water dispersible granule or tablet, water emulsion, emulsifiable concentrate, microemulsion, suspension, the total content of active ingredients in the preparation is 5-80%.

Adjuvant in the composition of the present invention includes solvent, dispersant, wetting agent, emulsifier, stabilizer, thickener, pH adjuster, antifreeze, excipient, filler and other beneficial active ingredients in the preparation and stability The known substances exhibiting medicinal effects are all commonly used and permitted ingredients in pesticide preparations, and are not particularly limited.

The processing techniques of various formulations of the composition of the present invention are prepared by known methods, which are commonly used methods in the processing techniques of pesticide formulations.

The composition of the present invention can be provided in the form of a finished preparation, that is, each substance in the composition has been mixed, and the components of the composition can also be provided in a single dose form, directly mixed in a barrel or tank before use, and then diluted to a desired concentration.

The acaricidal composition provided by the present invention is usually used by spraying, and other agricultural application techniques can also be used as required. For example, the commonly used spray method, poison bait method, seed treatment method, soil treatment method, smear method, fumigation method, fumigation method, smoke method, seed coating technology, trunk injection method, etc.

The acaricidal composition provided by the invention can be widely applied to various plants according to different control requirements, control objects, application dosage forms and other factors.

When applying the acaricidal composition provided by the present invention, it should be noted that the control time is recommended to be applied before the peak occurrence of harmful mites, so that the damage of pests can be more effectively controlled, and it is beneficial to take advantage of the long-lasting effect of the composition. When in use, it is necessary to evenly spray the front and back sides of the plant leaves and the surface of the fruit to maximize the efficacy of the medicine and provide more comprehensive protection. It is recommended that the composition be used no more than twice in one growing season, so as to extend the service life of the composition as much as possible.

In conjunction with tests and examples, it can be seen that the composition of the present invention has obvious synergistic effect, and has produced the following beneficial effects:

1. The composition of the present invention shows an excellent synergistic effect within a certain proportion range, and the acaricidal effect of the composition has been significantly improved compared with a single agent, which reduces the dosage of pesticides, the labor and cost of applying pesticides, and also reduces The adverse effects on the environment and pesticide residues are reduced.

2. The active ingredients in the composition of the present invention have different action mechanisms, and the application of the composition can delay or overcome the drug resistance of pest mites and prolong the service life of a single agent.

Detailed ways:

The applicant of the present invention first conducted an indoor biological activity measurement test and unexpectedly found that the mixed use of spirodiclofen and pyrazafen or tebufenpyrad has a significant synergistic effect on harmful mites, especially those that have developed drug resistance. Then use Sun Yunpei's method for quantitative analysis of synergistic effect to determine the optimal ratio. The specific discovery, improvement process and practical application of the composition of the present invention are illustrated in specific embodiments.

In order to make the object, technical solution and advantages of the present invention clearer, the content of the present invention will be further described in detail below in conjunction with the examples. It should be understood that the specific embodiments described here are only used to explain the present invention, not to limit the present invention. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present invention shall be included within the protection scope of the present invention. Therefore, the protection scope of the patent for the present invention shall be based on the appended claims .

The percentages in the proportioning ratio of all preparations are percentages by weight. The treatment doses in the bioassay part and drug efficacy test are all effective content.

Example 1, the processing and application of spirodiclofen-fenpyroximate suspending agent

The processing of Spirofen Fenzafen Suspending Concentrate adopts the superfine pulverization method and coagulation method in the conventional suspending agent processing technology, and the active ingredient, dispersant, wetting agent and water are mixed evenly according to the proportion of the formula, Obtained by grinding and or high-speed shearing.

The following are several formulas with different contents of suspending agent, which can be further optimized in actual use to obtain the optimal formula that meets the production process and application requirements.

Table 1. Processing formula of spirodiclofen-fenpyroxifen suspension concentrate

According to the formula requirements, add the pre-crushed original drug and carrier, surfactant, thickener, stabilizer, antifreeze, water, etc. into the sand mill, grind it finely, then mix it by high-speed shearing, and finally adjust the pH with acetic acid to 4 to prepare a suspending agent.

The test of spirodiclofen and pyraclofen suspending agent on the prevention and treatment of citrus Panonychus, the contrast agent is 240g/L spirodiclofen suspending concentrate (produced by Bayer Crop Science Company of Germany) and 5% pyraclofen suspending concentrate (Jixi Nonghua Biotechnology Co., Ltd. Co., Ltd.), the test uses spray treatment.

The test results are shown in Table 2. The control effect of each formulation of spirodiclofen-fenpyrofen suspension concentrate for 1 day is better than that of a single agent of spirodiclofen; the control effect of 7 days and 30 days is slightly better than or equivalent to Compared with single agent of spirodiclofen, it is significantly better than single agent of pyraclofen. It shows that the combination of spirodiclofen and pyraclofen has obvious synergistic effect.

Table 2. Field efficacy results of spirodiclofen-fenpyroxen SC in the control of citrus pest mites

Drugs to be tested Application concentration (mg/kg) 1 day control effect (%) 7-day control effect (%) 30-day control effect (%)

Control 1: 240g/L Spirodiclofen Suspending Concentrate 50 50.4 90.6 85.3  Contrast 2: 5% Fenzaclofen suspension concentrate 25 75.3 82.2 61.0 Formula LZ-1 50 87.3 93.2 86.1 Formula LZ-2 50 88.7 96.7 82.6 Formula LZ-3 50 87.1 94.6 84.5 Formula LZ-4 25 71.9 86.8 80.4

Example 2, 24% Spirodiclofen Fenzafen EC

Spirodifen 20%

Fenflux 4%

N-Methylpyrrolidone 4%

Farm milk 600# 8%

Farm milk 500# 5%

Isopropanol 3%

Xylene Supplement to 100%

The above-mentioned ingredients are sequentially added into the mixing kettle according to the proportion of the formula, and stirred evenly to obtain 24% spirodiclofen-fenpyroxifen emulsifiable concentrate.

The test of this formula preventing and controlling tobacco spider mite (Tetranychus urticae), the control agent is 240g/L spirodiclofen suspension concentrate (produced by Bayer Crop Science Company of Germany) and 5% pyraclofen EC (produced by Beijing Huarong Biohormone Factory). Treated with spray.

The formula is 6000 times liquid, and the control effect is 87.5%, 95.1% and 90.3% respectively in 1 day, 7 days and 30 days after the application, while the control agent 240 g/liter spirodiclofen suspension is treated with 6000 times liquid, and the corresponding control effect The effects were 50.1%, 86.6% and 80.2% respectively; the corresponding control effects were 84.6%, 81.9% and 73.2%.

It can be seen that the control effect of 24% spirodiclofen·fenpyroxifen EC is significantly better than that of the control agent, its quick-acting property is better than that of spirofenclofen single agent, and its lasting effect is better than that of fenpyrofen single agent, which shows that spirodiclofen and The pyraclofen composition has obvious synergistic effect.

Embodiment 3, 24% spirodiclofen-fenpyroxifen microemulsion

Spirodifen 12%

Fenflux 12%

Ammonium dodecylbenzenesulfonate 4%

N-Methylpyrrolidone 3%

Isopropanol 8%

Xylene 4%

Water up to 100%

Add the original drug, solvent, and emulsifier together to dissolve into a uniform oil phase, slowly add to water under stirring, then rapidly invert the phase after stirring and heating, and cool to room temperature to prepare a microemulsion.

The test of this formula for controlling cotton spider mite, the control agent is 240g/L spirodiclofen suspending concentrate (produced by Bayer Crop Science Co., Ltd., Germany) and 5% pyraclofen emulsifiable concentrate (produced by Beijing Huarong Biological Hormone Factory), and the test adopts spray treatment.

The formula is 4000 times liquid, and the control effect is 95.1%, 90.3% and 87.5% respectively in 1 day, 7 days and 30 days after the application, while the control agent 240 g/liter spirodiclofen suspension is treated with 6000 times liquid, and the corresponding control effect The effects were 52.4%, 87.6% and 80.5%, respectively; the corresponding control effects were 85.6%, 81.0% and 74.2% when treated with 2000 times solution of 5% Fenpyroximate EC.

It can be seen that the control effect of the 24% spirodiclofen-fenpyroxen microemulsion is significantly better than that of the single-dose variety, indicating that the combination of spirodiclofen and fenpyroxen has obvious synergistic effect.

Example 4, Processing and Application of Spirofen-Fenzafen Emulsion in Water

The processing of spirodiclofen-fenpyroxifen aqueous emulsion adopts conventional aqueous emulsion processing technology, adding active ingredients, emulsifiers and thickeners, etc., into the mixer in sequence according to the proportion of the formula, and stirring evenly.

The following are two formulas of water-in-water emulsions with different contents, which can be further optimized in practice to obtain the optimal formula that meets the production process and application requirements.

Table 3. Processing formula of spirodiclofen-fenpyroxate emulsion in water

Add the original drug, solvent, and emulsifier together to dissolve into a uniform oil phase; mix the water-soluble components with water to make a water phase; mix the oil phase with the water phase under high-speed stirring to make a water emulsion.

Formula LZ-6 was used to prevent and control tea yellow mites on cucumbers in the greenhouse. The control agents were 240g/L spirodiclofen suspension concentrate (produced by Bayer Crop Science Co., Ltd., Germany) and 5% pyraclofen emulsifiable concentrate (produced by Beijing Huarong Biological Hormone Factory). Treated with spray.

The test results are shown in Table 4. It can be seen that the control effects of the various formulations of spirofen-fenclofen-fenzafen water emulsion are better than those of the single-dose varieties, indicating that the combination of spirofen-fen-fen-fen-fen and fenpyroxen has obvious synergistic effect. .

Table 4. Field efficacy results of spirodiclofen-fenpyroxate emulsion in control of eggplant pest mites

Test drug Application rate (ga.i./ha) 1 day control effect (%) 7-day control effect (%) 30-day control effect (%) Control 1: 240g/L Spirodiclofen Suspending Concentrate 36 47.2 85.1 87.9 Control 2: 5% fenpyroximate EC 18.5 85.9 79.3 58.7 Formula LZ-5 22.5 88.7 92.8 80.6 Formula LZ-6 30 84.3 94.1 80.4

Example 5, 30% spirodiclofen · tebufenpyrad wettable powder

Spirodifen 25%

Tebufenpyr 5%

Sodium Lauryl Sulfate 1.5%

Sodium Lignosulfonate 4%

Sodium formaldehyde condensate sulfonate 4%

Kaolin Clay Supplement to 100%

After the above ingredients are coarsely pulverized, they are uniformly mixed according to the ratio of the formula, and then jet pulverized to obtain 30% spirodiclofen·tebufenpyrad wettable powder.

In the test of controlling apple spider mite with this formula, the control agents were 240g/L spirodiclofen suspension concentrate (produced by Bayer Crop Science Co., Ltd., Germany) and 20% tebufenfen EC (self-made), and the test was treated by spraying.

The formula is 6000 times liquid, and the control effect is 85.1%, 90.3% and 87.5% respectively in 1 day, 7 days and 30 days after the application, while the control agent 240 g/liter spirodiclofen suspension concentrate is treated with 6000 times liquid, and the corresponding control effect The effects were 52.7%, 87.6% and 80.5% respectively; 20% tebufenfen EC was treated with 2000 times solution, and the corresponding control effects were 85.6%, 81.0% and 64.2% respectively.

It can be seen that the control effect of 30% spirodiclofen·tebufenfen wettable powder is obviously better than that of the control agent, its quick-acting property is better than that of spirofen-difen alone, and its duration of effect is better than that of tebufenfen single agent, which shows that spirodiclofen The combination of ester and tebufenfen has obvious synergistic effect.

Example 6, Processing and Application of 20% Spirodiclofen Tebufenpyrad EC

Spirodifen 5%

Tebufenpyr 15%

N-Methylpyrrolidone 8%

Farm milk 500# 4%

Farm milk 600# 8%

Cyclohexanone Supplement to 100%

The above-mentioned ingredients are sequentially added into the mixing tank according to the proportion of the formula, and stirred evenly to obtain 20% spirodiclofen-tetrafenpyrad emulsifiable concentrate.

The formula controls spider mites on green beans. The control agents are 240g/L spirodiclofen suspension concentrate (produced by Bayer Crop Science Co., Ltd., Germany) and 20% tebufenchlor EC (self-made). The test uses spray treatment.

The formula is 2000 times liquid, and the control effect is 95.1%, 90.3% and 87.5% respectively in 1 day, 7 days and 30 days after the application, while the control agent 240 g/liter spirodiclofen suspension is treated with 6000 times liquid, and the corresponding control effect The effects were 47.3%, 87.6% and 80.5%, respectively; 20% tebufenfen EC was treated with 2000 times solution, and the corresponding control effects were 81.0%, 85.6% and 74.2%, respectively.

It can be seen that the control effect of 20% spirodiclofen·tebufenfen EC is obviously better than that of the single-dose variety, indicating that the combination of spirodiclofen and tebufenfen has obvious synergistic effect.

Example 7, Processing and application of spirodiclofen-tebufenpyrad microemulsion

The processing of spirodiclofen-pyramid microemulsion adopts conventional microemulsion processing technology. The following are the formulas of 4 microemulsions with different contents, which can be further optimized in actual application to obtain the optimal formula that meets the production process and application requirements .

Table 5. Processing formula of spirodiclofen-tebufenfen microemulsion

Add the original drug, solvent, and emulsifier together to dissolve into a uniform oil phase, slowly add to water under stirring, then rapidly invert the phase after stirring and heating, and cool to room temperature to prepare a microemulsion.

Formula LB-4 was used to control cotton spider mites. The control agents were 240g/L spirodiclofen suspension concentrate (produced by Bayer Crop Science Co., Ltd., Germany), and 20% tebufenchlor EC (self-made). The test was treated by spraying.

Formula LB-42000 times of liquid, the control effect of 1 day, 7 days and 30 days after the drug is respectively 95.1%, 90.3% and 87.5%, while the control agent 240 g/liter spirodiclofen suspension concentrate 6000 times of liquid treatment, the corresponding The control effects were 43.4%, 87.6% and 80.5% respectively; the corresponding control effects were 85.6%, 81.0% and 74.2%.

It can be seen that the control effect of the formula LB-4 is significantly better than that of the single-dose variety, indicating that the combination of spirodiclofen and tebufenfen has obvious synergistic effect.

Example 8. Processing and application of 20% spirodiclofen-tebufenpyrad suspension concentrate

Spirodifen 10%

Tebufenpyr 10%

Styrene phenol formaldehyde resin polyoxyethylene ether phosphate 2%

Methylene bis-naphthalene sulfonate 2%

Nonylphenol ethoxylates 2%

Propylene Glycol 4%

Xanthan Gum 0.2%

Silicone defoamer 0.4%

Water up to 100%

According to the formula requirements, add the pre-crushed original drug and carrier, surfactant, thickener, stabilizer, antifreeze, water, etc. into the sand mill, grind it finely, then mix it by high-speed shearing, and finally adjust the pH with acetic acid to 4 to prepare a suspending agent.

The test of this formula to prevent and control peanut spider mites, the control agent is 240g/L spirodiclofen suspending concentrate (produced by Bayer Crop Science Co., Ltd., Germany) and 20% tebufenchlor EC (self-made), and the test is treated by spraying.

The formula is 2000 times liquid, and the control effect is 95.1%, 90.3% and 87.5% respectively in 1 day, 7 days and 30 days after the application, while the control agent 240 g/liter spirodiclofen suspension is treated with 6000 times liquid, and the corresponding control effect The effects were 48.4%, 87.6% and 80.5%, respectively; 20% tebufenfen EC was treated with 2000 times liquid, and the corresponding control effects were 85.6%, 81.0% and 74.2%.

It can be seen that the control effect of the 20% spirodiclofen·pyrazafen suspension concentrate is significantly better than that of the single-dose variety, indicating that the combination of spirodiclofen and tebufenfen has obvious synergistic effect.

Biological Assay Example 1, Combined Effect of Mixed Use of Pesticides on Harmful Mites

In view of the fact that it is difficult for a single agent to meet the needs for the control of acarids, which are seriously harmful in agriculture, the inventors conducted a large number of composition screening tests in order to find an ideal agent for preventing and controlling harmful mites. The test adopts the leaf disc spray method in the "Agricultural Industry Standards of the People's Republic of China--Guidelines for Indoor Bioassays of Pesticides", and the biological test material is the female adult mite of Tetranychus cinnabarinnum.

Use the synergistic toxicity index proposed by Mansour et al. ("Phytochemical Protection Research Methods" edited by Mu Liyi, China Agricultural Press, pp. 116-120) to determine the nature of the toxicity of the mixed pesticides. When the synergistic toxicity index ≥ 20%, it is a synergistic effect; when the synergistic toxicity index ≤ -20%, it is an antagonistic effect; if it is between two values, it is an additive effect.

The test set up the compound screening of spirodiclofen and propargaben, dicofol, amitraz, pyrazafen, and tebufenpyrad. It was surprisingly found in the test that the mixed use of spirodiclofen and pyrazafen or tebufenpyrad After that, it showed obvious synergistic effect on harmful mites, and the synergistic effects were all greater than 20%.

Biological Assay Example 2, Determination of Co-toxicity Coefficient of Spirofen-Fenzafen, Spirofen-Tenzafen Composition

In order to further understand the toxicity of the combination of spirodiclofen-fenpyrofen and spirofen-pyrafen to harmful mites, and to find out the best mixing ratio, several groups of mixing combinations were designed in the experiment, and the test objects were resistant citrus Female adults of Panonychus mites.

The test refers to the method in biological assay example 1, and then calculates the co-toxicity coefficient (CTC value) of the composition according to Sun Yunpei's method. When CTC≤80, the composition exhibits antagonistic effect; when 80<CTC<120, the composition exhibits additive effect; when CTC≥120, the composition exhibits synergistic effect.

The test results are shown in Table 6. The spirodiclofen-pyrafenazole composition is in the ratio range of 10:1-1:10, and the spirodiclofen-pyrazafen composition is in the ratio range of 5:1-1: 50, can show obvious synergistic effect.

Table 6. Determination results of the co-toxicity coefficient of spirodiclofen·pyrafenazole and spirodiclofen·tebufenpyrad compositions

Drugs to be tested Proportion The actual toxicity index of the mixture The theoretical toxicity index of the mixture CTC value Spirodiclofen Fenzafen 10:1 114.3 93.8 121.9 Spirodiclofen Fenzafen 3:1 157.6 97.8 161.1 Spirodiclofen Fenzafen 1:3 143.9 104.9 137.2 Spirodiclofen Fenzafen 1:10 197.3 109.1 180.8 Spirodifen Tebufenpyrad 5:1 125.7 90.5 138.9 Spirodifen Tebufenpyrad 1:1 189.6 98.3 192.9 Spirodifen Tebufenpyrad 1:5 165.9 104.1 159.4 Spirodifen Tebufenpyrad 1:10 195.2 108.7 179.6 Spirodifen Tebufenpyrad 1:50 172.1 115.2 149.4

Claims (4)

1, a kind of miticide composition is characterized in that active ingredient is made up of spiral shell mite ester and azoles mite ester or tebufenpyrad, and the ratio of quality and the number of copies of spiral shell mite ester and azoles mite ester is 10: 1-1: 10, and the ratio of quality and the number of copies of spiral shell mite ester and tebufenpyrad is 5: 1-1: 50.

2, according to claim 1, it is characterized in that spiral shell mite ester and azoles mite ester or tebufenpyrad are composite, be processed into agricultural and go up applicable any one formulation.

3, according to claim 2, preferred formulation is wetting powder, aqueous emulsion, missible oil, microemulsion, water dispersible granules or tablet, suspension emulsion.

4, the miticide composition of claim 1 is used to prevent and treat the harmful mite on the plant.