CN110558326A

CN110558326A - Pesticide composition and application thereof

Info

Publication number: CN110558326A
Application number: CN201910923418.2A
Authority: CN
Inventors: 谭成侠; 王剑; 姚阳意; 陈丽
Original assignee: Zhejiang University of Technology ZJUT
Current assignee: Zhejiang University of Technology ZJUT
Priority date: 2019-09-27
Filing date: 2019-09-27
Publication date: 2019-12-13

Abstract

the invention discloses a pesticide composition and application thereof, wherein the pesticide composition contains two active ingredients, the first active ingredient is a compound A, the second active ingredient is a compound B, the chemical structural formula of the compound A is shown as a formula (A), and the chemical structural formula of the compound B is shown as a formula (B):

Description

Pesticide composition and application thereof

Technical Field

the invention relates to an acaricidal pesticide composition and application thereof.

Background

The agricultural pest mites are small in size, rapid in propagation, strong in adaptability and easy to generate resistance, and are one of pests which are difficult to control. The pest mites are important organisms of fruit trees, vegetables and agricultural and forestry crops, and mainly harm leaves and tender tips, buds and fruits. After the number of insect population is increased sharply, the plant leaves are fallen, and the growth is inhibited or even died. The crops in the damaged area are often shorter, and the quality and the yield are obviously reduced.

The resistance is easy to develop rapidly after a single acaricide variety is used for a long time, so that the development of a novel acaricide composition has important significance for delaying the service life of the acaricide and slowing the development of the resistance of harmful mites to the single acaricide.

Disclosure of Invention

compared with the prior art, the invention aims to provide the pesticide composition and the application thereof, which can improve the control effect, reduce the agricultural cost and delay the generation of the drug resistance of pests.

The pesticide composition is characterized by comprising two active ingredients, wherein the first active ingredient is a compound A, the second active ingredient is a compound B, the chemical structural formula of the compound A is shown as the formula (A), and the chemical structural formula of the compound B is shown as the formula (B):

In the pesticide composition, the weight ratio of the compound B to the compound A is 3-50: 1.

The pesticide composition is characterized in that the weight ratio of the compound B to the compound A in the pesticide composition is 5-20: 1.

The pesticide composition is characterized in that the pesticide composition is prepared into a suspending agent, granules or capsules; in the preparation of the pesticide composition, the total weight content of the compound A and the compound B is more than 10%.

The pesticide composition is applied to preventing and controlling agricultural pest mites.

The pesticide composition is applied to control of agricultural pests.

The pesticide composition is characterized in that the preparation of the pesticide composition comprises the pesticide composition, a carrier and an auxiliary agent; the carrier is a solid carrier or a liquid carrier, and the auxiliary agent is at least one of a surfactant, a defoaming agent, a thickening agent, a suspending agent and an antifreezing agent;

The solid carrier is one of mineral substances, plant substances, synthetic fillers and inorganic salts; wherein the mineral material includes silicate mineral, carbonate mineral or oxide mineral. The silicate mineral is kaolin, sepiolite, nacrite, montmorillonite, mica, vermiculite, pyrophyllite or talc, and the carbonate mineral is calcium carbonate or dolomite. The oxide mineral is quicklime, magnesium lime or diatomite. The plant material is selected from Mandarin orange residue, corn cob core, testa oryzae, soybean straw powder, tobacco powder, and walnut shell or sawmilling powder. The synthetic filler is precipitated calcium carbonate hydrate, precipitated calcium carbonate or white carbon black. The inorganic salt is potassium chloride, sodium chloride, ammonium sulfate, sodium sulfate or calcium sulfate.

The liquid carrier is at least one of water and an organic solvent. When the pesticide composition is prepared into an aqueous emulsion or a suspoemulsion, the organic solvent plays roles of solubilization and freeze prevention. Suitable organic solvents include: aromatic hydrocarbons such as benzene, xylene, toluene, alkylbenzene, alkylnaphthalene or chlorinated aromatic hydrocarbons; chlorinated aliphatic hydrocarbons such as vinyl chloride, chloroform, dichloromethane, chloroform, carbon tetrachloride or polychlorinated ethane; aliphatic hydrocarbons such as petroleum fractions, cyclohexane, light mineral oil or paraffin; alcohols such as methanol, ethanol, isopropanol, butanol, isobutanol, ethylene glycol, propylene glycol, glycerol, or fatty alcohols, etc.; ethers such as methyl glycol ether, ethyl glycol ether or petroleum ether; ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone or N-methyl-pyrrolidone; specialty solvents, such as dimethylformamide, dimethyl sulfoxide, polyethylene glycol or hexanenitrile; vegetable oils and methylated vegetable oils. The organic solvents mentioned above may be used alone, or in admixture with water.

The auxiliary agent of the invention can comprise at least one selected from a surfactant, an antifoaming agent, a thickening agent, a suspending agent and an antifreezing agent according to requirements, and can also comprise other auxiliary agents commonly used in the industry according to requirements.

The surfactant may be an emulsifier, dispersant, stabilizer or wetting agent, and may also be ionic or non-ionic. Suitable surfactants include at least one of the following: polyacrylic acid, sodium salts, calcium salts of lignosulfonic acid, polycondensation products of fatty acids or fatty amines having at least 12 carbon atoms in the molecule with ethylene oxide and/or propylene oxide, alkali metal or alkaline earth metal salts of sulfuric acid or sulfonic acid having at least 10 carbon atoms in the molecule, preferably sodium salts, such as sodium lauryl sulfate, secondary alkyl sulfate, sodium salts of sulfonated castor oil, sodium alkylaryl sulfonate and sodium dodecylbenzenesulfonate; polymers of ethylene oxide, copolymers of ethylene oxide and propylene oxide.

Emulsifiers include nonionic emulsifiers and commercially available emulsifiers. The nonionic emulsifier is preferably a polyoxyethylene fatty acid ester, a polyoxyethylene fatty alcohol ether and a polyoxyethylene fatty amine, such as ethoxylated castor oil, polyoxyethylene (n20) phenethylphenol ether oleate, alkylaryl polyoxyethylene polyoxypropylene ether, alkylaryl formaldehyde resin polyoxyethylene ether, tristyrylphenol polyoxyethylene (n20), ether phosphorylated triethanolamine salt, diphenylethylphenol polyoxyethylene ether (n18) formaldehyde condensate, diphenylphenol polyoxyethylene (n18) polyoxypropylene ether (n20) and the like. Commercially available emulsifiers include: nongru 0201B, Nongru 0203B, Nongru 100#, Nongru 500#, Nongru 600-2#, Nongru 1601, Nongru 2201, Nongru NP-10, Nongru NP-15, Nongru 507#, Nongru OX-635, Nongru OX-622, Nongru OX-653, Nongru OX-667, Nongru CS-7, Ningru 36 #.

the dispersant of the invention comprises at least one of the following substances: sodium lignosulfonate, nekal, calcium lignosulfonate, methylnaphthalenesulfonic acid-formaldehyde condensate, naphthalenesulfonic acid-formaldehyde condensate, sodium methylenenaphthalenesulfonate, sodium methylaminoethyloleate, epoxy polyether, p-t-butyl ether, dibutylnaphthalenesulfonic acid-formaldehyde condensate, phosphates such as sodium hexametaphosphate, alkylphenol polyoxyethylene phosphate, alkylphenol polyoxyethylene ether-formaldehyde condensate sulfate, N-methyl-fatty acyl-sodium taurate alkylphenol polyoxyethylene ether-formaldehyde condensate, aralkylphenol polyoxyethylene ether phosphate alkylphenol polyoxyethylene ether, castor oil ethylene oxide adduct, ethylene oxide-propylene oxide block copolymer alkylphenol polyoxyethylene ether-formaldehyde condensate, alkylphenol polyoxyethylene polyoxypropylene ether, and methyl cellulose.

The humectant of the present invention comprises at least one of the following: sodium lauryl sulfate, sodium alkylol polyoxyethylene ether sulfate, octylphenol polyoxyethylene ether sulfate, alkylphenol polyoxyethylene ether formaldehyde condensate sulfate, sodium alkylsulfonate, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, sulfosuccinic acid alkyl salt, sodium laurinol polyoxyethylene ether sulfonate, sodium alkylamido taurate, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, polyoxyethylene polyoxypropylene block polymer, sorbitan fatty acid ester polyoxyethylene ether, and the like.

The thickening agent of the invention can be artificially synthesized, such as carboxymethyl alcohol, polyvinyl alcohol or polyvinyl acetate; natural water-soluble polymers such as xanthan gum, gelatin, gum arabic, polyvinylpyrrolidone, magnesium aluminum silicate, polyvinyl alcohol, polyethylene glycol, phenol resin, shellac, carboxymethyl cellulose, sodium alginate, and the like are also possible.

The defoaming agent of the present invention is preferably: the foaming agent comprises the components of natural products such as foam, silicones, C8-C10 fatty alcohol, C10-C20 saturated fatty acids, amides and the like.

the pesticide composition of the invention can be prepared into suspending agents, granules or capsules.

When the acaricide is a suspending agent, the acaricide comprises the following components in percentage by weight: the total weight content of the compound A and the compound B is 0.1-60%, the wetting agent is 1-5%, the dispersant is 1-8%, the thickening agent is 0.1-1%, the antifreezing agent is 2-5%, and the balance is water.

when the acaricide is a water dispersible granule, the acaricide comprises the following components in percentage by weight: 0.1-80 percent of the total weight of the compound A and the compound B, 0-2 percent of surfactant, 1-15 percent of wetting agent, 1-15 percent of dispersant, 1-10 percent of disintegrant, 0-5 percent of stabilizer and the balance of synthetic filler.

When the acaricide is a microcapsule suspending agent, the acaricide comprises the following components in percentage by weight: 0.1-40 percent of the total weight of the compound A and the compound B, 1-20 percent of emulsifier, 1-20 percent of solvent, 0-10 percent of thickening agent, 0-10 percent of antifreeze, 0-5 percent of stabilizer, 0-5 percent of defoaming agent, 1-10 percent of microcapsule carrier and the balance of water.

The composition containing the two active ingredients can be directly prepared into a finished product preparation form, namely, all substances in the composition are mixed and directly used for killing insects; the components of the composition may also be provided in separate formulations which are mixed directly in the tank (jar) prior to use. The concentrates of the invention are typically mixed with water to give the desired active concentration.

The invention also comprises the use of a composition according to the invention comprising two active ingredients for controlling agricultural and forestry pests. The composition containing the two active ingredients is suitable for preventing and controlling agricultural pest mites. Is particularly suitable for controlling various important agricultural pests such as tetranychus gossypii, tetranychus vegetable, tetranychus crataegi, panonychus citri, rust citrus mites, tetranychus malabaricus, tetranychus urticae koch, gall mites, aleyrodids and the like. Are also suitable for controlling harmful mites in crops such as: fruit trees such as apple, pear, citrus litchi, etc.; cereals such as wheat, rice, etc.; beans such as soybean, kidney bean, etc.; vegetables such as cabbage, cauliflower, Chinese cabbage, rape, tomato, pepper, etc.; flowers such as Chinese rose, etc.; cotton, tea plant.

The compositions or acaricides containing two active ingredients according to the invention can be applied in the usual way, such as by casting, spraying, misting. The application rate varies with the climatic conditions or the state of the crop, and the application time can be before or after the pest is endangered. The duration of the protective action is generally related to the content of the individual compounds in the composition and also to external factors, such as the climate, but the effects of the climate can be reduced by using suitable dosage forms.

The composition containing two active ingredients can also be mixed with other compounds with insecticidal, herbicidal and bactericidal properties, and can also be mixed with nematocides, protective agents, growth regulators, plant nutrients or soil conditioners.

Compared with the prior art, the composition containing two active ingredients provided by the invention has the following advantages:

(1) The two active ingredients of the composition have strong synergistic effect, the acaricidal effect of the composition prepared by mixing the two active ingredients is obviously improved compared with that of one of the active ingredients, and the composition can kill eggs, young mites, nymph mites and adult mites and has the characteristic of long lasting period;

(2) The dosage of the two active ingredients is reduced, and the medication cost of farmers is reduced;

(3) The two active ingredients are reasonably mixed by utilizing different action modes and different action mechanisms of the two active ingredients on pest mites, so that the service life of the pesticide is prolonged, and the generation of drug resistance of the pest mites is delayed.

Detailed Description

The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.

Preparation of compositions and examples of biological Activity

1. Preparation of water dispersible granules

Mixing and crushing the original medicine, the powdery carrier, the wetting and spreading agent, the binder and the like, adding water, kneading, and adding into a granulator with a screen of a certain specification for granulation. Then drying and screening (according to the range of a screen) to obtain a granular product.

Example 1 Water dispersible granule with effective active ingredient Total weight concentration 40%

The water dispersible granule with the sum of the mass concentration of the two active ingredients being 40 percent comprises the following components in percentage by weight: 30% of a compound A, 10% of a compound B, 8% of N-methyl-oleoyl-sodium taurate, 10% of a naphthol sulfonic acid formaldehyde condensate, 8% of soluble starch, 10% of sodium sulfate and the balance of kaolin. The water dispersible granules prepared in example 1 were designated as 40% a · B water dispersible granules.

Example 2 Water dispersible granule with an effective active ingredient Total weight concentration of 60%

The water dispersible granule with the sum of the mass concentration of the two active ingredients being 60 percent comprises the following components in percentage by weight: 50% of compound A, 10% of compound B, 15% of sodium lignosulfonate, 5% of sodium methyl naphthalenesulfonate formaldehyde condensate (purchased from Nanjing Jiecun technology Co., Ltd.), 5% of epoxy polyether, 10% of bentonite and the balance of kaolin. The water dispersible granules prepared in example 2 were labeled as 60% a · B water dispersible granules.

2. Preparation of suspending agent

According to the formula requirement, water is used as a medium, the original medicine, the dispersing agent, the wetting agent, the suspending agent, the antifreezing agent and the like are uniformly mixed and then added into a sand mill, the mixture is subjected to sand milling until a certain particle size is obtained, and then the thickening agent is added, sheared and uniformly stirred.

Example 3 suspending agent with total concentration of active principle of 40%

The suspending agent with the sum of the mass concentration of the two active ingredients being 40 percent comprises the following components in percentage by weight: 30% of compound A, 10% of compound B, 5% of sodium lignosulfonate, 0.3% of white carbon black, 2.0% of a mixture of alkylnaphthalene sulfonate and an anionic wetting agent (EFW, available from Tokyo Jiruin technologies, Ltd.), 0.2% of potassium dihydrogen phosphate, 4% of ethylene glycol, 0.2% of tributyl phosphate and the balance of water. The suspension prepared in example 3 was labeled as 40% a · B suspension.

Example 4 suspending agent with a total concentration of active principle of 25%

The suspending agent with the sum of the mass concentration of the two active ingredients being 25 percent comprises the following components in percentage by weight: 20% of compound A, 5% of compound B, 2.5% of sodium methyl naphthalene sulfonate formaldehyde condensate, 2.0% of a mixture (EFW) of alkyl naphthalene sulfonate and an anionic wetting agent, OX-6563.0% of agricultural milk, 4% of glycerol, 0.2% of tributyl phosphate and the balance of water. The suspension prepared in example 4 was labeled as 25% a · B suspension.

Second, indoor biological activity determination

Example 5 efficacy test on tetranychus cinnabarinus:

To further understand the virulence of the combination of compounds a and B against pests, a number of formulation screening tests were performed. The test refers to the indoor biological determination test criterion of the pesticide (agricultural industry standard NY/T1154.7-2006) and the formulated pesticide biological activity evaluation SOP (pesticide volume), and adopts a spraying method.

Firstly, preparing a toxic liquid medicine: the liquid medicine in which the compound A is uniformly dispersed in clear water, or the liquid medicine in which the compound B is uniformly dispersed in clear water, or the liquid medicine in which the compound A and the compound B are mixed and dispersed in clear water is marked as the drug-containing liquid medicine.

The toxicity of the prepared toxic liquid medicine is detected, and the detection method comprises the following steps: the broad bean leaves with handles are cut off and inserted into a glass bottle added with water. A certain number of adult mites were inoculated. And after the adult mites lay eggs for 24 hours, removing the adult mites, spraying the leaves with enough eggs by using a toxic liquid medicine, uniformly wetting the surfaces of the leaves by using the toxic liquid medicine, putting the leaves into an ampere bottle again, and naturally drying the leaves. Then placing the mixture in an observation room (25 +/-2 ℃, humidity 70% -80% and illumination/d for 16 h) for culturing for 7 days. The test is repeated for 4 times, clear water blank control is set, and investigation is carried out after the control is completely incubated. The disease was considered to be dead insects when the disease could not be hatched. The toxicity-containing liquid medicine adopts liquid medicine in which the compound A is uniformly dispersed in clear water or liquid medicine in which the compound B is uniformly dispersed in clear water, and the results of half lethal concentration test of the compound A and the compound B are respectively shown in Table 1 when toxicity detection is carried out.

The observed virulence index of compound a was defined as 100, since LC50 of compound B is 1/7.3095 times greater than LC50 of compound a. Then the observed virulence index for compound B, when based on compound a, is 730.95.

when the toxicity-containing liquid medicine is prepared by mixing the compound A and the compound B and dispersing the liquid medicine in clear water for toxicity detection, the actually measured toxicity index, the theoretical toxicity index and the co-toxicity coefficient of the mixture of the two active ingredients are calculated according to the following formulas:

Theoretical mixed virulence index (TTI) ═ virulence index of compound a x percent of compound a in the mixture (%) + virulence index of compound B x percent of compound B in the mixture (%)

If the co-toxicity coefficient is more than 120, the mixing of the two active ingredients has a synergistic effect; if the content is less than 80, the mixture of the two active ingredients has antagonism; if the ratio is more than 80 and less than 120, the combination of the two active ingredients is shown to be additive.

The results of the combined action of compound a, compound B or a combination of compound a and compound B on tetranychus cinnabarinus are shown in table 1.

TABLE 1 toxicity test of toxic liquid medicine containing different active ingredients to Tetranychus cinnabarinus

As can be seen from table 1: the compound A and the compound B have high activity to a test target after being mixed, and show obvious synergistic effect after being mixed.

Third, field plot control experiment

Experimental example 6 field efficacy test on Panonychus citri

The control effect on citrus red mites is measured under field conditions. The test is carried out according to the regulation of pesticide field efficacy test criterion (I) -the pesticide for preventing and controlling citrus red spiders, citrus leaves in each test cell are marked by 5 fixed points according to east, south, west, north and middle 5 directions, 2 plants are investigated in each cell, and the number of all live insects on each plant is investigated.

The formulations prepared in examples 1-4, 11% B suspension and 20% A suspension were labeled as test agents. The drug solution obtained by dispersing the test drug in clear water was designated as a drug-containing drug solution (the dose in Table 2 means the concentration of the test drug in the drug-containing drug solution). The preparation method of the 11% B suspending agent and the 20% A suspending agent comprises the following steps:

20% a suspending agent: the suspending agent with the mass concentration of 20% of the active ingredient compound A comprises the following components in percentage by weight: compound a 20%, sodium lignosulfonate 5%, white carbon black 0.3%, mixture of alkyl naphthalene sulfonate and anionic wetting agent (EFW) 2.0%, monopotassium phosphate 0.2%, ethylene glycol 4%, tributyl phosphate 0.2%, and the balance water.

11% B suspending agent: the suspending agent with the mass concentration of 11% of the active ingredient compound B comprises the following components in percentage by weight: compound B11%, sodium lignosulfonate 5%, white carbon black 0.3%, mixture of alkyl naphthalene sulfonate and anionic wetting agent (EFW) 2.0%, monopotassium phosphate 0.2%, ethylene glycol 4%, tributyl phosphate 0.2%, and the balance of water.

The toxicity of the prepared toxic liquid medicine is detected, and the detection method comprises the following steps: the citrus leaves with the live citrus red spiders are sprayed with the toxic liquid medicine, the surfaces of the citrus leaves are uniformly wetted by the toxic liquid medicine, the sprayed leaves are cultured in the natural environment of the field, the control effect detection is carried out on the 7 th day, the 14 th day and the 21 st day after the pesticide spraying, and the detection results are shown in table 2.

The control effect is (1-residual number of live insects/number of live insects before spraying) × 100%.

In table 2, 11% B suspension and 20% a suspension were used as comparative example 1 and comparative example 2, respectively.

TABLE 2 field efficacy test results on citrus red spiders

As can be seen from table 2, on the 7 th day, the 14 th day and the 21 st day after the application of the toxin-containing liquid medicine, the control effect of the preparations prepared in examples 1 to 4 on citrus red spiders is 95.4 to 99.1 percent, and the control effect on citrus red spiders is better than that of a 11 percent suspending agent B and a20 percent suspending agent A, so that the compound A and the compound B have better synergistic effect when mixed.

Experimental example 7 field drug effect test on apple red spider

The control effect on apple red spider is determined under field conditions. The apple leaves in each test cell are marked by 5 fixed points according to east, south, west, north and middle 5 directions, 2 plants are investigated in each test cell, and all the live insects on each plant are investigated.

The formulations prepared in examples 1-4, 11% B suspension and 20% A suspension were labeled as test agents. The drug solution obtained by dispersing the test drug in clear water was designated as a drug-containing drug solution (the dose in Table 3 means the concentration of the test drug in the drug-containing drug solution). The preparation method of the 11% B suspending agent and the 20% A suspending agent comprises the following steps:

20% a suspending agent: the suspending agent with the mass concentration of 20% of the active ingredient compound A comprises the following components in percentage by weight: 20% of compound A, 5% of sodium lignosulfonate, 0.3% of white carbon black, 2.0% of a mixture (EFW) of alkyl naphthalene sulfonate and an anionic wetting agent, 0.2% of monopotassium phosphate, 4% of ethylene glycol, 0.2% of tributyl phosphate and the balance of water.

the toxicity of the prepared toxic liquid medicine is detected, and the detection method comprises the following steps: the apple leaves with live mites of red spider of apples are sprayed with the poison-containing liquid medicine, the surfaces of the leaves are uniformly wetted by the poison-containing liquid medicine, the sprayed leaves are placed in the natural environment of the field for cultivation, and the control effect detection is carried out on the 7 th day, the 14 th day and the 21 st day after spraying, and the detection results are shown in table 3.

In table 3, 11% B suspension and 20% a suspension were used as comparative example 1 and comparative example 2, respectively.

TABLE 3 field efficacy test results on European red spider

As can be seen from Table 3, the 7 th day, the 14 th day and the 21 st day after the application of the drug-containing liquid medicine have 94.2 to 99.4 percent of the effect of controlling the red mites on the apples respectively, and the effect of controlling the red mites on the apples is better than that of a 11 percent suspending agent B and a20 percent suspending agent A.

The data show that the acaricidal composition provided by the invention not only has obvious synergistic effect on controlling citrus red mites and has better effect than that of singly using the compound A or B, but also can reduce the dosage and delay the drug resistance problem caused by a single agent.

the statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.

Claims

1. A pesticide composition is characterized by comprising two active ingredients, wherein the first active ingredient is a compound A, the second active ingredient is a compound B, the chemical structural formula of the compound A is shown as a formula (A), and the chemical structural formula of the compound B is shown as a formula (B):

；

in the pesticide composition, the weight ratio of the compound B to the compound A is 3 ~ 50:1 ~ 9.

2. the pesticide composition as claimed in claim 1, wherein the weight ratio of the compound B to the compound A in the pesticide composition is 5 ~ 20:1 ~ 5.

3. The pesticide composition as set forth in claim 1, wherein the pesticide composition is formulated as a suspension, a granule or a capsule; in the preparation of the pesticide composition, the total weight content of the compound A and the compound B is more than 10%.

4. Use of the pesticidal composition of claim 1 for controlling agricultural mites.

5. Use of the pesticidal composition of claim 1 for controlling agricultural pests.