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CN110476960B - Clothianidin film slow-release seed treatment suspension and its preparation method and application - Google Patents

Clothianidin film slow-release seed treatment suspension and its preparation method and application Download PDF

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Publication number
CN110476960B
CN110476960B CN201910887462.2A CN201910887462A CN110476960B CN 110476960 B CN110476960 B CN 110476960B CN 201910887462 A CN201910887462 A CN 201910887462A CN 110476960 B CN110476960 B CN 110476960B
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clothianidin
agent
dispersant
suspending agent
seed treatment
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CN110476960A (en
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党志红
安静杰
李耀发
高占林
潘文亮
柴方堃
涂学为
陈新峰
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Institute of Plant Protection Hebei Academy of Agricultural and Forestry Sciences
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Institute of Plant Protection Hebei Academy of Agricultural and Forestry Sciences
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring

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  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Agronomy & Crop Science (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention relates to a clothianidin film slow-release type seed treatment suspending agent, and a preparation method and application thereof. The seed treatment suspending agent comprises clothianidin; wetting dispersant, specifically one or more of alkylphenol polyoxyethylene ether, polyoxyethylene phosphate, polyacrylic acid, alkylphenol, rosin dispersant, polycarboxylate dispersant, macromolecular amphiphilic dispersant, EO/PO polyether and alkyl alcohol alkoxylate; the film forming agent is one or more of polyethylene glycol 8000, polyvidone K30, polyvinyl alcohol 1788, and pullulan. The seed treatment suspending agent can improve the pesticide effect, reduce the cost, prolong the lasting period and achieve the aim of controlling pests in the whole growth period. The suspending agent is safe to wheat seed emergence, can reduce the dosage, prolong the duration, reduce the cost and has wide application prospect.

Description

Clothianidin film slow-release type seed treatment suspending agent as well as preparation method and application thereof
Technical Field
The invention belongs to the technical field of seed treatment suspending agents, and particularly relates to a thin film slow-release type seed treatment suspending agent containing clothianidin as an active ingredient. The invention also provides a preparation method and application of the slow-release seed treatment suspending agent.
Background
Wheat is a main grain crop in China, wheat aphids are common important pests of wheat, and the wheat aphids mainly stab and suck on the ear parts and the middle and upper leaves of the wheat to cause damage, absorb juice, spread diseases and often cause yield reduction of the wheat. The main species of the wheat aphids in the winter wheat producing area in China are three species of the sitobion avenae Macrosiphum microscatanthi Takahashi, the corn-derived aphid Rhopalosiphum padi Linnaeus and the Schizap hisgraminum Rondani. In recent years, along with improvement of water and fertilizer conditions of wheat fields and increase of planting density of wheat, wheat aphids tend to grow more and more year by year, and the thousand-grain weight of the wheat is generally reduced by 3-5 g, and the number of the wheat is more than 15 g.
The pest control is carried out by adopting a seed dressing pesticide applying mode, so that the labor input can be effectively reduced, the cost is saved, the environmental pollution is reduced, and natural enemies are protected. Therefore, the technique is usually used for preventing and controlling the insect pests in the seedling stage in production practice, but the conventional seed dressing agent has not ideal effect on preventing and controlling the insect pests in the later growth stage of crops.
At present, the most commonly used agent for preventing and controlling wheat aphids in production is neonicotinoid insecticide imidacloprid, and the agent is applied in a large amount due to the unique action mechanism and the super systemic activity. The problem of resistance is also gradually apparent due to improper administration. Clothianidin is a2 nd generation nicotine pesticide with a thiazole ring which is created and developed by pesticides for the Wuhan Huatian in Japan, is high-efficiency to pests of hemiptera, diptera, orthoptera, lepidoptera and the like of various crops such as rice, fruit trees, vegetables and the like, and can effectively kill the pests with high resistance to traditional pesticides such as organophosphorus pesticides, carbamate pesticides and pyrethroid pesticides. Is expected to become a substitute medicament of imidacloprid.
However, the pesticide using clothianidin as an active ingredient generally has a short duration in field pest control, and the digestion half-life of the spray preparation in plants is reported to be 3.5-17.3 days, the digestion half-life of the suspension seed coating in soil is 20.15 days after the suspension seed coating is treated, and the control effect on aphids can reach 43 days. But compared with the whole wheat growth period, the method cannot achieve the ideal long-acting slow-release pest control purpose.
Disclosure of Invention
Based on the defects, the clothianidin film slow-release type seed treatment suspending agent provided by the invention not only can improve the drug effect and reduce the cost, but also can prolong the lasting period and achieve the purpose of controlling pests in the whole growth period. The seed treatment suspending agent is convenient to use, can enhance the prevention and treatment effect, can treat underground pests at the same time, and reduces the investment of labor force.
The inventor of the invention unexpectedly finds that the seed treatment suspending agent prepared by selecting a certain specific wetting agent dispersing agent and a film-forming agent can achieve the purpose of long-acting and slow-release of clothianidin, and can also obviously improve the control effect of the clothianidin on wheat aphids.
Specifically, the present invention adopts the following technical solutions.
A clothianidin film slow-release type seed treatment suspending agent comprises:
the active ingredient clothianidin;
wetting dispersant, specifically one or more of alkylphenol polyoxyethylene ether, polyoxyethylene phosphate, polyacrylic acid, alkylphenol, rosin dispersant, polycarboxylate dispersant, macromolecular amphiphilic dispersant, EO/PO polyether and alkyl alcohol alkoxylate; and
the film forming agent is one or more of polyethylene glycol 8000, polyvidone K30, polyvinyl alcohol 1788, and pullulan.
The wetting dispersant selected by the invention can better promote wetting dispersion among active component particles and prevent the active component particles from mutually agglomerating; and under the interaction with the film-forming agent, limited pesticide components can be guaranteed to act on seeds and roots in a concentrated manner, the seeds and the roots are not easy to fall off and fly away, and the diffusion of pesticides in the environment and the contact of the pesticides with non-targets are reduced. The wetting dispersant and the film forming agent can ensure that the prepared coating is good in air permeability and water permeability and normal in seed germination and growth, and can also ensure that the prepared coating is insoluble in water, active ingredients in the coating can be slowly released, and the lasting time is long.
Preferably, the wetting dispersant is one or more selected from rosin dispersants, polycarboxylate dispersants and macromolecular amphiphilic dispersants, and more preferably the composition of the three. The research shows that the wetting dispersant can better improve the long-acting property and the slow-release property of the suspending agent for seed treatment. Particularly, after the three wetting dispersants are mixed in proportion, the lubrication among particles can be enhanced, the system viscosity is reduced, and the solubility of the original medicine in the surfactant is reduced; the function performance of the auxiliary agent can be improved, the dosage of a single wetting agent is reduced, and the austenite curing caused by the dissolution of the original medicine in the low-molecular wetting agent is reduced.
In some embodiments of the invention, the wetting dispersant is a combination of a rosin dispersant, a polycarboxylate dispersant and a macromolecular amphiphilic dispersant in a mass ratio of (3-5) to (1-1.5).
In some embodiments of the invention, the wetting dispersant is a combination of a rosin dispersant, a polycarboxylate dispersant and a macromolecular amphiphilic dispersant in a mass ratio of 3:1: 1.
In some embodiments of the present invention, the wetting dispersant is a combination of rosin dispersant, polycarboxylate dispersant and macromolecular amphiphilic dispersant in a mass ratio of 5:1.5: 1.5.
In some embodiments of the invention, the wetting dispersant is a combination of a rosin dispersant, a polycarboxylate dispersant and a macromolecular amphiphilic dispersant in a mass ratio of 4:1.5: 1.5.
In the wetting dispersant, alkylphenol polyoxyethylene ether can be selected from Igepal BC/10, polystyrol polyoxyethylene ether phosphate can be selected from Soprophor SC, polyacrylic acid can be selected from TERSPERSE2500, alkylphenol can be selected from TERSPERSE4894, rosin dispersant can be selected from SC29, polycarboxylate dispersant can be selected from SP-27001, macromolecular amphiphilic dispersant can be selected from Y6325, EO/PO polyether can be selected from D800, and alkyl alcohol alkoxylate can be selected from W600; all of which are commercially available.
In some embodiments of the present invention, the content of the wetting and dispersing agent in the clothianidin film slow release type seed treatment suspending agent is preferably 1wt% to 8 wt%.
In some embodiments of the present invention, the content of the wetting and dispersing agent in the clothianidin film slow release type seed treatment suspending agent is 4 wt% to 5 wt%.
In some embodiments of the present invention, the content of the wetting and dispersing agent in the clothianidin film slow release type seed treatment suspending agent is 1wt%, 4 wt%, 4.5 wt%, 5wt%, 6 wt%, 7 wt%, 8 wt%.
In some preferred embodiments of the present invention, the wetting and dispersing agent is a combination of rosin dispersant (SC29), polycarboxylate dispersant (SP-27001) and macromolecule amphiphilic dispersant (Y6325), and the content of each wetting and dispersing agent in the clothianidin film slow release type seed treatment suspending agent is 3wt%, 1wt% and 1wt%, respectively.
In some embodiments of the invention, the film-forming agent is preferably one or both of polyethylene glycol 8000 or polyvinyl alcohol 1788.
In some embodiments of the present invention, the content of the film forming agent in the clothianidin film slow release type seed treatment suspending agent is preferably 0.1 wt% to 5wt%, for example 0.1 wt% and 5 wt%.
In some embodiments of the present invention, the content of the film forming agent in the clothianidin film slow release type seed treatment suspending agent is 2.5 wt% to 3wt%, for example, 0.3 wt%, 0.5wt%, 0.6 wt%, 1wt%, 2.5 wt%, 3 wt%.
In some embodiments of the invention, the wetting dispersant is a composition of rosin dispersant, polycarboxylate dispersant and macromolecular amphiphilic dispersant in a mass ratio of 3:1:1, and the content of the composition in the suspending agent is 5 wt%; the film-forming agent is polyethylene glycol 8000, the content of which in the suspending agent is 3wt%, or the film-forming agent is polyvinyl alcohol 1788, the content of which in the suspending agent can be 0.5 wt%.
In some embodiments of the invention, the clothianidin is present in the seed treatment suspension in an amount of 20wt% to 50 wt%.
In some embodiments of the invention, the clothianidin is present in the seed treatment suspension in an amount of 30 wt% to 40 wt%.
In some embodiments of the invention, the clothianidin is present in the seed treatment suspension in an amount of 20wt%, 30 wt%, 35wt%, 40 wt%, 50 wt%.
Besides the film forming agent and the wetting and dispersing agent, the seed treatment suspending agent also contains auxiliary materials or auxiliary agents commonly used in the pesticide field, such as thickening agent, antifreezing agent, coloring agent (warning color), defoaming agent, preservative, pH regulator or other fillers, and the dosage of the auxiliary materials or auxiliary agents can be selected and adjusted according to the general knowledge in the field.
Specifically, in some embodiments of the present invention, the pesticide adjuvant further comprises a thickener to increase the viscosity of the dispersion medium, reduce the settling rate of the particles, and thus improve the stability of the formulation. The thickener is preferably one or more of xanthan gum, arabic gum, methylcellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, sodium acrylate, sodium alginate, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, sodium polyacrylate, magnesium aluminum silicate, bentonite and white carbon black.
In some specific embodiments of the invention, the thickening agent is formed by mixing xanthan gum, magnesium aluminum silicate and white carbon black according to a mass ratio (1.8-2):5:5, and the thickening agent has the effects that magnesium aluminum silicate with strong hydration and high polymer xanthan gum with good hydrophilicity have good thixotropy in medium water, the viscosity is reduced when the xanthan gum is shaken, and the xanthan gum has good pourability; at rest, a gelled network is formed and the viscosity increases. Due to the characteristics of the clothianidin technical material, the white carbon black is added into the system, so that the stability and the high suspension rate of the product are facilitated. The product mixed according to the proportion has good stability, and good dispersibility and fluidity.
To further improve the low temperature storage stability of the seed treatment suspension concentrate of the present invention, in some embodiments of the present invention, the pesticide adjuvant further comprises an anti-freeze agent. The antifreezing agent is one or more than two of ethylene glycol, propylene glycol, glycerol, hexanediol, urea, ammonium sulfate, sodium chloride and calcium chloride.
The defoaming agent is preferably one or more than two of organic silicone, AF1500, C8-10 fatty alcohol, C10-20 saturated fatty acid and ester thereof.
The preservative is preferably one or more than two of benzoic acid, benzaldehyde, sodium benzoate, potassium benzoate, sorbic acid, sodium salicylate, 2-hydroxybiphenyl, p-hydroxybenzaldehyde and 1, 2-benzothiazolin-3-one.
In the seed treatment suspending agent, in order to avoid high clothianidin decomposition rate caused by high pH value, one or more of pH regulators such as acetic acid, citric acid, sodium citrate, sodium bicarbonate and triethanolamine can be used for adjusting the pH value of a sample, and the pH regulator is preferably citric acid or sodium citrate.
In some embodiments of the invention, the seed treatment suspending agent has a pH of 5 to 7, for example 5.4.
In order to ensure safe production and use, the pesticide auxiliary agent also comprises a coloring agent, also called a policeman, wherein the coloring agent is preferably one or more than two of dekema, alkaline rose essence, aqueous rose bengal and acid scarlet.
In some embodiments of the invention, the seed treatment suspending agent comprises the following components: 20 to 50 weight percent of clothianidin as an active component, 0.2 to 12 weight percent of wetting dispersant, 0.1 to 5 weight percent of film forming agent, 0.15 to 3 weight percent of defoaming agent, 0.1 to 5 weight percent of preservative, 0.1 to 3 weight percent of thickening agent, 1 to 8 weight percent of antifreezing agent, pH regulator, 0.5 to 5 weight percent of colorant and the balance of water to 100 percent; the pH of the seed treatment suspending agent is 5-7.
In some embodiments of the invention, the seed treatment suspending agent comprises the following components: 30-40 wt% of clothianidin as an active ingredient, 1-5 wt% of wetting dispersant, 0.1-3 wt% of film forming agent, 0.1-1 wt% of defoaming agent, 0.1-1 wt% of preservative, 0.1-1 wt% of thickening agent, 3-5 wt% of antifreezing agent, pH regulator, 1-3 wt% of colorant and the balance of water to 100%; the pH of the seed treatment suspending agent is 5-6.
In some embodiments of the invention, the seed treatment suspending agent comprises the following components: 20-35 wt% of clothianidin as an active ingredient, SC 293% of rosin wetting dispersant, SP-270011% of polycarboxylate dispersant, Y63251% of macromolecular amphiphilic dispersant, 80003% of polyethylene glycol, AF 15000.3%, 0.18% of xanthan gum, 0.5% of magnesium aluminum silicate, 0.5% of white carbon black, 4% of ethylene glycol, 0.2% of citric acid, 3% of Texima and 100% of ionized water.
The clothianidin film slow-release type seed treatment suspending agent can be prepared by a method well known by a person skilled in the art, such as a wet sanding ultramicro grinding method.
In some embodiments of the present invention, the method of preparing the suspension for seed treatment comprises: the clothianidin, the wetting dispersant, the antifreezing agent, the defoaming agent, part of the thickening agent and the water are dispersed into uniform slurry, grinding (for example, pouring the slurry into a sand mill and uniformly mixing with a grinding medium according to a proper proportion, starting the sand mill, sampling and detecting until the requirement is met), adding the rest thickening agent, the film forming agent and the warning color, shearing (for example, shearing by using a high-speed emulsification shearing machine) until the particle size of a detected sample is qualified (for example, the particle size of the detected sample is more than 1-5 mu m, and the average particle size is less than 3 mu m), and filtering (separating and filtering the obtained liquid medicine from the grinding medium).
In some embodiments of the invention, the seed treatment suspension is prepared as a bright red, flowable suspension that is acceptable for low temperature, thermal storage stability.
In some embodiments of the invention, the prepared seed treatment suspending agent has a thermal storage decomposition rate of less than 5%, a suspension rate of more than 90%, a wet sieve test of 98% passing through a standard sieve of 45 μm, and a particle fineness D50 of 2-3 μm.
The invention also provides application of the clothianidin film slow-release type seed treatment suspending agent in pest control. Further, the pests comprise wheat aphids, golden insects and wheat leafworms.
The clothianidin film slow-release type seed treatment suspending agent provided by the invention can play a better role in preventing and controlling various pests, has long lasting period, can particularly effectively control the harm of wheat aphids in the whole growth period of wheat, and can ensure that the effect of preventing and controlling the wheat aphids in the whole growth period reaches more than 90% by carrying out seed dressing treatment on wheat seeds before sowing. Meanwhile, the pesticide also has a certain effect of treating soil insects of wheat, leaf bees and the like. The suspending agent is safe to wheat seed emergence, can reduce the dosage, prolong the duration, reduce the cost and has wide application prospect.
Particularly, the invention also provides application of the clothianidin film slow-release type seed treatment suspending agent in prevention and control of wheat aphids in the whole growth period of wheat.
The application dosage of the clothianidin film slow-release type seed treatment suspending agent in field prevention and control of aphid pests is generally 200g of clothianidin dosage per 100kg of seeds as an effective component for seed treatment.
The application amount of the invention is slightly changed according to the wheat variety, the sowing time, the weather condition and the occurrence degree of pests, and the application purpose can be achieved by proper adjustment.
Compared with the prior art, the invention has the following beneficial effects:
1. the pesticide has long lasting period, can prevent and control wheat aphids by more than 90 percent in the whole growth period of wheat, is safe to crops and does not influence the germination of seeds.
2. Under the same control effect, the dosage of the clothianidin long-acting slow-release suspended seed coating agent is reduced by 17 percent compared with other clothianidin suspended seed coating agent commodities; compared with the neonicotinoid insecticide imidacloprid of the same kind, the dosage is reduced by 40 percent.
3. The pesticide composition can prevent and control wheat aphids, and also has a function of controlling soil insects, wheat leafworms and the like.
Detailed Description
The following examples further describe embodiments of the present invention in detail. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The clothianidin technical material used in the following is purchased from Bayer crop science (China) GmbH.
If not specifically indicated, the contents of all the components in the suspension concentrate for seed treatment provided by the invention are mass percent.
Example 1: 20% clothianidin film slow-release type seed treatment suspending agent
The formula is as follows: 20% of clothianidin as an active ingredient, 4% of Soprophor SC as a wetting dispersant, 100.5% of Igepal BC/100.5%, 0.3% of film-forming agent povidone, 0.5% of fatty alcohol of a defoaming agent C8-10, 0.5% of sorbic acid as a preservative, 1% of white carbon black as a thickening agent, 5% of glycerol as an anti-freezing agent, 1% of sodium bicarbonate as a pH regulator, 2% of rose bengal as a colorant and 100% of ionized water.
The preparation method comprises the following steps: the clothianidin, the wetting dispersant, the antifreezing agent, the defoaming agent, part of the thickening agent and the water are dispersed into uniform slurry, the uniform slurry is poured into a sand mill and uniformly mixed with a grinding medium according to a proper proportion, the sand mill is started, sampling detection is carried out until the requirement is met, the rest thickening agent, the film forming agent and the warning color are added, a high-speed emulsification shearing machine is used for shearing, the grain size of a detected sample is qualified (more than 95 percent is 1-5 mu m, and the average grain size is less than 3 mu m), and the liquid medicine and the grinding medium are separated and filtered.
Example 2: 30% clothianidin film slow-release type seed treatment suspending agent
The formula is as follows: 30% of clothianidin as an active ingredient, Y63254% of a macromolecular amphiphilic dispersant as a wetting dispersant, 3% of pullulan as a film forming agent, 0.8% of fatty alcohol with C8-10 as a defoaming agent, 0.5% of sorbic acid as a preservative, 1% of sodium alginate as a thickening agent, 5% of glycerol as an antifreeze, 0.3% of sodium citrate as a pH regulator, 2% of a colorant and 100% of ionized water.
The preparation method comprises the following steps: essentially as in example 1.
Example 3: 40% clothianidin film slow-release type seed treatment suspending agent
The formula is as follows: the pesticide composition comprises the following active ingredients of clothianidin 40%, a wetting dispersant polycarboxylate dispersant EO/PO polyether D8002%, an alkyl alcohol alkoxylate W6002%, a film forming agent polyvinyl alcohol 17883%, a defoaming agent AF 15000.5%, a preservative sorbic acid 0.5%, a thickening agent sodium alginate 1%, an antifreezing agent glycerol 3%, a pH regulator acetic acid 2%, a coloring agent Dekma 2% and ionized water which are supplemented to 100%.
The preparation method comprises the following steps: essentially as in example 1.
Example 4: 50% clothianidin film slow-release type seed treatment suspending agent
The formula is as follows: 50% of clothianidin as an active ingredient, 295% of wetting dispersant, namely rosin dispersant, SC 295%, Y63251.5% of macromolecular amphiphilic dispersant, SP-270011.5% of polycarboxylate dispersant, 17882.5% of film-forming agent polyvinyl alcohol, 15000.8% of defoaming agent AF, 0.8% of preservative sodium benzoate, 1% of thickening agent xanthan gum, 3% of antifreezing agent ethylene glycol, 3.5% of pH regulator acetic acid, 2% of colorant debarkma and 100% of ionized water.
The preparation method comprises the following steps: essentially as in example 1.
Example 5: 35% clothianidin film slow-release type seed treatment suspending agent
The formula is as follows: 35% of clothianidin as an active ingredient, 4% of a wetting dispersant, 80002.5% of polyvinyl alcohol as a film forming agent, 15000.3% of a defoaming agent, 0.2% of sodium benzoate as a preservative, 0.3% of a thickening agent, 3% of ethylene glycol as an antifreezing agent, 0.3% of sodium citrate as a pH regulator, 2% of a colorant and 100% of ionized water.
In the implementation, the wetting dispersant is a mixture of rosin wetting dispersant, polycarboxylate dispersant and macromolecular amphiphilic dispersant in a mass ratio of 4:1.5: 1.5; the thickening agent is a mixture of xanthan gum, magnesium aluminum silicate and white carbon black according to the mass ratio of 1.8:5: 5.
The preparation method comprises the following steps: essentially as in example 1.
Example 6: 35% clothianidin film slow-release type seed treatment suspending agent
The formula is as follows: 35% of clothianidin as an active ingredient, SC 293% of rosin wetting dispersant, SP-270011% of polycarboxylate dispersant, Y63251% of macromolecular amphiphilic dispersant, 80003% of polyethylene glycol, AF 15000.3% of xanthan gum, 0.18% of magnesium aluminum silicate, 0.5% of white carbon black, 4% of ethylene glycol, 0.2% of citric acid, 3% of Derma and 100% of ionized water.
The preparation method comprises the following steps: essentially as in example 1.
Experiment 1: selection of wetting and dispersing agent
According to the processing theory of the suspending agent, a primary screening experiment with different proportions is carried out by using dispersing agents and wetting agents of different manufacturers, and screening of the wetting dispersing agents is tested by using a French Solvay Soprophor SC \ Igepal BC/10, a American Hounsfield TERSPERSE2500 \4894, a Nanjing engine auxiliary agent SC29\ SP-27001\ Y6325, a Tao's auxiliary agent and the like. Compounding various wetting dispersants according to different proportions, preparing 6 formulas in total, and primarily screening out which wetting dispersant is used according to indexes such as appearance phenomenon, dispersibility and the like of a sample in the grinding process. The formulations (table 1) and experimental results (table 2) are as follows:
TABLE 1 screening of wetting dispersants
Figure BDA0002207754640000101
Table 2 wetting dispersant screening test results
Figure BDA0002207754640000102
Figure BDA0002207754640000111
As can be seen from tables 1 and 2, the wetting and dispersing agent used in formulation A, E, F exhibited a sticky or fluid consistency during grinding, and could not be used in this product; the wetting dispersant used in the formula B, C has no creaming phenomenon after grinding a sample, has good dispersibility, can be used in the product, and can be layered after heat storage; only the cold and hot storage sample of the formula D is qualified in appearance, does not stick to the wall and is easy to pour. The wetting dispersant composition is determined to be SC29\ SP-27001\ Y6325, and the addition amounts are 3%, 1% and 1% respectively.
Experiment 2: indoor toxicity assay
The toxicity of the myzus avenae is measured by adopting an immersion method, a clothianidin original drug is diluted into a mother solution by acetone, the mother solution is diluted into liquid medicine with 5-7 concentration gradients by using 0.1% Tween 80 aqueous solution, wingless adult myzus with the same size and leaves are picked to be immersed in the liquid medicine for 5 seconds by using 0.1% Tween aqueous solution as a contrast, the residual liquid medicine is taken out and sucked by using filter paper, the box is placed in an insect breeding box, each box is repeated for 3 times at 20-30 times, the box is raised in an insect breeding room at the temperature of (22 Shi 1), and the result is checked after 24 and 48 hours, and the death is recorded by using a person who only moves one leg or does not move at all in a light touch pen.
The toxicity of the golden insect is measured by soaking the golden insect in water, the original clothianidin is prepared into mother liquor with a certain concentration by acetone, and the mother liquor is diluted into 5-6 gradient concentrations by 0.1% Tween 80 water. Putting the wheat seeds which are tidy and have consistent germination degree into a steel mesh enclosure, soaking the wheat seeds in the liquid medicine for 10s, taking out the wheat seeds, putting the wheat seeds on filter paper, absorbing redundant liquid medicine, putting the wheat seeds into a glass insect culturing tube (the diameter is 1.8cm, the height is 8cm), taking 2 grains per tube, simultaneously putting the test insects into the liquid medicine, soaking the test insects for 10s, taking out the test insects, absorbing redundant liquid medicine by using absorbent paper, putting the test insects into the insect culturing tube, testing 1 head of the test insects, putting wet soil with proper water content (about 18%), plugging a rubber plug to prevent the test insects from escaping, and carrying out single-tube feeding. 30 test insects are treated. And (3) feeding the treated test insects in a greenhouse with the temperature of about 24 ℃ and the humidity of about 60%. After 5d, the death condition of the test insects is checked (death standard: the insects shrink obviously or the test insects contacted with the test insects can not crawl normally).
Calculating toxicity regression formula (Y ═ A + BX) and lethal medium concentration LC (concentration of C) according to death probability value and concentration logarithm value by using DPS software50The value is obtained. The results are given in Table 3 below.
TABLE 3 indoor toxicity assay results of clothianidin against Aphis gramineus and Enoki
Figure BDA0002207754640000121
As can be seen from Table 3, clothianidin has high toxicity to the common wheat pest Entomophthorales piricola and the soil pest Entomophtheilus.
Experiment 3: screening experiment of film Forming agent
A 35% film slow release type seed treatment suspending agent (hereinafter referred to as '35% clothianidin FS') formulation without a film forming agent: 35% of clothianidin as an active ingredient, SC 293% of rosin wetting dispersant, SP-270011% of polycarboxylate dispersant, Y63251% of macromolecular amphiphilic dispersant, AF 15000.3% of the rosin wetting dispersant, 0.18% of xanthan gum, 0.5% of magnesium aluminum silicate, 0.5% of white carbon black, 4% of ethylene glycol, 0.2% of citric acid, 3% of dekema and 100% of ionized water.
After different film-forming agents are added into the 35% clothianidin FS, the wheat is subjected to seed treatment according to the seed proportion, the prevention and control effect of the wheat on wheat aphids in the growth period of the wheat is investigated, and the film-forming agents which are safe to the wheat and have the sustained-release effect on medicaments are screened. The results are shown in tables 4 and 5.
Wherein A, B, C, D respectively represents polyethylene glycol 8000, polyvidone K30, polyvinyl alcohol 1788, and pullulan; A1-D1 show that the addition amount of each film forming agent is 3%, 0.3%, 0.5% and 3%, and A2-D2 show that the addition amount of each film forming agent is 5%, 0.6%, 1% and 5%.
TABLE 4 influence of clothianidin series of agents on wheat seed germination
Figure BDA0002207754640000122
Figure BDA0002207754640000131
As can be seen from Table 4: the 35% clothianidin FS is added with different film forming agents and then is treated by dressing seeds, the germination potential of wheat seeds is between 78.7% and 90.0%, the germination rate is between 91.3% and 96.7%, and the treatment of each agent has no obvious difference from blank control treatment; the bud length of 35% clothianidin FS + C1 treated is obviously longer than that of the blank control, and the bud lengths of other treatments are not obviously different from that of the blank control; the root length and number of each treatment were not significantly different from those of the blank control treatment. Therefore, after the clothianidin FS is added with different film forming agents, the seed dressing treatment has no influence on the germination of the wheat seeds when the dosage of the effective components is 200g/100kg of the seeds.
TABLE 5 seed dressing treatment with different film-forming agents for controlling wheat aphids
Figure BDA0002207754640000132
Note: 70% imidacloprid ZF is a commonly used medicament in local production, so the imidacloprid ZF is taken as a reference medicament and purchased from North Hebei West Biochemical pesticide Co.
As can be seen from Table 5, in the full-growth period of wheat aphids, 5 months, 8 days and 14 days, the control effect of the seed treatment of the clothianidin FS + auxiliary agent A1 and the clothianidin FS + auxiliary agent C1 on the wheat aphids is higher than that of the seed treatment of 35% of the seed treatment of the clothianidin FS with 200g/100kg of the effective component, and the control effects of the seed dressing of clothianidin on the wheat aphids can be improved by the auxiliary agents A1 and C1.
The control effect of the clothianidin FS + auxiliary agent A1 and the clothianidin FS + auxiliary agent C1 on wheat aphids in the seed treatment of 200g/100kg of effective components is similar to the control effect of the clothianidin FS effective component in the seed treatment of 240g/100 kg. Under the condition of similar control effect, the formula is improved by adding a proper film-forming agent, so that the dosage of clothianidin can be reduced by 17%, and the dosage is obviously reduced.
Experiment 4: experiment of field drug effect
The wheat variety to be tested is 'Jimai 22'. The wheat seeds are treated by the agent before being sown, and according to the proportion of the seeds, the agent is mixed with water and then is uniformly stirred with the wheat seeds, and the wheat seeds can be used after being dried in the shade.
The experiment was conducted in Shijiazhuang Zhao county in Hebei province and Baoding Gaoyang.
Experimental samples: the 35% clothianidin film sustained-release type seed treatment suspending agent (hereinafter referred to as "35% clothianidin FS") prepared in example 6.
Control agents: in production, 70% imidacloprid seed treatment dispersible powder (hereinafter referred to as '70% imidacloprid ZF') which is commonly used as a medicament is purchased from North Hebei West Biochemical pesticide Co., Ltd.
Seed without seed dressing treatment was used as a blank control.
The results are shown in tables 6 and 7 below.
Influence of the surface 635% clothianidin FS seed dressing treatment on field wheat emergence
Figure BDA0002207754640000141
Wheat seedlings were grown for 5 m rows 30 days after sowing. The seeding rate in Zhao county is 30 jin/mu, and the seeding rate in Gaoyang county is 50 jin/mu.
The results of the field seed dressing treatment experiments show that (table 6), the emergence situation of the wheat treated by the ' 35% clothianidin FS ' is not obviously different from that of a blank control, and the safety of the 35% clothianidin FS ' to the germination of wheat seeds is superior to that of a control medicament ' 70% imidacloprid ZF '.
TABLE 735% control Effect of clothianidin FS dressing treatment on wheat aphids
Figure BDA0002207754640000151
From table 7, it can be seen that the control effect of the seed dressing treatment of the '35% clothianidin FS' in the outbreak period of wheat aphids can still reach more than 90%, and the control effect is superior to that of the control medicament '70% imidacloprid ZF'. Compared with the pesticide, under the condition of similar control effect, the dosage of the '35% clothianidin FS' can be reduced by more than 40%.
Experiment 5: effect of field experiment for treating wheat leaf wasp
The wheat seeding treatment method and the used medicament are the same as experiment 4.
The prevention and control effects on the soil insects and the leaf bees are respectively counted by investigating the number of the damaged plants and the number of the larvae of the leaf bees in the seedling stage of the wheat. The results are shown in Table 8.
Control effect of seed dressing treatment of thiamethoxam FS with surface concentration of 835% on wheat leaf wasps and underground pests
Figure BDA0002207754640000152
As can be seen from Table 8, the comprehensive control effect of 35% of clothianidin FS on the leaf wasps and the soil insects is more than 90%, namely the wheat aphids are controlled, and meanwhile, the growth of wheat is protected from the harm of the leaf wasps and the soil insects.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (10)

1. A clothianidin film slow-release type seed treatment suspending agent is characterized by comprising:
the active ingredient clothianidin;
wetting dispersant, specifically a composition of rosin dispersant, polycarboxylate dispersant and macromolecular amphiphilic dispersant; the rosin dispersant is SC29, the polycarboxylate dispersant is SP-27001, and the macromolecular amphiphilic dispersant is Y6325; the contents of the rosin dispersant, the polycarboxylate dispersant and the macromolecular amphiphilic dispersant in the clothianidin film slow-release type seed treatment suspending agent are respectively 3wt%, 1wt% and 1 wt%; and
the film-forming agent is polyethylene glycol 8000, and the content of the film-forming agent in the suspending agent is 3 wt%; or the film forming agent is polyvinyl alcohol 1788, and the content of the film forming agent in the suspending agent is 0.5 wt%.
2. The clothianidin film slow-release type seed treatment suspending agent according to claim 1, wherein in the seed treatment suspending agent: the content of clothianidin is 20-50 wt%.
3. A clothianidin film slow release type seed treatment suspending agent as claimed in claim 1 or 2, wherein the pH value of the suspending agent is 5-7.
4. A clothianidin film slow release type seed treatment suspending agent as claimed in claim 3, wherein the pH value of the suspending agent is 5.4.
5. A clothianidin film slow release type seed treatment suspending agent as claimed in any one of claims 1,2 and 4, wherein the suspending agent further comprises one or more of the following auxiliary materials or auxiliary agents:
a thickener;
an anti-freezing agent;
defoaming agents;
a preservative;
a pH adjusting agent;
a colorant.
6. The clothianidin film slow-release type seed treatment suspending agent as claimed in claim 5, wherein the thickening agent is prepared by mixing xanthan gum, magnesium aluminum silicate and white carbon black according to a mass ratio of (1.8-2) to 5: 5;
the antifreezing agent is one or more than two of ethylene glycol, propylene glycol, glycerol, hexanediol, urea, ammonium sulfate, sodium chloride and calcium chloride;
the defoaming agent is one or more than two of organosilicone, AF1500, C8-10 fatty alcohol, C10-20 saturated fatty acid and ester thereof;
the colorant is one or more of Deskman, alkaline rose essence, aqueous rose bengal and acid scarlet.
7. The clothianidin film slow-release type seed treatment suspending agent according to claim 1, wherein the suspending agent comprises the following components: 20-35 wt% of clothianidin as an active ingredient, SC 293% of rosin wetting dispersant, SP-270011% of polycarboxylate dispersant, Y63251% of macromolecular amphiphilic dispersant, 80003% of polyethylene glycol, AF 15000.3%, 0.18% of xanthan gum, 0.5% of magnesium aluminum silicate, 0.5% of white carbon black, 4% of ethylene glycol, 0.2% of citric acid, 3% of Texima and 100% of ionized water.
8. A method for preparing a clothianidin film slow-release type seed treatment suspending agent as claimed in any one of claims 1 to 7, which comprises the following steps: the clothianidin, the wetting dispersant, the antifreezing agent, the defoaming agent, part of the thickening agent and water are dispersed into uniform slurry, the slurry is ground, the rest thickening agent, the film forming agent and the warning color are added, the mixture is sheared to the required particle size, and the mixture is filtered.
9. Use of a clothianidin film slow-release type seed treatment suspending agent as defined in any one of claims 1 to 7 or the clothianidin film slow-release type seed treatment suspending agent prepared by the method as defined in claim 8 for controlling pests; the pests are wheat aphids, golden insects and wheat leaf bees.
10. The use according to claim 9, wherein the use is for controlling wheat aphid during the whole growth period of wheat.
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