WO2022037442A1 - 一种包含纳米噻唑锌的悬浮剂及其制备方法 - Google Patents

一种包含纳米噻唑锌的悬浮剂及其制备方法 Download PDF

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WO2022037442A1
WO2022037442A1 PCT/CN2021/111791 CN2021111791W WO2022037442A1 WO 2022037442 A1 WO2022037442 A1 WO 2022037442A1 CN 2021111791 W CN2021111791 W CN 2021111791W WO 2022037442 A1 WO2022037442 A1 WO 2022037442A1
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nano
zinc thiazole
particles
particle size
suspending agent
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PCT/CN2021/111791
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English (en)
French (fr)
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魏方林
魏晓林
徐沛东
李俊
张军
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浙江新农化工股份有限公司
江苏新农化工有限公司
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Publication of WO2022037442A1 publication Critical patent/WO2022037442A1/zh

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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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P3/00—Fungicides

Definitions

  • the invention belongs to the field of agricultural chemistry, relates to nanometer fungicide pesticide products, and in particular relates to a suspension agent containing nanometer zinc thiazole for improving crop disease control effect and a preparation method thereof.
  • the chemical name of zinc thiazole is 2-amino-5-mercapto-1,3,4-zinc thiadiazole, and the molecular formula is C 4 H 4 N 6 S 4 Zn.
  • Zinc thiazole is an off-white powder with poor solubility in water and organic solvents such as methanol, ethanol, DMF, acetone, isopropanol, acetonitrile, ethyl acetate, and methane, and is almost insoluble.
  • the commercialized zinc thiazole preparation products are mainly suspending agents containing zinc thiazole.
  • the particle size D 90 of the zinc thiazole particles in "Bisson" (the trade name of 20% zinc thiazole suspending agent) is about 3-5 microns. It has a good effect on preventing and controlling crop diseases (especially bacterial diseases).
  • the micronized zinc thiazole drug can form a wider application range than the non-micronized zinc thiazole drug, such as reducing the preparation of zinc thiazole suspensions and other preparations.
  • the particle size of zinc thiazole particles in the formula helps to improve the efficacy of the preparation.
  • the particle size is reduced below a certain size, for example, when the particle size D 50 is reduced to below 300 nm, the particle size distribution range is unreasonable, resulting in the micronized zinc thiazole suspension for some parts of some crops.
  • phytotoxicity for details, please refer to the activity test results of the zinc thiazole suspension in CN109122699A).
  • the present invention needs to solve the problems of drug efficacy and drug damage of the zinc thiazole suspension agent, that is, to improve the drug efficacy of the zinc thiazole suspension agent, and simultaneously reduce the drug damage of the zinc thiazole suspension agent.
  • the present invention provides a suspending agent containing nano-zinc thiazole, wherein the suspending agent contains nano-zinc thiazole particles, and the total weight of the nano-zinc thiazole particles accounts for 1%-70% of the weight of the suspending agent,
  • the particle size D 90 of the nano zinc thiazole particles is 400 nm ⁇ D 90 ⁇ 1100 nm
  • the particle size D 50 of the nano zinc thiazole particles is D 50 ⁇ 90 nm.
  • the particle size D 90 of the zinc thiazole particles is 400nm ⁇ D 90 ⁇ 1100nm, and the particle size D 50 of the zinc thiazole particles is 40nm ⁇ D 50 ⁇ 90nm.
  • the particle size D 90 of the zinc thiazole particles is 430nm ⁇ D 90 ⁇ 850nm, and the particle size D 50 of the zinc thiazole particles is 45nm ⁇ D 50 ⁇ 90nm.
  • the particle size D 90 of the zinc thiazole particles is 430nm ⁇ D 90 ⁇ 1090nm, and the particle size D 50 of the zinc thiazole particles is 45nm ⁇ D 50 ⁇ 85nm.
  • the particle size D 90 of the zinc thiazole particles is 420nm ⁇ D 90 ⁇ 630nm, and the particle size D 50 of the zinc thiazole particles is 45nm ⁇ D 50 ⁇ 80nm.
  • the present invention also provides a suspending agent comprising nano-zinc thiazole particles, wherein the suspension agent comprises nano-zinc thiazole particles, the total weight of the nano-zinc thiazole particles accounts for 1%-70% of the weight of the suspending agent, and the nano-zinc thiazole particles are
  • the diameter D 90 is D 90 ⁇ 400 nm
  • the particle size D 50 of the nano zinc thiazole particles is 90 nm ⁇ D 50 ⁇ 120 nm.
  • the particle size D 90 of the zinc thiazole particles is 110nm ⁇ D 90 ⁇ 400nm, and the particle size D 50 of the zinc thiazole particles is 90nm ⁇ D 50 ⁇ 120nm.
  • the particle size D 90 of the zinc thiazole particles is 110nm ⁇ D 90 ⁇ 350nm, and the particle size D 50 of the zinc thiazole particles is 90nm ⁇ D 50 ⁇ 110nm.
  • the particle size D 90 of the zinc nano thiazole particles is 260nm ⁇ D 90 ⁇ 390nm, and the particle size D 50 of the zinc nano thiazole particles is 95nm ⁇ D 50 ⁇ 115nm .
  • the particle size D 90 of the zinc thiazole particles is 220nm ⁇ D 90 ⁇ 395nm, and the particle size D 50 of the zinc thiazole particles is 95nm ⁇ D 50 ⁇ 115nm.
  • the particle size D 10 of the zinc thiazole particles is 10 nm ⁇ D 10 ⁇ 50 nm; preferably, the particle size D 10 of the zinc thiazole particles is 17 nm ⁇ D 10 ⁇ 49 nm.
  • the diameter of the nano-zinc thiazole particles ranges from 0.705 to 22.060.
  • the diameter of the nano-zinc thiazole particles ranges from 0.705 to 17.410.
  • the diameter of the nano-zinc thiazole particles ranges from 1.898 to 22.060.
  • the diameter range of the nano-zinc thiazole particles is 1.636-12.442.
  • the percentage of the total weight of the nano-zinc thiazole particles in the weight of the suspending agent is 5%-60%.
  • the suspending agent contains one or more adjuvants among surfactants, thickeners, preservatives, defoaming agents, and antifreeze agents.
  • the surfactant is selected from EO/PO block polyether, naphthalenesulfonic acid condensate sodium salt, phenolsulfonic acid condensate sodium salt, sodium methylnaphthalenesulfonate Formaldehyde condensate, sodium methylene dinaphthalene sulfonate, sodium dioctyl sulfosuccinate, sodium starch octenyl succinate, alkylphenol formaldehyde resin polyoxyethylene ether sulfate, polyoxyethylene lauryl alcohol Propylene ether sulfate, alkylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, alkylnaphthalene sulfonate, lignosulfonate, fatty alcohol polyoxyethylene ether sulfate, acrylic acid homopolymer sodium salt, high One or more of molecular polycarboxylate and maleic acid-acryl
  • the thickener is selected from one or more of xanthan gum, sodium carboxymethyl cellulose, polyvinyl alcohol, and magnesium aluminum silicate;
  • the agent is selected from phenyl salicylate, butyl p-hydroxybenzoate, potassium sorbate, 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazoline- 3-ketone, 1,2 benzisothiazolin-3-one, 2-bromo-2-nitro-1,3-propanediol, 3-iodo-2-propynyl-butylcarbamate
  • the defoamer is selected from one or more of silicone defoamer, GP polyether defoamer, GPE polyether defoamer, and GPES polyether defoamer; the antifreeze
  • the agent is selected from one or more of ethylene glycol, propylene glycol, gly
  • the present invention also provides a method for preparing the above-mentioned suspension agent comprising zinc thiazole, the method being:
  • Zinc thiazole one or more of surfactants, thickeners, preservatives, defoaming agents, antifreeze agents, and water are stirred and mixed evenly, and then passed through a sand mill for circular sanding or multi-stage sanding. After the diameter reaches the nanometer level, the sanding medium is filtered and removed to obtain a suspension agent containing zinc thiazole, wherein the diameter of the sanding medium in at least one sand mill in the sand mill is 0.1 mm-0.6 mm.
  • the sanding medium is zirconia beads
  • the medium filling factor is 0.7-0.8
  • the sanding temperature is controlled below 30°C.
  • the sanding temperature is controlled at 25°C or below.
  • the nano-suspension agent may also contain other fungicides, and the ratio of the weight of other fungicides to the weight of zinc thiazole is 1:100-100:1 .
  • the present invention also provides the use of the above-mentioned suspending agent containing the nano-zinc thiazole for preventing and treating crop diseases.
  • the crop disease is a bacterial disease.
  • the suspending agent containing nano-Zn thiazole provided by the present invention is relative to the suspending agent of zinc thiazole with particle size D 50 >120 nm and D 90 ⁇ 400 nm, especially the particle size D 50 developed in the process of developing micronized zinc thiazole drug
  • the distribution of the particle size D 90 and D 50 of the zinc thiazole of the present invention has a more unique situation, on the other hand, although the zinc thiazole of the present invention
  • the particle size D 50 is smaller, but through the distribution of large particles of zinc thiazole and small particles of zinc thiazole, the suspension of zinc thiazole will not cause crop damage.
  • the zinc thiazole suspending agent provided by the invention has a special particle size distribution. Compared with the control effect of 90 ⁇ 400nm zinc thiazole suspension, the control effect can be increased by about 13% at 17 days after treatment, 16% at 6 days after treatment, and 10 days after treatment. Compared with the control effect of zinc thiazole suspension with particle size D 50 >120nm and D 90 ⁇ 400nm, the control effect of 2 days after treatment can be improved by 18%, The control effect in the last 3 days can be increased by 36% at most, and the improvement effect of the nano-zinc thiazole of the present invention on the quick-acting and lasting effect of diseases is also very obvious.
  • the nanometer thiazole zinc suspending agent provided by the present invention has little change in particle size and control effect. , the difference of control effect in 2 days after treatment was about 1%, and the difference in control effect in 3 days after treatment was about 5%.
  • the sanding medium used in the sand mill is zirconia beads with a diameter of 1.2mm, and the sanding time is 40 minutes.
  • the sanding medium used in the second-stage sand mill is zirconia beads with a diameter of 0.6mm, and the sanding time is 30 minutes.
  • the sanding medium used in the third-stage sand mill is 0.3mm diameter zirconia beads and 0.1mm yttrium-stabilized zirconia beads (the ratio of the two is 2/1), starting from the third-stage sand mill, after sanding Samples were taken from the 15th minute, and subsequently every 10 minutes, to measure the particle size of the zinc thiazole particles in each sample. The particle size is shown in Table 1 below.
  • the quality of the zinc thiazole suspension agent still meets the quality requirements of the suspension agent, and there is no stratification and agglomeration.
  • the particle size of the zinc thiazole particles in the zinc thiazole suspension agent is measured again. The particle size is shown in Table 2 below.
  • Bioassay Example 1 Rice Bacterial Blight Test
  • the suspending agent samples used in the rice bacterial blight test mainly include:
  • Besun (20% thiazole zinc suspending agent) and Long Kejun (20% thiazide copper suspending agent) are commercially available products.
  • Suspension sample Dilution factor Active ingredient concentration (mg/L) FF-024-1 700 286 FF-024-2 700 286 FF-024-3 700 286 FF-024-4 700 286 FF-024-5 700 286 FF-024-6 700 286 FF-024-7 700 286 FD-024-1 700 286 FD-024-2 700 286 Beison 700 286 Long Kejun 700 286
  • the control test of rice bacterial blight was carried out in the Xianju Bioassay Center of the applicant of the present patent, and the control test was carried out by inoculating the bacteria in pots.
  • Test method refer to "SOP-SC-1113 Potted Method for Rice Bacterial Blight” edited by Kang Zhuo and Gu Baogen in "Standard Practice for Pesticide Biological Activity Testing - Fungicide Volume", select rice at the end of tillering, 2cm away from the tip of the leaf Inoculate with bacteria suspension (OD 600 : 1.0), cut leaves 10-15 pieces per pot, keep moist at 28°C for 24h in the dark (RH>90%); spray application according to the experimental treatment, 3 pots of rice ( 1 pot/repeated), the amount of spraying solution for each treatment was 50 mL; after spraying, 28 °C, light cultivation, RH>60%.
  • Investigation method Adjust the investigation method of the "Specification” according to the needs, from measuring the lesion area to the lesion length: after culturing for 17 days, measure the lesion length of the clear water control and the chemical treatment, and calculate the average of the lesion length of each treatment. value, and then calculate the control effect according to the following formula:
  • Control effect (spot length of clear water control - lesion length of chemical treatment) / length of clear water control lesion ⁇ 100%
  • the suspending agent with a particle size D 90 of 110.6 nm-849.7 nm and a D 50 of 47.8 nm-90.2 nm prepared by the present invention can achieve a control effect of more than 52%, and No phytotoxicity occurred, but the D 90 of thiazole zinc FD-024-1 and FD-024-2 with particle size D 50 >120 nm were 243.9 nm and 362.3 nm, and the D 50 was 126.8 nm and 193.5 nm.
  • the control effect is better than that of Bisheng and Longke, but it has the problem of phytotoxicity.
  • the phytotoxicity is mainly manifested in the presence of heart-shaped tubular leaves and stiffness on the rice leaves.
  • FD-024-1 The rice with phytotoxicity The ratio of the number of plants was 34.5%, and the ratio of the number of rice plants with phytotoxicity in FD-024-2 was 28.7%.
  • the control effect of the nano-zinc thiazole suspensions FF-024-1 to FF-024-7 prepared by the present invention is 73% in 6 days after the medicine
  • the preventive effect of suspending agent FD-024-1 and FD-024-2 is lower than the efficacy of the nano-thiazole zinc suspending agent of the present invention, the difference is not obvious, but it can be seen 10 days after the medicine, this
  • the invented nano-thiazole zinc suspending agents FF-024-1 to FF-024-7 are significantly higher than the suspending agents FD-024-1 and FD-024-2, and the preventive effect is increased by about 6%-18%.
  • the nano thiazole zinc suspending agents FF-024-1 to FF-024-7 of the invention have better persistence than the thiazole zinc suspending agents FD-024-1 and FD-024-2 with particle diameter D 50 >120
  • Bioassay Example 2 Test of green cabbage soft rot
  • the main suspension samples for green cabbage soft rot are:
  • Besun (20% zinc thiazole suspension) and Long Kejun (20% copper thiazole suspension) are commercially available products.
  • the above suspending agent samples were respectively diluted 400 times, and the concentration of zinc thiazole and copper thiazide diluted into the liquid medicine were 500 mg/L.
  • the blank control was clear water, and the dosage of clear water was the same as that of medicinal liquid. The specific situation is shown in Table 7 below.
  • Suspension sample Dilution factor Diluted liquid concentration (mg/L) FF-024-1 400 500 FF-024-2 400 500 FF-024-3 400 500 FF-024-4 400 500 FF-024-5 400 500 FF-024-6 400 500 FF-024-7 400 500 FD-024-1 400 500 FD-024-2 400 500 Beison 400 500 Long Kejun 400 500
  • the control test of green cabbage soft rot was carried out in the Xianju Bioassay Center of the applicant of the present patent.
  • Test method choose 3 leaves and 1 heart stage cabbage, spray and spray according to the test treatment, 3 replicates for each treatment, 4 pots of cabbage for each replicate (2 plants/pot), and the amount of spraying liquid for each treatment is 50 mL; 24h after the drug, Poke holes at each petiole and drip 10 ⁇ L of bacterial solution (OD 600 : 0.2), keep moisturizing at 25-28°C for 24h; after moisturizing for 24h (ie, 2 days after the drug), move out of the moisturizing room to investigate the control effect, and then after moving out of the moisturizing room 24 hours (ie, 3 days after the drug), the control effect investigation and safety investigation were carried out.
  • Grade 1 The length of the lesion accounts for 1-10% of the length of the petiole
  • Grade 3 The length of the lesions accounts for 11%-30% of the length of the petiole
  • Grade 5 The length of the lesions accounts for 31%-50% of the length of the petiole
  • Grade 7 The length of the lesion accounts for 51-100% of the length of the petiole
  • Level 9 The whole plant is soft and rotten.
  • the calculation method of the disease index is as follows:
  • Control effect [(control disease index-treatment disease index)/control disease index] ⁇ 100%.
  • the 3-day control effect of the nano-zinc thiazole suspension agents FF-024-1 to FF-024-7 prepared by the present invention is higher than 45% on the soft rot of green vegetables, and the highest reaches 76%, and No symptoms of phytotoxicity occurred.
  • the control effect of FD-024-1 and FD-024-2 on green cabbage soft rot after 3 days was about 37%, which was higher than that of Bisheng and Longkejun.
  • the phytotoxic symptoms of light yellow spots were observed, the ratio of the number of leaves with the phytotoxic symptoms in the FD-024-1 treatment was 23.2%, and the ratio of the number of leaves with the phytotoxic symptoms in the FD-024-1 treatment was 19.5% .
  • Bioassay Example 3 Effect Verification of Storage Zinc Thiazole Suspension
  • Samples FF-024-1C, FF-024-2C, FF-024-3C, FF-024-4C, FF-024-5C, FF after storage of the suspension containing nano-thiazole zinc prepared in Preparation Example 1 for 2 years -024-6C and FF-024-7C were diluted 400 times respectively, and the concentration of zinc thiazole diluted into the liquid was 500 mg/L.
  • the blank control was clear water, and the dosage of clear water was the same as that of medicinal liquid. The specific situation is shown in Table 9 below.
  • Suspension sample Dilution factor Diluted liquid concentration (mg/L) FF-024-1C 400 500 FF-024-2C 400 500 FF-024-3C 400 500 FF-024-4C 400 500 FF-024-5C 400 500 FF-024-6C 400 500 FF-024-7C 400 500
  • the control test of green cabbage soft rot was carried out in the Xianju Bioassay Center of the applicant of the present patent.
  • Test method choose 3 leaves and 1 heart stage cabbage, spray and spray according to the test treatment, 3 replicates for each treatment, 4 pots of cabbage for each replicate (2 plants/pot), and the amount of spraying liquid for each treatment is 50 mL; 24h after the drug, Poke holes at each petiole and drip 10 ⁇ L of bacterial solution (OD 600 : 0.2), keep moisturizing at 25-28°C for 24h; after moisturizing for 24h (ie, 2 days after the drug), move out of the moisturizing room to investigate the control effect, and then after moving out of the moisturizing room 24 hours (that is, 3 days after the drug), the prevention and control effect investigation and the safety investigation were carried out, and the investigation method was the same as above.
  • Table 10 The specific results are shown in Table 10 below.
  • the control effect of FF-024-1C to FF-024-7C on the soft rot of green vegetables is similar to the newly prepared nano thiazole zinc suspending agent FF-024-1 to FF-024- 7 There is no obvious difference in the control effect of green cabbage soft rot.
  • the average control effect of FF-024-1 to FF-024-7 of the new nano thiazole zinc suspension on green cabbage soft rot after 2 days is 65.54%
  • the average value of the control effect of FF-024-1C to FF-024-7C of the nano-zinc thiazole suspension stored for two years on green cabbage soft rot after 2 days is 64.39%, and the difference in control effect is not obvious.
  • the average value of the control effect of the newly prepared nano-zinc thiazole suspension from FF-024-1 to FF-024-7 on green cabbage soft rot after 3 days is 60.42%
  • the FF-024 of the nano-zinc thiazole suspension stored for two years is 60.42%.
  • the average control effect of -1C to FF-024-7C on green cabbage soft rot after 3 days was 55.85%, and the difference in control effect was not obvious.
  • test results in Table 10 show that after 2 years of storage, the particle size of the zinc thiazole particles in the zinc thiazole suspension of the present invention does not change significantly, and the control effect on green cabbage soft rot does not change much.
  • the sanding medium used in the first-stage sander is zirconia beads with a diameter of 1.2 mm, and the sanding is carried out for 30 minutes.
  • the sanding used in the second-stage sanding machine The medium is zirconia beads with a diameter of 1.0mm, and the sanding time is 40 minutes.
  • the sanding medium used in the third-stage sand mill is zirconia beads with a diameter of 0.3mm. 10 minutes, sampling every 5 minutes, to the 105th minute last sampling, obtain 60% thiazole zinc suspending agent of different particle size, measure the thiazole zinc particle size of each sampling, the particle size measurement result of thiazole zinc is as shown in table 11 below. Show.
  • the above suspending agent samples were respectively diluted 1200 times, and the concentration of zinc thiazole and copper thiazide diluted into the liquid medicine were 500 mg/L.
  • the blank control was clear water, and the dosage of clear water was the same as that of medicinal liquid.
  • the control test of green cabbage soft rot was carried out in the Xianju Bioassay Center of the applicant of the present patent.
  • Test method choose 3 leaves and 1 heart stage cabbage, spray and spray according to the test treatment, 3 replicates for each treatment, 4 pots of cabbage for each replicate (2 plants/pot), and the amount of spraying liquid for each treatment is 50 mL; 24h after the drug, Poke holes at each petiole and drip 10 ⁇ L of bacterial solution (OD 600 : 0.2), keep moisturizing at 25-28°C for 24h; after moisturizing for 24h (ie, 2 days after the drug), move out of the moisturizing room to investigate the control effect, and then after moving out of the moisturizing room 24 hours (that is, 3 days after the drug), the prevention and control effect investigation and the safety investigation were carried out, and the investigation method was the same as above.
  • Table 12 The specific results are shown in Table 12 below.
  • the particle size D 90 of FF-Y-01 to FF-Y-013 is in the range of 224.4nm-628.6nm, and the particle size D 50 is in the range of 49.1nm-111.6nm, which is suitable for the soft rot of green vegetables.
  • the average value of the control effect of 2 days after the treatment of the disease was 64.17%, which was 65.54 compared with the average value of the control effect of FF-024-1 to FF-024-7 on the 2 days after the treatment of green vegetable soft rot in Table 8. %quite.
  • the average value of the control effect of FF-Y-01 to FF-Y-013 on green cabbage soft rot 3 days after the drug is 55.62%, which is comparable to that of FF-024-1 to FF-024-7 in Table 8 on green cabbage
  • the average value of the control effect of soft rot disease in 3 days after the drug treatment was 60.42%, and FF-Y-01 to FF-Y-013 did not have any phytotoxicity on the control of green vegetable soft rot disease.

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Abstract

本发明涉及一种包含纳米噻唑锌的悬浮剂及其制备方法，所述悬浮剂中包含纳米噻唑锌颗粒，纳米噻唑锌颗粒总重量占悬浮剂重量的百分比为1％-70％，纳米噻唑锌颗粒粒径D 90为400nm＜D 90≤1100nm并且纳米噻唑锌颗粒粒径D 50为D 50＜90nm；或者，纳米噻唑锌颗粒粒径D 90为D 90≤400nm并且纳米噻唑锌颗粒粒径D 50为90nm≤D 50＜120nm。本发明提供的噻唑锌悬浮剂具有特殊的粒径分布状况，所述噻唑锌悬浮剂能够提高对作物病害的防治效果，且速效性和持效性方面的效果提高也非常显著。

Description

一种包含纳米噻唑锌的悬浮剂及其制备方法 技术领域
本发明属于农业化学领域，涉及纳米杀菌剂农药产品，具体的，涉及一种提高作物病害防治效果的包含纳米噻唑锌的悬浮剂及其制备方法。
背景技术
噻唑锌的化学名称为2-氨基-5-巯基-1,3,4-噻二唑锌，分子式为C 4H 4N 6S 4Zn。噻唑锌原药为灰白色粉末，在水和甲醇、乙醇、DMF、丙酮、异丙醇、乙腈、乙酸乙酯、甲烷等有机溶剂中的溶解度差，几乎不溶解。为了实现噻唑锌药效的更好发挥，需要制备具有更小颗粒粒径的噻唑锌制剂。目前商业化的噻唑锌制剂产品主要是含噻唑锌的悬浮剂，“碧生”(20％噻唑锌悬浮剂的商品名)中噻唑锌颗粒的粒径D 90为3-5微米左右，“碧生”在防治作物病害(特别是细菌性病害)上有较好效果。
发明人在研究噻唑锌颗粒微粒化的过程中发现，微粒化后的噻唑锌原药相较于未微粒化的噻唑锌原药，可形成更宽的应用范围，例如降低噻唑锌悬浮剂等制剂中的噻唑锌颗粒粒径有助于提高制剂药效。但是当粒径降低到一定大小以下的程度，例如颗粒粒径D 50降低到300nm以下的时候，由于粒径分布范围不合理，导致微粒化后的噻唑锌悬浮剂对某些作物的某些部位会有药害(具体可参见CN109122699A中的噻唑锌悬浮剂的活性试验结果)。
本发明因此需要解决噻唑锌悬浮剂的药效和药害问题，也就是需要改进噻唑锌悬浮剂的药效，同时降低噻唑锌悬浮剂的药害。
发明内容
为解决上述技术问题，本发明提供了一种包含纳米噻唑锌的悬浮剂，所述悬浮剂中包含纳米噻唑锌颗粒，纳米噻唑锌颗粒总重量占悬浮剂重量的百分比为1％-70％，纳米噻唑锌颗粒粒径D 90为400nm＜D 90≤1100nm，纳米噻唑锌颗粒粒径D 50为D 50＜90nm。
优选的，上述包含纳米噻唑锌的悬浮剂中，纳米噻唑锌颗粒粒径D 90为400nm＜D 90≤1100nm，纳米噻唑锌颗粒粒径D 50为40nm≤D 50＜90nm。
优选的，上述包含纳米噻唑锌的悬浮剂中，纳米噻唑锌颗粒粒径D 90为430nm≤D 90≤850nm，纳米噻唑锌颗粒粒径D 50为45nm≤D 50≤90nm。
优选的，上述包含纳米噻唑锌的悬浮剂中，纳米噻唑锌颗粒粒径D 90为430nm≤D 90≤1090nm，纳米噻唑锌颗粒粒径D 50为45nm≤D 50≤85nm。
优选的，上述包含纳米噻唑锌的悬浮剂中，纳米噻唑锌颗粒粒径D 90为420nm≤D 90≤630nm，纳米噻唑锌颗粒粒径D 50为45nm≤D 50≤80nm。
本发明还提供了一种包含纳米噻唑锌的悬浮剂，所述悬浮剂中包含纳米噻唑锌颗粒，纳米噻唑锌颗粒总重量占悬浮剂重量的百分比为1％-70％，纳米噻唑锌颗粒粒径D 90为D 90≤400nm，纳米噻唑锌颗粒粒径D 50为90nm≤D 50＜120nm。
优选的，上述包含纳米噻唑锌的悬浮剂中，纳米噻唑锌颗粒粒径D 90为110nm≤D 90≤400nm，纳米噻唑锌颗粒粒径D 50为90nm≤D 50＜120nm。
优选的，上述包含纳米噻唑锌的悬浮剂中，纳米噻唑锌颗粒粒径D 90为110nm≤D 90≤350nm，纳米噻唑锌颗粒粒径D 50为90nm≤D 50≤110nm。
优选的，上述包含纳米噻唑锌的悬浮剂中，纳米噻唑锌颗粒粒径D 90为260nm≤D 90≤390nm，纳米噻唑锌颗粒粒径D 50为95nm≤D 50≤115nm。
优选的，上述包含纳米噻唑锌的悬浮剂中，纳米噻唑锌颗粒粒径D 90为220nm≤D 90≤395nm，纳米噻唑锌颗粒粒径D 50为95nm≤D 50≤115nm。
优选的，上述包含纳米噻唑锌的悬浮剂中，纳米噻唑锌颗粒粒径D 10为10nm≤D 10≤50nm；优选的，纳米噻唑锌颗粒粒径D 10为17nm≤D 10≤49nm。
优选的，上述包含纳米噻唑锌的悬浮剂中，纳米噻唑锌颗粒的径距范围是0.705-22.060。
优选的，上述包含纳米噻唑锌的悬浮剂中，纳米噻唑锌颗粒的径距范围是0.705-17.410。
优选的，上述包含纳米噻唑锌的悬浮剂中，纳米噻唑锌颗粒的径距范围是1.898-22.060。
优选的，上述包含纳米噻唑锌的悬浮剂中，纳米噻唑锌颗粒的径距范围是1.636-12.442。
上述悬浮剂中，其中纳米噻唑锌颗粒的径距的计算公式为：
径距＝(D 90-D 10)/D 50。
优选的，上述包含纳米噻唑锌的悬浮剂中，所述纳米噻唑锌颗粒总重量占悬浮剂重量的百分比为5％-60％。
优选的，上述包含纳米噻唑锌的悬浮剂中，所述悬浮剂中含有表面活性剂、增稠剂、防腐剂、消泡剂、防冻剂中的一种或多种助剂。
优选的，上述包含纳米噻唑锌的悬浮剂中，所述表面活性剂选自EO/PO嵌段聚醚、萘磺酸缩合物钠盐、苯酚磺酸缩合物钠盐、甲基萘磺酸钠甲醛缩合物、亚甲基二萘磺酸钠、二辛基磺基琥珀酸钠盐、辛烯基琥珀酸淀粉钠、烷基酚甲醛树脂聚氧乙烯醚硫酸盐、月桂醇聚氧乙烯聚氧丙烯醚硫酸盐、烷基酚聚氧乙烯醚，脂肪醇聚氧乙烯醚、烷基萘磺酸盐、木质素磺酸盐、脂肪醇聚氧乙烯醚硫酸盐、丙烯酸均聚物钠盐、高分子聚羧酸盐、马来酸-丙烯酸共聚物钠盐中的一种或多种。
优选的，上述包含纳米噻唑锌的悬浮剂中，所述增稠剂选自黄原胶、羧甲基纤维素钠、聚乙烯醇、硅酸铝镁中的一种或多种；所述防腐剂选自水杨酸苯酯、对羟基苯甲酸丁酯、山梨酸钾、2-甲基-4-异噻唑啉-3-酮、5-氯-2-甲基-4-异噻唑啉-3-酮、1,2苯并异噻唑啉-3-酮、2-溴-2-硝基-1,3-丙二醇、3-碘-2-丙炔基-丁基氨基甲酸酯中的一种或多种；所述消泡剂选自有机硅消泡剂、GP聚醚消泡剂、GPE聚醚消泡剂、GPES聚醚消泡剂中的一种或多种；所述防冻剂选自乙二醇、丙二醇、丙三醇、异丙醇、尿素中的一种或多种。
优选的，本发明还提供了制备上述包含纳米噻唑锌的悬浮剂的方法，所述方法为：
将噻唑锌，和表面活性剂、增稠剂、防腐剂、消泡剂、防冻剂中的一种或多种，及水搅拌混合均匀后经砂磨机循环砂磨或多级砂磨，粒径达到纳米级后过滤除去砂磨介质，即得到包含纳米噻唑锌的悬浮剂，其中，所述砂磨机中至少一台砂磨机中的砂磨介质的直径大小为0.1mm-0.6mm。
优选的，上述方法中，所述砂磨介质为氧化锆珠，介质填充系数0.7-0.8，砂磨温度控制在30℃以下。
优选的，上述方法中，砂磨温度控制在25℃及以下。
优选的，上述方法中，所述砂磨后再经高速剪切得到包含纳米噻唑锌的悬浮剂。
优选的，上述纳米悬浮剂中，所述根据作物病害防治的需要，所述纳米悬浮剂中还可包含其他杀菌剂，其他杀菌剂的重量与噻唑锌重量的比例为 1:100-100:1。
本发明还提供了上述包含纳米噻唑锌的悬浮剂用于防治作物病害的用途。
优选的，上述用途中，所述作物病害为细菌性病害。
本发明的有益效果
本发明提供的包含纳米噻唑锌的悬浮剂相对于颗粒粒径D 50＞120nm、D 90＜400nm的噻唑锌悬浮剂，尤其是在开发微粒化噻唑锌原药过程中开发的颗粒粒径D 50＞120nm、D 90＜400nm的噻唑锌悬浮剂来说，一方面，本发明的噻唑锌的粒径D 90和D 50的分布状况具有更加独特的状况，另一方面，虽然本发明的噻唑锌粒径D 50更小，但是通过大颗粒噻唑锌和小颗粒噻唑锌的分布使得噻唑锌悬浮剂不会导致作物的药害状况发生。
本发明提供的噻唑锌悬浮剂具有特殊的粒径分布状况，所述噻唑锌悬浮剂能够提高对作物病害的防治效果，对水稻白叶枯病的防治，与颗粒粒径D 50＞120nm、D 90＜400nm的噻唑锌悬浮剂的防效相比，药后17天的防效能够最高提高13％左右，药后6天的防效最高能够提高16％，药后10天的防效最高能够提高22％，对青菜软腐病的防治，与颗粒粒径D 50＞120nm、D 90＜400nm的噻唑锌悬浮剂的防效相比，药后2天的防效最高能够提高18％，药后3天的防效最高能够提高36％，本发明的纳米噻唑锌对于病害的速效性和持效性方面的提高效果也非常明显。
本发明提供的纳米噻唑锌悬浮剂经过2年存储后，其粒径变化和防效变化都不大，存储的纳米噻唑锌悬浮剂与新制的纳米噻唑锌悬浮剂对青菜软腐病的防治中，药后2天的防治效果差异在1％左右，药后3天的防治效果差异在5％左右。
具体实施方式
一、制备实施例
制备实施例1：
按重量比分别称取噻唑锌原药20.0％、月桂醇聚氧乙烯聚氧丙烯醚硫酸盐3.0％、辛烯基琥珀酸淀粉钠2.0％、丙烯酸均聚物钠盐1.0％、高分子聚羧酸盐2.0％、黄原胶0.1％、硅酸铝镁2.0％、丙三醇3.0％、1,2苯并异噻唑啉-3-酮0.01％、2-甲基-4-异噻唑啉-3-酮0.01％、GPES聚醚消泡剂0.2％、水补至100％，投入到搅拌分散釜中，搅拌分散均匀后输送到砂磨机中砂磨，采用三级砂磨，第一级砂磨机所用砂磨介质为直径1.2mm的氧化锆珠，砂磨时间为40分钟，第二级砂磨机 所用砂磨介质为直径0.6mm的氧化锆珠，砂磨时间为30分钟，第三级砂磨机所用砂磨介质为直径0.3mm氧化锆珠与0.1mm的钇稳定氧化锆珠(两者比例为2/1)，从第三级砂磨机开始砂磨起，在砂磨第15分钟起取样，后续每隔10分钟取一次样，测量每个样品中噻唑锌颗粒的粒径，粒径情况如下表1所示。
表1噻唑锌悬浮剂新制的粒径数据
悬浮剂编号 取样时间(min) D 10(nm) D 50(nm) D 90(nm) 径距
FF-024-1 75 47.0 90.2 110.6 0.705
FF-024-2 65 46.4 96.2 182.4 1.414
FF-024-3 55 47.4 103.1 211.0 1.587
FF-024-4 45 37.6 107.3 349.8 2.910
FF-024-5 35 23.6 85.7 439.1 4.848
FF-024-6 25 18.0 52.8 767.6 14.197
FF-024-7 15 17.5 47.8 849.7 17.410
上述样品在经过2年的静置后，噻唑锌悬浮剂的质量依然满足悬浮剂的质量要求，没有分层和结块，再次测量噻唑锌悬浮剂中噻唑锌颗粒的粒径，噻唑锌颗粒的粒径情况如下表2。
表2噻唑锌悬浮剂存放2年后的颗粒粒径数据
悬浮剂编号 D 10(nm) D 50(nm) D 90(nm) 径距
FF-024-1C 46.6 114.1 263.2 1.898
FF-024-2C 46.9 114.8 257.5 1.834
FF-024-3C 46.7 110.6 242.3 1.769
FF-024-4C 29.2 97.0 385.4 3.672
FF-024-5C 22.5 80.7 436.9 5.135
FF-024-6C 18.3 54.6 660.8 11.767
FF-024-7C 17.6 48.2 1080.9 22.060
制备实施例2
按照上述制备实施例1的方法，按重量比分别称取噻唑锌原药20.0％、月桂醇聚氧乙烯聚氧丙烯醚硫酸盐3.0％、辛烯基琥珀酸淀粉钠2.0％、丙烯酸均聚物钠盐1.0％、高分子聚羧酸盐2.0％、黄原胶0.1％、硅酸铝镁2.0％、丙三醇3.0％、1,2苯并异噻唑啉-3-酮0.01％、2-甲基-4-异噻唑啉-3-酮0.01％、GPES聚醚消泡剂0.2％、水补至100％，投入到搅拌分散釜中，搅拌分散均匀后输送到砂磨机中砂磨，砂磨机所用砂磨介质为直径1.2mm的氧化锆珠，砂磨时长为160分钟、180 分钟时分别取样一次，分别得到颗粒粒径D 50＞120nm的噻唑锌悬浮剂样品，纳米噻唑锌的悬浮剂中的粒径情况如下表3。
表3砂磨制备颗粒粒径D 50＞120nm的噻唑锌悬浮剂的颗粒粒径情况
悬浮剂编号 取样时间(min) D 10(nm) D 50(nm) D 90(nm) 径距
FD-024-1 180 67.4 126.8 243.9 1.392
FD-024-2 160 80.3 193.5 362.3 1.457
二、生物活性测试
生测实施例1：水稻白叶枯病试验
1、药液配制
进行水稻白叶枯病试验的悬浮剂样品主要有：
制备实施例1制备的包含纳米噻唑锌的悬浮剂FF-024-7、FF-024-6、FF-024-5、FF-024-4、FF-024-3、FF-024-2、FF-024-1。
实施例2制备的颗粒粒径D 50＞120nm的噻唑锌的悬浮剂FD-024-1和FD-024-2。
碧生(20％噻唑锌悬浮剂)和龙克均(20％噻菌铜悬浮剂)为市售商品。
将上述悬浮剂样品分别稀释700倍，稀释到药液中的噻唑锌的浓度和噻菌铜的浓度为286mg/L。空白对照为清水，清水施用量与药液施用量相同。具体的情况如下表4。
表4噻唑锌悬浮剂样品稀释倍数和浓度
悬浮剂样品 稀释倍数 有效成分浓度(mg/L)
FF-024-1 700 286
FF-024-2 700 286
FF-024-3 700 286
FF-024-4 700 286
FF-024-5 700 286
FF-024-6 700 286
FF-024-7 700 286
FD-024-1 700 286
FD-024-2 700 286
碧生 700 286
龙克均 700 286
2、试验评价
2.1悬浮剂对水稻白叶枯病的长期防治效果及安全性
在本专利的申请人的仙居生测中心进行水稻白叶枯病的防治试验，防治试验是采用盆栽接种病菌的方式进行。
试验方法：参考康卓、顾宝根主编的《农药生物活性测试标准操作规范-杀菌剂卷》“SOP-SC-1113水稻白叶枯病盆栽法”进行，选用分蘖末期水稻，距叶尖2cm处蘸菌剪叶接种菌悬液(OD 600:1.0)，每盆剪叶10-15片，28℃黑暗保湿24h(RH>90％)；根据试验处理进行喷雾施药，每处理3盆水稻(1盆/重复)，每处理施药液量50mL；施药后28℃，光照培养，RH>60％。
调查方法：根据需要对《规范》的调查方法进行调整，由测量病斑面积改为病斑长度：培养17d后测量清水对照和药剂处理的病斑长度，计算每个处理的病斑长度的平均值，然后按照如下公式计算防效：
防效＝(清水对照病斑长度-药剂处理病斑长度)/清水对照病斑长度×100％
下面试验中，安全性评价中，“++++”表示无药害，当安全性评价中加号“+”的数量少于4个，例如“+++”、“++”、“+”表示有药害发生，加号“+”数量越少，表示药害越严重。
具体试验结果如下表5所示。
表5包含纳米噻唑锌的悬浮剂对水稻白叶枯病的长期防治效果
Figure PCTCN2021111791-appb-000001
Figure PCTCN2021111791-appb-000002
从表5中的防效数据能够看出，本发明制备的粒径D 90在110.6nm-849.7nm，D 50在47.8nm-90.2nm之间的悬浮剂能够实现防效在52％以上，而且没有药害发生，但是颗粒粒径D 50＞120nm的噻唑锌FD-024-1和FD-024-2的D 90在243.9nm和362.3nm，D 50在126.8nm和193.5nm的情况下，虽然防治效果比碧生和龙克均防效好，但是其存在药害的问题，药害主要表现为水稻叶片上存在心叶筒状叶和僵硬的状况，FD-024-1发生药害的水稻株数的比率在34.5％，FD-024-2发生药害的水稻株数的比率在28.7％。
2.2悬浮剂对水稻白叶枯病的短期防治效果
选用分蘖初期水稻，距叶尖3cm处蘸菌剪叶接种菌悬液(OD 600:1.0)，每盆剪叶10-15片，28℃黑暗保湿24h(RH>90％)；根据试验处理进行喷雾施药，每处理3盆水稻(1盆/重复)，每处理施药液量50mL；施药后放于培养室内(28-30℃、RH>60％)光照培养，培养6天和10天后调查并分级。试验结果如下表6所示。
表6包含纳米噻唑锌的悬浮剂对水稻白叶枯病的短期防治效果
Figure PCTCN2021111791-appb-000003
从表6能够看出，针对分蘖初期水稻的白叶枯病的防治，本发明制备的纳米噻唑锌悬浮剂FF-024-1至FF-024-7在药后6天的防效在73％以上，悬浮剂FD-024-1和FD-024-2的防治效果虽然比本发明的纳米噻唑锌悬浮剂的药效低，但是差异并不明显，但是在药后10天可以看出，本发明的纳米噻唑锌悬浮剂FF-024-1至FF-024-7显著高于悬浮剂FD-024-1和FD-024-2的防效，防效提高 6％-18％左右，说明本发明的纳米噻唑锌悬浮剂FF-024-1至FF-024-7的持效性好于颗粒粒径D 50＞120nm的噻唑锌悬浮剂FD-024-1和FD-024-2。
生测实施例2：青菜软腐病的试验
1、药液配制
进行青菜软腐病的悬浮剂样品主要有：
制备实施例1制备的包含纳米噻唑锌的悬浮剂FF-024-7、FF-024-6、FF-024-5、FF-024-4、FF-024-3、FF-024-2、FF-024-1。
实施例2制备的颗粒粒径D 50＞120nm的噻唑锌悬浮剂FD-024-1和FD-024-2。
碧生(20％噻唑锌悬浮剂)和龙克均(20％噻菌铜悬浮剂)为市售商品。
将上述悬浮剂样品分别稀释400倍，稀释到药液中的噻唑锌的浓度和噻菌铜的浓度为500mg/L。空白对照为清水，清水施用量与药液施用量相同。具体的情况如下表7。
表7噻唑锌悬浮剂样品稀释倍数和浓度
悬浮剂样品 稀释倍数 稀释后的药液浓度(mg/L)
FF-024-1 400 500
FF-024-2 400 500
FF-024-3 400 500
FF-024-4 400 500
FF-024-5 400 500
FF-024-6 400 500
FF-024-7 400 500
FD-024-1 400 500
FD-024-2 400 500
碧生 400 500
龙克均 400 500
2.试验评价
在本专利的申请人的仙居生测中心进行青菜软腐病的防治试验，防治试验是采用盆栽接种病菌的方式进行。试验方法：选用3叶1心期青菜，根据试验处理进行喷雾施药，每处理3个重复，每个重复4盆青菜(2株/盆)，每处理施药液量50mL；药后24h，每片叶柄处扎孔并点滴菌液10μL(OD 600:0.2)，25-28℃黑暗保湿24h；保湿24h后(即药后2天)搬出保湿房进行防治效果调查，然后在搬 出保湿房后24小时(即药后3天)进行防治效果调查和安全性调查。
调查方法：调查接菌叶片，以每叶片病斑长度占整个叶柄长度的百分率分级。分级方法(以叶片为单位)：
0级：无病斑；
1级：病斑长度占叶叶柄长度的1-10％；
3级：病斑长度占叶叶柄长度的11％-30％；
5级：病斑长度占叶叶柄长度的31％-50％；
7级：病斑长度占叶叶柄长度的51-100％；
9级：整株软烂。
病情指数计算方法如下：
病情指数＝[Σ(各级病叶数×相应病级数值)/调查总叶数×最高级代表值]×100
防治效果的计算方法如下：
防治效果＝[(对照病情指数-处理病情指数)/对照病情指数]×100％。
处理药剂对青菜软腐病的防治效果参见如下表8。
表8噻唑锌悬浮剂对青菜软腐病的防治及安全性调查
Figure PCTCN2021111791-appb-000004
Figure PCTCN2021111791-appb-000005
从表8能够看出，本发明制备的纳米噻唑锌悬浮剂FF-024-1至FF-024-7对青菜软腐病的药后3天防效高于45％，最高达到76％，而且没有任何药害症状发生。FD-024-1和FD-024-2对青菜软腐病的药后3天防效在37％左右，高于碧生和龙克均，但是经过该药剂处理的部分青菜的部分叶片正面产生了淡黄色点状斑点的药害症状，FD-024-1处理发生该药害症状的叶片数的比率在23.2％，FD-024-1处理发生该药害症状的叶片数的比率在19.5％。
生测实施例3：存储噻唑锌悬浮剂的效果验证
1、药液配制
制备实施例1制备的包含纳米噻唑锌的悬浮剂存储2年后的样品FF-024-1C、FF-024-2C、FF-024-3C、FF-024-4C、FF-024-5C、FF-024-6C、FF-024-7C分别稀释400倍，稀释到药液中的噻唑锌的浓度为500mg/L。空白对照为清水，清水施用量与药液施用量相同。具体的情况如下表9。
表9存储2年的纳米噻唑锌悬浮剂样品稀释倍数和浓度
悬浮剂样品 稀释倍数 稀释后的药液浓度(mg/L)
FF-024-1C 400 500
FF-024-2C 400 500
FF-024-3C 400 500
FF-024-4C 400 500
FF-024-5C 400 500
FF-024-6C 400 500
FF-024-7C 400 500
2.试验评价
在本专利的申请人的仙居生测中心进行青菜软腐病的防治试验，防治试验是采用盆栽接种病菌的方式进行。试验方法：选用3叶1心期青菜，根据试验处理进行喷雾施药，每处理3个重复，每个重复4盆青菜(2株/盆)，每处理施药液量50mL；药后24h，每片叶柄处扎孔并点滴菌液10μL(OD 600:0.2)，25-28℃黑暗保湿24h；保湿24h后(即药后2天)搬出保湿房进行防治效果调查，然后在搬出保湿房后24小时(即药后3天)进行防治效果调查和安全性调查，调查方法 同上。具体结果如下表10所示。
表10存储2年的纳米噻唑锌悬浮剂对青菜软腐病的防治效果
Figure PCTCN2021111791-appb-000006
本发明的纳米噻唑锌悬浮剂存储2年后,FF-024-1C至FF-024-7C对青菜软腐病的防治效果与新制的纳米噻唑锌悬浮剂FF-024-1至FF-024-7在青菜软腐病的防治效果方面差异不明显，新制纳米噻唑锌悬浮剂的FF-024-1至FF-024-7对青菜软腐病药后2天防效的平均值为65.54％，存储两年的纳米噻唑锌悬浮剂的FF-024-1C至FF-024-7C对青菜软腐病药后2天的防效的平均值为64.39％，防治效果差异不明显。新制纳米噻唑锌悬浮剂的FF-024-1至FF-024-7对青菜软腐病药后3天的防效的平均值为60.42％，存储两年的纳米噻唑锌悬浮剂的FF-024-1C至FF-024-7C对青菜软腐病药后3天的防效的平均值为55.85％，防治效果差异不明显。
表10的试验结果表明，本发明的纳米噻唑锌悬浮剂经过2年的存储，纳米噻唑锌悬浮剂中噻唑锌颗粒粒径的变化不明显，对青菜软腐病的防治效果变化不大。
三、验证实施例
1、包含纳米噻唑锌的悬浮剂制备
按重量比分别称取噻唑锌60％、月桂醇聚氧乙烯聚氧丙烯醚硫酸盐3％、辛烯基琥珀酸淀粉钠3.0％、高分子聚羧酸盐2.0％、马来酸-丙烯酸共聚物钠盐1.0％、黄原胶0.1％、异丙醇2.0％、2-溴-2-硝基-1,3-丙二醇0.02％、水补至100％，投 入到搅拌分散釜中，搅拌分散均匀后输送到砂磨机中砂磨，采用三级砂磨，第一级砂磨机所用砂磨介质为直径1.2mm的氧化锆珠，砂磨30分钟，第二级砂磨机所用砂磨介质为直径1.0mm的氧化锆珠，砂磨时间40分钟，第三级砂磨机所用砂磨介质为直径0.3mm的氧化锆珠，在第三级砂磨机中砂磨中，从第5分钟开始，每隔5分钟取样，到第105分钟最后一次取样，得到不同粒径的60％噻唑锌悬浮剂，测量每次取样的噻唑锌粒径，噻唑锌的粒径测量结果如下表11所示。
表11分段取样获得的包含纳米噻唑锌的悬浮剂的粒径
Figure PCTCN2021111791-appb-000007
2、药液配制
将上述悬浮剂样品分别稀释1200倍，稀释到药液中的噻唑锌的浓度和噻菌铜的浓度为500mg/L。空白对照为清水，清水施用量与药液施用量相同。
3、试验评价
在本专利的申请人的仙居生测中心进行青菜软腐病的防治试验，防治试验是采用盆栽接种病菌的方式进行。试验方法：选用3叶1心期青菜，根据试验处理进行喷雾施药，每处理3个重复，每个重复4盆青菜(2株/盆)，每处理施药液量50mL；药后24h，每片叶柄处扎孔并点滴菌液10μL(OD 600:0.2)，25-28℃黑暗保湿24h；保湿24h后(即药后2天)搬出保湿房进行防治效果调查，然后在搬出保湿房后24小时(即药后3天)进行防治效果调查和安全性调查，调查方法 同上。具体结果参见如下表12。
表12噻唑锌悬浮剂对青菜软腐病的防治及安全性调查
Figure PCTCN2021111791-appb-000008
从表12能够看出，FF-Y-01至FF-Y-013的粒径D 90在224.4nm-628.6nm范围内，粒径D 50在49.1nm-111.6nm范围内，其对青菜软腐病的药后2天的防效的平均值在64.17％，其与表8中的FF-024-1至FF-024-7对青菜软腐病的药后2天的防效的平均值65.54％相当。FF-Y-01至FF-Y-013对青菜软腐病的药后3天的防效的平均值在55.62％，其与表8中的FF-024-1至FF-024-7对青菜软腐病的药后3天的防效的平均值60.42％相当，而且，FF-Y-01至FF-Y-013对青菜软腐病的防治没有任何药害。通过对纳米噻唑锌悬浮剂的验证，证明纳米噻唑锌粒径D 90在224.4nm-628.6nm范围内，粒径D 50在49.1nm-111.6nm范围内的情况下，其能够实现与噻唑锌粒径D 90在110.6nm-849.7nm范围内，粒径D 50在47.8nm-90.2nm范围内相当的防治效果。

Claims (15)

  1. 一种包含纳米噻唑锌的悬浮剂，所述悬浮剂中包含纳米噻唑锌颗粒，纳米噻唑锌颗粒总重量占悬浮剂重量的百分比为1％-70％，纳米噻唑锌颗粒粒径D 90为400nm＜D 90≤1100nm，纳米噻唑锌颗粒粒径D 50为D 50＜90nm。
  2. 根据权利要求1所述的悬浮剂，其特征在于，纳米噻唑锌颗粒粒径D 90为400nm＜D 90≤1100nm，纳米噻唑锌颗粒粒径D 50为40nm≤D 50＜90nm。
  3. 根据权利要求2所述的悬浮剂，其特征在于，纳米噻唑锌颗粒粒径D 90为430nm≤D 90≤850nm，纳米噻唑锌颗粒粒径D 50为45nm≤D 50≤90nm，
  4. 根据权利要求2所述的悬浮剂，其特征在于，纳米噻唑锌颗粒粒径D 90为430nm≤D 90≤1090nm，纳米噻唑锌颗粒粒径D 50为45nm≤D 50≤85nm。
  5. 根据权利要求2所述的悬浮剂，其特征在于，纳米噻唑锌颗粒粒径D 90为420nm≤D 90≤630nm，纳米噻唑锌颗粒粒径D 50为45nm≤D 50≤80nm。
  6. 一种包含纳米噻唑锌的悬浮剂，所述悬浮剂中包含纳米噻唑锌颗粒，纳米噻唑锌颗粒总重量占悬浮剂重量的百分比为1％-70％，纳米噻唑锌颗粒粒径D 90为D 90≤400nm，纳米噻唑锌颗粒粒径D 50为90nm≤D 50＜120nm。
  7. 根据权利要求6所述的悬浮剂，其特征在于，纳米噻唑锌颗粒粒径D 90为110nm≤D 90≤400nm，纳米噻唑锌颗粒粒径D 50为90nm≤D 50＜120nm。
  8. 根据权利要求7所述的悬浮剂，其特征在于，纳米噻唑锌颗粒粒径D 90为110nm≤D 90≤350nm，纳米噻唑锌颗粒粒径D 50为90nm≤D 50≤110nm。
  9. 根据权利要求7所述的悬浮剂，其特征在于，纳米噻唑锌颗粒粒径D 90为260nm≤D 90≤390nm，纳米噻唑锌颗粒粒径D 50为95nm≤D 50≤115nm。
  10. 根据权利要求7所述的悬浮剂，其特征在于，纳米噻唑锌颗粒粒径D 90为220nm≤D 90≤395nm，纳米噻唑锌颗粒粒径D 50为95nm≤D 50≤115nm。
  11. 根据权利要求1-10任一项所述的悬浮剂，其特征在于纳米噻唑锌颗粒粒径D 10为10nm≤D 10≤50nm；优选的，纳米噻唑锌颗粒粒径D 10为17nm≤D 10≤49nm。
  12. 根据权利要求1-11任一项所述的悬浮剂，其特征在于纳米噻唑锌颗粒的径距范围是0.705-22.060。
  13. 根据权利要求1-12任一项所述的悬浮剂，其特征在于所述包含纳米噻唑锌的悬浮剂中含有表面活性剂、增稠剂、防腐剂、消泡剂或防冻剂中的一种或多种助剂。
  14. 权利要求1-13任一项所述的包含纳米噻唑锌的悬浮剂的制备方法，所述方法为：
    将噻唑锌，和表面活性剂、增稠剂、防腐剂、消泡剂、防冻剂中的一种或多种，及水搅拌混合均匀后经砂磨机循环砂磨或多级砂磨，粒径达到纳米级后过滤除去砂磨介质，即得到包含纳米噻唑锌的悬浮剂，其中，所述砂磨机中至少一台砂磨机中的砂磨介质的直径大小为0.1mm-0.6mm。
  15. 权利要求1-13任一项所述的包含纳米噻唑锌的悬浮剂用于防治作物病害的用途；优选的，所述作物病害为细菌性病害。
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CN109122699A (zh) * 2017-06-16 2019-01-04 浙江新农化工股份有限公司 一种包含噻唑锌颗粒的组合物及其制备方法
CN110272651A (zh) * 2018-03-13 2019-09-24 浙江新农化工股份有限公司 一种包含噻唑锌的涂料及噻唑锌涂料抗菌用途

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