WO2018228552A1 - 一种包含噻唑锌颗粒的组合物及其制备方法 - Google Patents

一种包含噻唑锌颗粒的组合物及其制备方法 Download PDF

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WO2018228552A1
WO2018228552A1 PCT/CN2018/091593 CN2018091593W WO2018228552A1 WO 2018228552 A1 WO2018228552 A1 WO 2018228552A1 CN 2018091593 W CN2018091593 W CN 2018091593W WO 2018228552 A1 WO2018228552 A1 WO 2018228552A1
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Prior art keywords
particles
zinc
composition
thiazole
particle diameter
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PCT/CN2018/091593
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English (en)
French (fr)
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徐群辉
沈海峰
李俊
张军
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浙江新农化工股份有限公司
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Publication of WO2018228552A1 publication Critical patent/WO2018228552A1/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
    • 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
    • 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
    • A01N25/12—Powders or granules
    • A01N25/14—Powders or granules wettable
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/01—Five-membered rings
    • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
    • C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
    • C07D285/12—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles
    • C07D285/125—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/01—Five-membered rings
    • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
    • C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
    • C07D285/12—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles
    • C07D285/125—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
    • C07D285/135—Nitrogen atoms

Definitions

  • the invention belongs to the field of pesticides, and particularly relates to the development of granular pesticide products, and in particular to a composition comprising zinc thiazol particles and a preparation method thereof.
  • Zinc thiazol is an important fungicide and its chemical name is zinc 2-amino-5-mercapto-1,3,4-thiadiazole.
  • the structure of zinc thiazole is composed of two groups to sterilize. One is the thiazole group, which has no inhibitory effect on bacteria in vitro, but it is a highly effective therapeutic agent in plants. In the pore channel of the plant, the bacteria are seriously damaged, and the cell wall becomes thinner and then collapses, resulting in bacteria. death. The second is zinc ion, which has both fungicidal and bactericidal effects.
  • the patent document CN00132119.6 discloses a thiadiazole metal complex and a preparation method and use thereof. Specifically, in the first embodiment, a preparation method of thiazole zinc is disclosed, but the thiazole zinc particle obtained by the preparation method is granulated. The diameter is not clear, and since the method used is a laboratory method, the particle size of the thiazole zinc is relatively large, and in the subsequent process of preparing the water-dispersible granule or suspending agent, it is necessary to increase the grinding strength to achieve the particle size satisfying the preparation. Requirements, but subsequent studies have found that the synthetic methods in this literature lead to loss of activity of thiazole zinc during subsequent applications.
  • the patent CN101953346B discloses that in the preparation of the zinc thiazole suspension, the particle size of the thiazole zinc needs to be ground to a D90 particle size of 3-5 ⁇ m.
  • the problem it solves is to achieve stability of the suspension comprising zinc thiazole, which does not explore the value of this particle size for the activity of zinc thiazolium.
  • the research content is also directed to the stability study of particle size greater than for pesticide formulations.
  • the present invention provides a particle size requirement of a formulation composition capable of solving the optimal effect of the thiazole zinc active action and an optimum activity of the formulation composition, and the provided product solves the current thiazole.
  • the original drug composition of zinc can be applied to the problem of controlling crop diseases and increasing the activity of controlling diseases, and solving the problem that the effect of the thiazole zinc original drug composition on the thiazole zinc preparation composition can be improved.
  • the present invention provides a prodrug composition comprising zinc thiazide, characterized in that the prodrug composition is composed of particles, and the mass of the thiazole zinc component in the granules accounts for greater than or equal to 95% by mass of the total mass of the granules.
  • the particle diameter D50 value is 6.0 ⁇ 1.0 ⁇ m to 26.0 ⁇ 1.0 ⁇ m, and the particle diameter D90 of the particles is less than or equal to 60.0 ⁇ m.
  • the mass of the thiazole zinc component in the granules is greater than or equal to 98% by mass of the total mass of the granules.
  • the above-mentioned original drug composition is actually also referred to as a thiazole zinc original drug composition granule, since the original drug of thiazolyl zinc generally contains impurities, which is a composition itself, and the active ingredient substance is insoluble to the thiazole zinc original drug.
  • Water and organic solvents exist in the form of solid particles. Therefore, it is generally required to be processed into a preparation to be used, and in the process of preparation into a preparation, the particles of zinc thiazolate must be ground, otherwise the original thiazole zinc cannot be used.
  • the invention solves the problem that the current thiazole zinc original drug cannot be applied, and obtains a new thiazole zinc particle satisfying the above particle size condition, and the thiazole zinc particle can be directly used for soil-borne diseases or bacteriality existing on crop branches. Disease or fungal disease.
  • the particle size of the thiazole zinc particles in the thiazole zinc prodrug composition is critical to the loss of the original drug activity during the processing of the back-end formulation.
  • the particle size of the thiazole zinc original drug composition is not required, and the effect of the particle size of the thiazole zinc original drug composition on the activity of the preparation in the preparation of the rear-end preparation is not considered, and the inventors of the present invention have studied It has been found that the particle size of the thiazole zinc original drug composition affects the activity of the preparation product after processing, and the particle size of the thiazole zinc original drug composition within the above particle size range is minimized after processing into a preparation, that is,
  • the original drug composition of the zinc thiazole has a particle size range of D50 of about 6-26 ⁇ m and a particle diameter D90 of 60 ⁇ m or less, and the processed drug mixture has a specific drug composition of a suspension agent having a particle diameter D90 of more than 60 ⁇ m.
  • the particle diameter D50 of the thiazole zinc original drug composition particle is 6.0 ⁇ 0.5 ⁇ m to 9.0 ⁇ 0.5 ⁇ m, and the particle diameter D90 value of the thiazole zinc original drug composition particle is 12.0 ⁇ . 1.0 ⁇ m to 18.0 ⁇ 1.0 ⁇ m.
  • the particle size of the thiazole zinc original drug composition particle satisfies a D50 value of about 6-9 ⁇ m, and the particle diameter D90 of the thiazole zinc original drug composition particle is about 12-18 ⁇ m, which can be directly used for an applicator, and can be realized.
  • the anti-effect of the spreader is improved. If the conventional thiazole zinc original drug is used, the anti-disease property of the spreader cannot be achieved, and it is necessary to be subjected to grinding processing to have a control effect.
  • the present inventors have found that in the case where the granules of the thiazole zinc original drug composition satisfy the above requirements, the smear prepared by directly preparing the original drug can effectively prevent diseases such as kiwi canker, tomato ulcer disease and/or apple tree rot disease.
  • the particle diameter D50 of the thiazole zinc original drug composition particle is 21.0 ⁇ 0.5 ⁇ m to 26.0 ⁇ 0.5 ⁇ m
  • the particle diameter D90 value of the thiazol zinc original drug composition particle is 42.0 ⁇ 1.0 ⁇ m to 52.0 ⁇ 1.0 ⁇ m.
  • the particle size of the thiazole zinc original drug composition particle reaches a D50 value of about 21-26 ⁇ m, and the particle diameter D90 of the thiazole zinc original drug composition particle is about 42-52 ⁇ m, it is suitable for the prevention and control of soil-borne diseases.
  • it can be processed directly into a wettable powder or a water-dispersible granule, which can prevent and cure diseases such as tomato bacterial wilt and other diseases without any grinding and maintaining the same particle size.
  • the quick-acting effect of prevention and control can be achieved, and the effectiveness of soil-borne diseases can also be achieved, because the zinc azole particles need to be combined with the soil on the one hand to fully contact the harmful microorganisms that cause the disease, and on the other hand, it is necessary to prevent the impact due to water. It leads to the loss of groundwater, so it solves the quick-acting and effective control of soil-borne diseases.
  • the thiazole zinc original drug composition particles are particles obtained by synthesis or without grinding or pulverization, or particles obtained by grinding or pulverization.
  • the thiazole zinc particle size and the existing thiazole zinc original drug composition which do not satisfy the above particle size requirements are directly obtained by changing the synthesis method.
  • the granules are obtained by grinding, and the granules of the original thiazole zinc obtained by the two methods exhibit different effects on the activity, and the particles obtained by direct synthesis have better effects on quick-acting properties, of course, large particles in the past.
  • the particles satisfying the particle size range obtained by grinding the thiazole zinc original drug composition particles can also achieve the control effect thereof, but the prior art does not consider that the original drug ground to the particle size range can be directly applied or not prepared.
  • the thiazole zinc original drug composition in the above particle size range can also achieve the control effect thereof, but the prior art does not consider that the original drug ground to the particle size range can be directly applied or not prepared.
  • the effect of controlling the disease is relatively small, and the thiazole satisfying the particle size requirement is obtained by grinding.
  • the preparation composition of the same thiazole zinc particle size is obtained after the zinc original drug composition is ground again, and the effect of controlling the disease has a certain loss.
  • the present invention also provides a formulation composition comprising zinc thiazide particles, wherein the total mass of the thiazole zinc particles is greater than or equal to 1%, less than or equal to 70% by mass of the mass of the formulation composition. It is characterized in that the thiazolyl zinc particles in the formulation composition have a particle diameter D50 value of 0.40 ⁇ 0.05 ⁇ m to 1.30 ⁇ 0.05 ⁇ m and a particle diameter D90 of less than or equal to 2.8 ⁇ m.
  • the present invention prepares a particle size change of a formulation composition of zinc thiazole by changing the particle size of the thiazole zinc original drug composition to cause a change in the control effect of the crop disease.
  • thiazole zinc is prepared as a suspending agent
  • the preparation of the suspending agent is to grind the particle size of the thiazole zinc to 3-5 ⁇ m.
  • the problem considered is that the formulation of the suspending agent is stable, because if the grinding is continued, the preparation is prolonged. Preparation time, and the cost of preparation increases. Therefore, it has not been considered in the past the relationship between the change in the particle size of thiazolyl zinc in the suspending agent and the control effect of crop diseases.
  • a thiazole zinc suspending agent which satisfies the above particle size requirements is obtained, which can achieve an effect of improving the control of fungal diseases and bacterial diseases, which is not thought of.
  • the change in particle size of thiazole zinc does not cause the activity to change too much or even change.
  • the thiazole zinc particle size becomes smaller, which may lead to an unknown reduction in the control effect or the occurrence of phytotoxicity, but it has been proved by practice that the particle size of the thiazole zinc particles in the formulation composition of the thiazole zinc is adjusted.
  • To the above range can significantly improve the control effect on the disease, such as improving the quick-acting effect of controlling bacterial diseases of crops, especially for the sudden bacterial diseases of certain crops.
  • the formulation composition of zinc thiazole will cause phytotoxicity on some crops, especially the seedlings of the crop, causing burnt spots on the leaves, and even the leaves are withered, so the preparation of zinc thiazole
  • the particle size of the thiazole zinc particles in the composition should not be too small. For example, when the particle diameter D50 of the particles is less than 300 nm, the disease control effect of some crops at the flowering or young fruit stage cannot be counted, which means that the disease statistics are affected. The phytotoxicity.
  • the thiazole zinc particles in the preparation composition are particles obtained by grinding or pulverizing the particles of the original drug composition having a particle diameter of D90 ⁇ 60 ⁇ m after synthesis, or thiazole in the preparation composition.
  • the zinc particles are particles obtained by grinding or pulverizing the particles of the thiazole zinc original drug composition having a particle diameter of D90 > 60 ⁇ m and grinding or pulverizing.
  • the preparation composition is prepared from the particles of the above-mentioned thiazole zinc original drug composition.
  • the particle size requirement of the thiazole zinc particles in the original drug composition for obtaining the above-mentioned thiazole zinc can be prepared by the above-mentioned thiazole zinc original drug composition capable of directly controlling the disease, or by large particles (particle diameter D90> 60 ⁇ m) was prepared by direct grinding.
  • the thiazole zinc preparation composition obtained by grinding the thiazole zinc preparation composition is more effective if the existing particle diameter D90 is applied.
  • the thiazole zinc preparation composition of the same particle diameter is prepared by preparing the zirconia zinc preparation composition of the same size of 60 ⁇ m, the effect is relatively poor, but the effect of the preparation composition can still be achieved.
  • the thiazole zinc particles in the formulation composition have a particle diameter D50 value of 0.70 ⁇ 0.05 ⁇ m to 1.30 ⁇ 0.05 ⁇ m, and a particle diameter D90 of 1.30 ⁇ 0.1 ⁇ m to 2.80 ⁇ 0.1 ⁇ m.
  • the zinc thiazide particles have a particle diameter D50 of about 0.70-1.30 ⁇ m, and the particle size D90 is about 1.30-2.80 ⁇ m, which is quick-acting in controlling conventional bacterial diseases. The effect, and there is not much change in terms of effectiveness.
  • the thiazole zinc particles in the formulation composition have a particle diameter D50 value of 0.40 ⁇ 0.05 ⁇ m to 0.60 ⁇ 0.05 ⁇ m, and a particle diameter D90 of 0.70 ⁇ 0.1 ⁇ m to 1.10 ⁇ 0.1 ⁇ m.
  • the thiazole zinc particles have a particle diameter D50 value of about 0.4 to 0.6 ⁇ m, and a particle size D90 of 0.7 to 1.1 ⁇ m, which has a quick-acting effect in controlling bacterial diseases, and It can solve sudden bacterial diseases and has not changed in terms of effectiveness.
  • the present invention also provides an agricultural medicament obtained by dilution of the above formulation composition.
  • the present invention also provides a method for preparing the above-mentioned thiazole zinc original drug composition, characterized in that the method comprises the following steps:
  • high-speed stirring is shear stirring, and the shear stirring speed is more than 1500 rpm.
  • the above stirring speed is the stirring speed requirement of general equipment in chemical production. Because the mixing efficiency of different reaction equipment is different, there will be differences in the specific stirring speed index. In short, the stirring speed is improved. The particles of the thiazole zinc prodrug composition become smaller, and the specific stirring speed is related to the equipment used.
  • the present invention also provides the use of the above-mentioned thiazolyl zinc original drug composition for controlling bacterial diseases or soil-borne diseases.
  • the use is achieved by directly preparing a thiazole zinc original drug composition into a spreader and water-dispersible particles. Agent or wettable powder.
  • the invention can find that the particle size D90 of the original drug composition is less than 60 ⁇ m by preparing the particles of different particle diameters of the thiazole zinc original drug composition, and can directly serve as an active ingredient of the medicament for controlling diseases, and does not need to be ground. machining.
  • the thiazole zinc original drug composition particles having the particle diameter D90>60 ⁇ m which have existed in the prior art cannot be directly prepared into a suspension agent without processing, and directly preparing other pharmaceutical dosage forms cannot solve the disease problem.
  • the particle size of the thiazole zinc original drug composition is D90 ⁇ 60 ⁇ m, although it cannot be directly prepared into a suspending agent without being processed, it is prepared as a spreading agent, a water-dispersible granule or a wettable powder without being processed by grinding or the like. After the formulation, it is possible to directly control certain diseases of certain crops.
  • the invention adopts the preparation of the particles of the optimal particle size range of the thiazole zinc original drug composition particles, and is used for preparing the thiazole zinc preparation, which not only improves the control effect of the bacterial disease of the thiazole zinc preparation composition, but also, in the thiazole
  • the slightly larger particle size thiazole zinc preparation composition can achieve the persistence of conventional diseases, and the slightly smaller particle size thiazole zinc preparation can solve the suddenness. Bacterial diseases or increase their quick-acting properties.
  • the thiazole zinc particles were prepared by a reaction for 3 hours, and the thiazole zinc particles were filtered, washed with water and dried to obtain thiazole zinc original drug composition particles.
  • the shear stirring speed is adjusted between 100 rpm and 4000 rpm to obtain zirconia zinc original drug composition particles of different particle sizes, and after adjusting the shear stirring speed to 1500 rpm or more, A thiazole zinc original drug composition particle having a particle diameter of D90 ⁇ 60 ⁇ m. The larger the stirring speed, the smaller the particle diameter of the prepared thiazole zinc original drug composition particles.
  • the thiazole zinc original drug composition particles shown in Table 1 below were obtained by adjusting the shear agitation speed. The particles of the original drug composition were tested, and the purity of the thiazole zinc was above 98%.
  • Example 2 Direct use efficacy of the thiazole zinc original drug composition
  • the thiazole zinc original drug composition granules of the above Table 1 were respectively prepared into a 2% thiazole zinc spreader and a 20% thiazole zinc water dispersion granule, and the original drug composition was directly subjected to no grinding treatment, and the thiazole zinc original drug composition was directly assisted.
  • the agent is mixed to prepare a medicament.
  • the 2% thiazole zinc spreader and the 20% thiazole zinc water dispersible granule were prepared, the particle size of the original drug used was different, and the other auxiliary components and their contents were the same.
  • the 2% thiazole zinc smear was used to control the kiwifruit ulcer disease.
  • the plants with the symptoms were selected for labeling, and the diseased shoots were uniformly smeared, and then treated with the drug, and blank control was set up, 3 treatments per treatment. Repeat, apply once every 5 days, and conduct a control investigation 7 days and 14 days after the last dose.
  • the potato black shank was controlled by using 20% thiazole zinc water dispersible granules by stirring and ditching the water-dispersible granules with 200 times by weight of the soil. Cut the potato pieces with black rickets with a knife, bring the bacteria to the knife, cut the seed potatoes, and bring the seed potatoes to the bacteria. When planting, use the medicine to carry out the ditch treatment, set a blank control, each treatment is repeated 3 times, 7 days after the treatment and A 21-day community survey was conducted to dig up potato chips for disease identification investigation.
  • Kiwifruit ulcer disease is a relatively serious area, and potato black shank is an artificially inoculated pathogen-inducing disease area.
  • the control plot is completely isolated from other plots, and all tests are carried out under the same conditions.
  • the incidence index of the blank control kiwi canker disease was 30%, and the incidence index of potato black shank disease was 57%.
  • the data in Table 2 indicates that the particle size D90 of the thiazole zinc original drug composition is less than 60 ⁇ m, and it can be used as a coating agent and a water-dispersible granule to achieve prevention and treatment of kiwi canker and potato black shank, and the best control effect
  • the particle diameter D90 of the thiazole zinc original drug composition was 51.8 ⁇ m or less, and the D50 was 25.6 ⁇ m or less, which was significantly different (5%).
  • the particle diameter D90 of the thiazole zinc original drug composition is 42.5-51.8 ⁇ m, the effect is good, and when the particle diameter D90 is 11.7-18.5 ⁇ m, the quick-acting property is good.
  • Example 3 The efficacy of a zinc thiazole formulation composition
  • the thiazole zinc original drug granules in the above Table 1 were processed into a 20% suspension, and a suspension of different thiazole zinc particle diameters was prepared by adjusting the time and the number of times of grinding.
  • A1-A15 in Table 1 was prepared as a 20% thiazole zinc suspension, wherein only the A2 thiazole zinc sample having a particle diameter D90 greater than 60 ⁇ m of the thiazole zinc original drug composition was prepared as a thiazole zinc suspension sample, and the thiazole zinc was prepared.
  • the thiazole zinc sample A12 having a particle size D90 of less than 20 ⁇ m was prepared as a thiazole zinc suspension.
  • the particle size of the thiazole zinc suspending agent of the following Table 3 obtained by grinding the A2 thiazole zinc original drug.
  • the particle size of the thiazole zinc suspending agent of the following Table 4 obtained by grinding the A12 thiazole zinc original drug.
  • the 20% thiazole zinc suspension prepared by the A2 and A12 original drug composition is used to control kiwi canker and tomato ulcer disease, and the 20% thiazole zinc suspension is diluted 400 times when used, and tested for 7 days, 10 days and 14 days respectively.
  • the control effect is 7 days.
  • the zinc thiazole formulation composition is more excellent in the case where the particle diameter D90 is less than 2.8 ⁇ m and the D50 is less than 1.4 ⁇ m, and the particle diameter D90 is 1.28-2.75 ⁇ m.
  • the effect of the drug has a long-lasting effect, and when the particle diameter D90 is 0.68-1.16 ⁇ m, the efficacy is particularly effective, and the difference is significant (5%).
  • the 20% thiazole zinc suspension prepared by A2 is generally The efficacy of the drug is relatively higher than that of the 20% thiazole zinc suspension prepared by A12, that is to say, the suspension prepared by the particle of the thiazole zinc original composition having a particle diameter D90 of less than 60 ⁇ m is more effective.

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Abstract

本发明涉及一种包含噻唑锌颗粒的组合物及其制备方法，所述组合物由颗粒组成，颗粒中包含噻唑锌成分的质量占颗粒总质量的质量分数大于或等于95％，颗粒的粒径D50值为6.0±1.0μm至26.0±1.0μm，颗粒的粒径D90小于或等于60.0μm。本发明发现在原药组合物的粒径D90小于60μm的情况下，其能够直接作为防治病害的药剂活性成分，并不需要对其进行研磨就能够满足其防治某些作物的某些病害的制剂成分。

Description

一种包含噻唑锌颗粒的组合物及其制备方法
相关申请的交叉引用
本申请要求于2017年06月16日提交中国专利局的申请号为CN201710456045.3、名称为“一种包含噻唑锌颗粒的组合物及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明属于农药领域，具体涉及颗粒状农药产品的开发，尤其具体的，涉及一种包含噻唑锌颗粒的组合物及其制备方法。
背景技术
噻唑锌是一种重要的杀菌剂，其化学名称为2-氨基-5-巯基-1,3,4-噻二唑锌。噻唑锌的结构由二个基团组成杀菌。一是噻唑基团，在植物体外对细菌无抑制力，但在植物体内却是高效的治疗剂，药剂在植株的孔纹导管中，细菌受到严重损害，其细胞壁变薄继而瓦解，导致细菌的死亡。二是锌离子，具有既杀真菌又杀细菌的作用。药剂中的锌离子与病原菌细胞膜表面上的阳离子(H+，K+等)交换，导致病菌细胞膜上的蛋白质凝固杀死病菌；部分锌离子渗透进入病原菌细胞内，与某些酶结合，影响其活性，导致机能失调，病菌因而衰竭死亡。在二个基团的共同作用下，杀病菌更彻底，防治效果更好，防治对象更广泛。
专利文献CN00132119.6公开了噻二唑类金属络合物及其制备方法和用途，具体地，在实施例1中公开了噻唑锌的制备方法，但是其制备方法所得到的噻唑锌颗粒的粒径是不明确的，而且由于采用的方法为实验室方法，获得噻唑锌粒径比较大，在后续制备水分散粒剂或悬浮剂的过程中，需要加大研磨力度，以实现粒径满足制剂的要求，但是后续的研究发现，该文献中的合成方法导致了噻唑锌在后续应用过程中的活性损失。
对于噻唑性的活性研究，通过噻唑基团的作用和锌离子的作用的结合来理解噻唑锌的杀菌机理只是一个方面，还有噻唑锌颗粒表面的界面作用对于作物和有害微生物的作用并没有研究清楚，所以噻唑锌的活性不能用一个统一的标准来研究。
目前，针对噻唑锌的研究中，专利CN101953346B公开了在制备包含噻唑锌悬浮剂的过程中，需要将噻唑锌的粒径研磨到D90粒径为3-5μm。其解决的问题是实现包含噻唑锌的悬浮剂的稳定，其并没有探究该粒径对于噻唑锌活性的价值。
专利文献CN104336081A中也有描述，是将噻唑锌在球磨机中球磨2-3小时，使微粒粒径全部在5μm以下，其所要解决的问题也是悬浮剂的稳定性问题。
在浙江大学魏方林博士的《农药新剂型微乳粒剂及其微乳液形成与稳定机理》的研究中，提到微乳粒剂的制备对于颗粒的要求，其明确了大多数情况下，粒径越小，制剂的透明度越高。但一些乳状液的透明度明显高于其它乳状液，但却大于其它乳状液。这表明，利用透明度高低来比较不同乳状液之间的粒径大小具有不确定性，同时也明确，对于乳化剂相同的乳状液，粒径越小，离心稳定性越高；但对于不同乳化体系的乳状液，粒径越小并不意味着离心稳定性越高。
其研究内容也是针对粒径大于对于农药制剂的稳定研究。
但是，对于噻唑锌而言，原药粒径的大小对于其活性的影响是什么样的，什么样的粒径最能够发挥噻唑锌原药的直接应用性能和制剂应用性能，制剂中噻唑锌粒径对于活性的影响以及采用不同粒径的原药噻唑锌颗粒制备的制剂活性效果会有什么变化，截至目前为止，并没有研究清楚。
发明内容
为解决上述技术问题，本发明提供了能够解决噻唑锌活性作用最佳发挥的原药组合物的粒径要求和最佳活性发挥的制剂组合物的粒径要求，所提供的产品解决了目前噻唑锌的原药组合物能否应用于防治作物病害和防治病害活性增加的问题，同时解决了噻唑锌原药组合物对噻唑锌制剂组合物效果是否能够提升的问题。
本发明提供了一种包含噻唑锌的原药组合物，其特征在于所述原药组合物由颗粒组成，颗粒中包含噻唑锌成分的质量占颗粒总质量的质量分数大于或等于95％，颗粒的粒径D50值为6.0±1.0μm至26.0±1.0μm，颗粒的粒径D90小于或等于60.0μm。
上述原药组合物中，优选的，颗粒中包含噻唑锌成分的质量占颗粒总质量的质量分数大于或等于98％。
上述的原药组合物实际上也称为噻唑锌原药组合物颗粒，因为噻唑锌的原药一般包含杂质，其本身为组合物，对于噻唑锌原药来说，其活性成分物质难溶于水和有机溶剂，以固体颗粒形式存在，因此，一般情况下需要进行加工成制剂才能够使用，而加工成制剂过程中，必须对噻唑锌的颗粒进行研磨，否则噻唑锌原药无法使用。本发明解决目前噻唑锌原药无法应用的问题，获得了一种新的满足上述粒径条件的噻唑锌颗粒，该噻唑锌颗粒能够直接用于土传病害或者是作物枝干上存在的细菌性病害或真菌性病害。
另一方面，噻唑锌原药组合物中的噻唑锌颗粒的粒径大小对于后端制剂加工过程中原药活性的损失至关重要。一般情况下，噻唑锌原药组合物的粒径大小没有要求，也没有考虑过噻唑锌原药组合物的粒径对于后端制剂加工中对制剂活性的影响，通过本发明的发明人的研究发现，噻唑锌原药组合物的颗粒粒径影响制剂产品加工后的活性，在上述粒径范 围内的噻唑锌原药组合物的颗粒粒径，其加工成制剂后的活性损失最小，也就是噻唑锌的原药组合物的颗粒粒径的D50的粒径范围约在6-26μm，粒径D90小于或等于60μm的情况下，其加工成的悬浮剂比粒径D90大于60μm的原药组合物颗粒加工成的制剂活性增加。
上述原药组合物中，优选的，所述噻唑锌原药组合物颗粒的粒径D50值为6.0±0.5μm至9.0±0.5μm，噻唑锌原药组合物颗粒的粒径D90值为12.0±1.0μm至18.0±1.0μm。
噻唑锌原药组合物颗粒的粒径满足D50值约为6-9μm，噻唑锌原药组合物颗粒的粒径D90值约为12-18μm的情况下，其能够直接用于涂抹剂，能够实现涂抹剂的防效提高，如果采用以往的噻唑锌原药，则无法实现涂抹剂的抗病性能，必需经过研磨加工才能够具有防治效果。而本发明发现在噻唑锌原药组合物的颗粒满足上述要求的情况下，其原药直接制备得到的涂抹剂能够有效防止猕猴桃溃疡病、番茄溃疡病和/或苹果树腐烂病等病害。
上述原药组合物中，优选的，所述噻唑锌原药组合物颗粒的粒径D50值为21.0±0.5μm至26.0±0.5μm，噻唑锌原药组合物颗粒的粒径D90值为42.0±1.0μm至52.0±1.0μm。
当噻唑锌的原药组合物颗粒的粒径达到D50值约为21-26μm，噻唑锌原药组合物颗粒的粒径D90值约为42-52μm的情况下，其适合于土传病害的防治，一方面其直接加工成可湿性粉剂或水分散粒剂，其不需要经过任何研磨，保持粒径不变的情况下，能够实现对土传病害如番茄青枯病等病害的防治，不仅能够实现防治的速效性，而且还能够实现土传病害的持效性，因为噻唑锌颗粒一方面需要与土壤进行结合，充分接触导致病害的有害微生物，另一方面又需要防止其因为水的冲击而导致流失到地下水中，所以解决了土传病害的速效性和持效性的防治。
上述原药组合物中，优选的，所述噻唑锌原药组合物颗粒为合成后未经过任何研磨或粉碎所获得的颗粒或经过研磨或粉碎获得的颗粒。
本发明在制备满足上述粒径的噻唑锌颗粒的原药组合物过程中，通过改变合成方法直接获得所述噻唑锌粒径和对现有的不满足上述粒径要求的噻唑锌原药组合物颗粒进行研磨获得，两种方式获得的噻唑锌的原药组合物的颗粒在活性上表现出不同的效果，直接合成获得的满足要求的颗粒在速效性上的效果更优，当然，以往大颗粒的噻唑锌原药组合物颗粒进行研磨获得的满足粒径范围的颗粒也能够实现其防治效果，但是现有技术中并没有认为研磨到该粒径范围的原药能够直接应用，也没有制备出上述粒径范围的噻唑锌原药组合物。
对于通过合成获得的噻唑锌原药组合物颗粒，其一般情况下再次研磨制备成噻唑锌颗粒的制剂组合物的时候，其防治病害的效果损失比较小，而经过研磨获得满足粒径要求的噻唑锌原药组合物再次研磨后获得相同噻唑锌颗粒粒径的制剂组合物，其防治病害的效果会有一定的损失。
本发明还提供了一种包含噻唑锌颗粒的制剂组合物，所述制剂组合物中，噻唑锌颗粒的总质量占制剂组合物质量的质量分数大于或等于1％，小于或等于70％，其特征在于所述制剂组合物中噻唑锌颗粒的粒径D50值为0.40±0.05μm至1.30±0.05μm，粒径D90小于或等于2.8μm。
本发明通过对噻唑锌原药组合物的粒径变化导致其作物病害的防治效果发生变化的原理出发，对噻唑锌的制剂组合物进行粒径更改。一般情况下，噻唑锌制备成悬浮剂，而以往制备悬浮剂都是将噻唑锌的粒径研磨到3-5μm，当时考虑的问题是满足悬浮剂的制剂稳定，因为如果继续进行研磨会延长制剂制备时间，且制备成本增加。因此说以往并没有考虑悬浮剂中噻唑锌粒径的变化与作物病害防效之间的关系。经过对噻唑锌粒径的调整，制备获得满足上述粒径要求的噻唑锌悬浮剂，其能够实现对真菌性病害和细菌性病害的防治效果提高，这是没有想到的。一般情况下，一般会认为噻唑锌的粒径变化不会导致活性变化过大，甚至是不会变化。又或者是有些学者理论上认为噻唑锌粒径变小反而会导致未可知的防效降低或者是药害的发生，但是经过实践证明，调整噻唑锌的制剂组合物中的噻唑锌颗粒的粒径到如上范围能够明显的提高其对病害的防治效果，例如提高防治作物细菌性病害的速效性，尤其是对某些作物的突发性细菌性病害具有良好的防治效果。
但是如果粒径过小，则会导致噻唑锌的制剂组合物会在某些作物上，尤其是作物的幼苗上产生药害，导致叶面烧灼斑，甚至是叶面枯萎，因此噻唑锌的制剂组合物中的噻唑锌颗粒的粒径不能过于小，例如当颗粒的粒径D50小于300nm的情况下，对于某些作物的花期或幼果期的病害防治效果无法统计，以为会导致影响病害统计的药害。
上述制剂组合物中，优选的，所述制剂组合物中的噻唑锌颗粒为合成后粒径D90≤60μm的原药组合物颗粒经过研磨或粉碎获得的颗粒，或者是，制剂组合物中的噻唑锌颗粒为粒径D90＞60μm的噻唑锌原药组合物颗粒经过研磨或粉碎后再次研磨或粉碎获得的颗粒。
上述制剂组合物中，优选的，所述制剂组合物由上述的噻唑锌的原药组合物的颗粒制备。
为获得上述满足要求的噻唑锌的原药组合物中的噻唑锌颗粒的粒径要求，可以通过上述的能够直接防治病害的噻唑锌原药组合物制备，也可以通过大颗粒(粒径D90＞60μm)直接研磨制备。如上所述，如果噻唑锌原药组合物的颗粒是直接合成获得的，则噻唑锌原药组合物经过研磨获得的噻唑锌制剂组合物的效果会更好一些，如果应用现有的粒径D90＞60μm的噻唑锌原药组合物的颗粒制备相同粒径的噻唑锌制剂组合物，则效果相对会差一些，但是依然能够实现制剂组合物所具有的效果。
上述制剂组合物中，优选的，所述制剂组合物中噻唑锌颗粒的粒径D50值为0.70±0.05μm至1.30±0.05μm，粒径D90为1.30±0.1μm至2.80±0.1μm。
上述噻唑锌制剂组合物中，噻唑锌颗粒的粒径D50值约为0.70-1.30μm，粒径D90约为1.30-2.80μm的制剂组合物，其在防治常规性细菌性病害方面具有速效性的效果，并且在持效性方面并没有发生太大变化。
上述制剂组合物中，优选的，所述制剂组合物中噻唑锌颗粒的粒径D50值为0.40±0.05μm至0.60±0.05μm，粒径D90为0.70±0.1μm至1.10±0.1μm。
上述噻唑锌制剂组合物中，噻唑锌颗粒的粒径D50值约为0.4-0.6μm，粒径D90为0.7-1.1μm的制剂组合物，其在防治细菌性病害方面具有速效性的效果，并且能够解决突发性的细菌性病害，并且在持效性方面并没有发生变化。
本发明还提供了通过上述制剂组合物稀释获得的农用药剂。
本发明还提供了上述噻唑锌的原药组合物的制备方法，其特征在于所述方法包括如下步骤：
将噻二唑的溶液和锌盐溶液混合，在高速搅拌下反应；
其中高速搅拌为剪切搅拌，剪切搅拌速度大于1500转/分钟。
通过研究发现，为实现噻唑锌的原药的颗粒变小，需要加大搅拌速度，因为通过降低反应底物浓度或提高反应温度或降低反应温度都无法解决噻唑锌原药组合物的粒径变化。
上述搅拌速度均为化工生产中的一般设备的搅拌速度要求，因为不同的反应设备，其搅拌的效率不同，所以在具体的搅拌的速度指标上也会有差异，总之是通过提高搅拌速度来实现噻唑锌原药组合物的颗粒变小，具体的搅拌速度的大小与所用的设备相关。
搅拌反应完成后所进行的过滤、洗涤和烘干均为常规技术，可按照已有的技术解决。
本发明还提供了上述噻唑锌原药组合物用于防治细菌性病害或土传病害的用途，优选的，所述用途的实现通过将噻唑锌原药组合物直接制备成涂抹剂、水分散粒剂或可湿性粉剂。
有益效果
本发明通过对噻唑锌原药组合物不同粒径颗粒的制备，发现原药组合物的粒径D90小于60μm的情况下，其能够直接作为防治病害的药剂活性成分，并不需要对其进行研磨加工。
另外，现有技术中已经存在的粒径D90＞60μm的噻唑锌原药组合物颗粒，其无法不加工直接制备成悬浮剂，直接制备成其他的药剂剂型也无法解决病害问题。但是当噻唑锌原药组合物的粒径D90≤60μm后，虽然也无法未加工直接制备成悬浮剂，但是作为涂抹剂、水分散粒剂或可湿性粉剂来说，其不经过研磨等加工制备成所述制剂后，则能够直接防治某些作物的某些病害。
本发明通过噻唑锌原药组合物颗粒的最佳粒径范围颗粒的制备，将其用于制备噻唑锌制剂，其不仅提高了噻唑锌制剂组合物的细菌性病害的防治效果，而且，在噻唑锌制剂组合物中，粒径的D90小于2.8μm的情况下，稍大粒径的噻唑锌制剂组合物能够实现常规病害的持效性，稍小粒径的噻唑锌制剂能够解决突发性的细菌性病害或提高其速效性。
具体实施方式
实施例1 噻唑锌原药组合物的制备
在0.5立方米的反应釜中加入0.09立方米的水，投入氢氧化钠27Kg，搅拌溶解之后，再投入噻二唑90Kg，搅拌得完全溶解的A液，在另一个0.2立方米的反应釜中，放置0.1立方米的水，然后投入硫酸锌20Kg溶解得B液。A液在剪切搅拌的状态下，将B液以0.05立方米/小时速度加入到含A液的反应釜中，持续剪切搅拌，维持温度范围在70-80℃，从加B液开始，经过3小时反应制备得到噻唑锌颗粒，将噻唑锌颗粒过滤、水洗和干燥后得到噻唑锌原药组合物颗粒。剪切搅拌的速度在100转/分钟至4000转/分钟之间进行调节，以获得不同粒径大小的噻唑锌原药组合物颗粒，当调节剪切搅拌速度达到1500转/分钟以上后，获得粒径D90≤60μm的噻唑锌原药组合物颗粒。搅拌速度越大，所制备得到的噻唑锌原药组合物颗粒的粒径越小。
根据上述方法，通过剪切搅拌速度的调整，获得如下表1所示的噻唑锌原药组合物颗粒。所述原药组合物颗粒经过检测，其噻唑锌纯度均在98％以上。
表1 噻唑锌样品的颗粒粒径分布情况和纯度情况
Figure PCTCN2018091593-appb-000001
Figure PCTCN2018091593-appb-000002
实施例2 噻唑锌原药组合物的直接使用药效
应用上述表1的噻唑锌原药组合物颗粒分别制备成2％噻唑锌涂抹剂和20％噻唑锌水分散粒剂，原药组合物不经过任何研磨处理，噻唑锌原药组合物直接与助剂混合制备药剂。制备2％噻唑锌涂抹剂和20％噻唑锌水分散粒剂时，除所采用的原药的粒径有差异，其余助剂成分及其含量均相同。
应用2％噻唑锌涂抹剂进行猕猴桃溃疡病防治，选取有发病症状的植株进行标记，将已发病的枝杆统一进行刮皮处理，然后分别用药剂进行处理，设空白对照，每个处理3个重复，隔5天涂抹一次，最后一次药后7天和14天进行防效调查。
应用20％噻唑锌水分散粒剂进行马铃薯黑胫病防治，通过将水分散粒剂与其200倍重量土壤搅拌并沟施。用刀切带黑胫病的薯块，使刀带菌，再切种薯，使种薯带菌，播种时用药剂进行沟施处理，设空白对照，每个处理3个重复，处理后7天和21天进行小区调查，挖取田间薯块进行病害鉴定调查。
猕猴桃溃疡病为发病比较严重的区域，马铃薯黑胫病为人工接种病菌诱导发病区域，所述防治地块与其他地块完全隔离，所有试验均在相同条件下实施。
空白对照猕猴桃溃疡病的发病指数为30％，马铃薯黑胫病的发病指数为57％。
上述药剂防治猕猴桃溃疡病和马铃薯黑胫病的结果如下表2。
表2 噻唑锌涂抹剂和水分散粒剂防治猕猴桃溃疡病和马铃薯黑胫病效果
Figure PCTCN2018091593-appb-000003
Figure PCTCN2018091593-appb-000004
表2的数据说明噻唑锌原药组合物的粒径D90小于60μm的情况下，其作为涂膜剂和水分散粒剂能够实现对猕猴桃溃疡病和马铃薯黑胫病的防治，最好的防治效果是在噻唑锌原药组合物的粒径D90为51.8μm以下，D50为25.6μm以下，同比差异显著(5％)。
在噻唑锌原药组合物的粒径D90为42.5-51.8μm的情况下，其持效性较好，而在粒径D90为11.7-18.5μm的情况下，其速效性较好。
实施例3 噻唑锌制剂组合物的药效
将上述表1中的噻唑锌原药颗粒加工成20％悬浮剂，通过调整研磨的时间和次数制备得到不同噻唑锌粒径的悬浮剂。
分别将表1中的A1-A15制备成20％噻唑锌悬浮剂，其中仅对噻唑锌原药组合物的粒径D90大于60μm的A2噻唑锌样品制备成噻唑锌悬浮剂样品，和将噻唑锌原药组合物粒径D90小于20μm的噻唑锌样品A12制备成噻唑锌悬浮剂。
通过A2噻唑锌原药研磨获得的如下表3粒径的噻唑锌悬浮剂粒径情况。
表3 D90大于60μm噻唑锌原药样品制备噻唑锌悬浮剂粒径
制剂编号 D50(μm) D90(μm)
A2-01 2.65 5.42
A2-02 1.61 3.32
A2-03 1.34 2.75
A2-04 0.89 1.99
A2-05 0.69 1.28
A2-06 0.59 1.16
A2-07 0.47 0.96
A2-08 0.33 0.68
A2-09 0.24 0.49
A2-10 0.17 0.35
A2-11 0.13 0.28
通过A12噻唑锌原药研磨获得的如下表4粒径的噻唑锌悬浮剂粒径情况。
表4 D90小于20μm噻唑锌原药样品制备噻唑锌悬浮剂粒径情况
制剂编号 D50(μm) D90(μm)
A12-01 2.24 4.58
A12-02 1.63 3.29
A12-03 1.38 2.78
A12-04 0.96 1.99
A12-05 0.76 1.34
A12-06 0.62 1.18
A12-07 0.47 0.97
A12-08 0.36 0.74
A12-09 0.26 0.53
A12-10 0.18 0.35
A12-11 0.12 0.26
通过A2和A12原药组合物制备获得的20％噻唑锌悬浮剂防治猕猴桃溃疡病和番茄溃疡病，使用时将20％噻唑锌悬浮剂稀释400倍，分别测试其7天、10天和14天的防效，用药间隔期为7天。
具体防治效果案件如下表5和表6。
表5 A2制备的20％噻唑锌悬浮剂对猕猴桃溃疡病和番茄溃疡病的防效
Figure PCTCN2018091593-appb-000005
Figure PCTCN2018091593-appb-000006
表6 A12制备的20％噻唑锌悬浮剂对猕猴桃溃疡病和番茄溃疡病的防效
Figure PCTCN2018091593-appb-000007
通过表5和表6可以看出，噻唑锌制剂组合物在粒径D90小于2.8μm，D50小于1.4μm的情况下，药效表现得更加优异，而且在粒径D90为1.28-2.75μm的情况下，其药效表现出持效期长的效果，而粒径D90为0.68-1.16μm的情况下，其药效表现为速效性特别好的效果，同比差异都显著(5％)。
通过表5和表6可以看出，虽然A2和A12制备的20％噻唑锌悬浮剂对猕猴桃溃疡病和番茄溃疡病的防效相差较小，但是总体上A2制备的20％噻唑锌悬浮剂的药效相对于A12制备的20％噻唑锌悬浮剂的药效要偏高一些，也就是说通过噻唑锌原药组合物的粒径D90小于60μm的颗粒制备的悬浮剂药效更优。
在20％噻唑锌悬浮剂的活性实验中，发现A2-9、A2-10、A2-11、A12-9、A12-10和A12-11在某些作物的幼苗期偶尔会有药害发生，尤其是大棚蔬菜的某些作物幼苗的叶片上会形成斑点，并且出现部分叶片枯萎的现象，也就是噻唑锌悬浮剂中D50小于300nm需要进一步明确其药效和药害之间的关系，并通过制剂的药害减缓助剂来解决此问题。

Claims (12)

  1. 一种包含噻唑锌的原药组合物，其特征在于所述原药组合物由颗粒组成，所述颗粒中包含噻唑锌成分的质量占颗粒总质量的质量分数大于或等于95％，颗粒的粒径D50值为6.0±1.0μm至26.0±1.0μm，颗粒的粒径D90小于或等于60.0μm。
  2. 根据权利要求1所述的原药组合物，其特征在于所述颗粒中包含噻唑锌成分的质量占颗粒总质量的质量分数大于或等于98％。
  3. 根据权利要求1所述的原药组合物，其特征在于所述噻唑锌原药组合物颗粒的粒径D50值为6.0±0.5μm至9.0±0.5μm，噻唑锌原药组合物颗粒的粒径D90值为12.0±1.0μm至18.0±1.0μm。
  4. 根据权利要求1所述的原药组合物，其特征在于所述噻唑锌原药组合物颗粒的粒径D50值为21.0±0.5μm至26.0±0.5μm，噻唑锌原药组合物颗粒的粒径D90值为42.0±1.0μm至52.0±1.0μm。
  5. 根据权利要求1-4任一项所述的原药组合物，其特征在于所述噻唑锌原药组合物颗粒为合成后未经过任何研磨或粉碎获得的颗粒或经过研磨或粉碎获得的颗粒。
  6. 一种包含噻唑锌颗粒的制剂组合物，其特征在于所述制剂组合物中，噻唑锌颗粒的总质量占制剂组合物质量的质量分数大于或等于1％，小于或等于70％，其特征在于所述制剂组合物中噻唑锌颗粒的粒径D50值为0.40±0.05μm至1.30±0.05μm，粒径D90小于或等于2.8μm。
  7. 根据权利要求6所述的制剂组合物，其特征在于所述制剂组合物中的噻唑锌颗粒为合成后粒径D90≤60μm的原药组合物颗粒未经过研磨或粉碎获得的颗粒，或者是，制剂组合物中的噻唑锌颗粒为粒径D90＞60μm的噻唑锌原药组合物颗粒经过研磨或粉碎后再次研磨或粉碎获得的颗粒。
  8. 根据权利要求7所述的制剂组合物，其特征在于所述制剂组合物由权利要求1所述的噻唑锌的原药组合物的颗粒制备。
  9. 根据权利要求6所述的制剂组合物，其特征在于所述制剂组合物中噻唑锌颗粒的粒径D50值为0.70±0.05μm至1.30±0.05μm，粒径D90为1.30±0.1μm至2.80±0.1μm。
  10. 根据权利要求6所述的制剂组合物，其特征在于所述制剂组合物中噻唑锌颗粒的粒径D50值为0.40±0.05μm至0.60±0.05μm，粒径D90为0.70±0.1μm至1.10±0.1μm。
  11. 由权利要求6-10所述的制剂组合物稀释获得的农用药剂。
  12. 一种权利要求1所述的原药组合物的制备方法，其特征在于所述方法包括如下步骤：
    将噻二唑的溶液和锌盐溶液混合，在高速搅拌下反应；
    其中，所述高速搅拌为剪切搅拌，所述剪切搅拌速度大于1500转/分钟。
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