TWI239807B - Covered type controlled release of agrochemical granular agent - Google Patents

Covered type controlled release of agrochemical granular agent Download PDF

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Publication number
TWI239807B
TWI239807B TW090130661A TW90130661A TWI239807B TW I239807 B TWI239807 B TW I239807B TW 090130661 A TW090130661 A TW 090130661A TW 90130661 A TW90130661 A TW 90130661A TW I239807 B TWI239807 B TW I239807B
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Taiwan
Prior art keywords
pesticide
granules
thermoplastic material
active ingredient
core
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TW090130661A
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Chinese (zh)
Inventor
Daisuke Kishi
Koichi Nagashima
Takashi Watanabe
Shinji Sakurai
Shigeru Ueno
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Mitsui Chemicals Inc
Meiji Seika Kaisha
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Application filed by Mitsui Chemicals Inc, Meiji Seika Kaisha filed Critical Mitsui Chemicals Inc
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Publication of TWI239807B publication Critical patent/TWI239807B/en

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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N25/00Biocides, 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
    • A01N25/26Biocides, 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 in coated particulate form
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N25/00Biocides, 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
    • A01N25/08Biocides, 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 solids as carriers or diluents
    • A01N25/10Macromolecular compounds
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N25/00Biocides, 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
    • A01N25/30Biocides, 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
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N25/00Biocides, 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
    • A01N25/34Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72Biocides, 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
    • A01N43/80Biocides, 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 one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2

Abstract

The invention provides a mixed agrochemical granular agent capable of performing a controlled release of two or more different kinds of agrochemical active ingredients having especially different solubility in water from each other and suitable for the treating method of a seedling box of rice at an individual eluting rate, and a method for producing the same. This controlled releasing mixed agrochemical granular agent is obtained by preparing a granulated material consisting of more than one kind of agrochemical active ingredient having a high water solubility, an inorganic diluting carrier and a first thermoplastic material hardly soluble in water, setting the granulated material as an inner core and covering the surface of the core with a mixture of more than one kind of agrochemical active ingredient different from the agrochemical active ingredients contained in the inner core and having a low water solubility, an inorganic diluting carrier and a second thermoplastic material hardly soluble in water to make an outer surface.

Description

1239807 A7 B7 五、發明說明(I ) 技術領域 本發明涉及含有兩種或者兩種以上不同種類的農藥活性成 分,爲了將各農藥活性成分溶出供給水介質所使用的緩釋性農 藥粒劑及其製造方法,更具體的說,涉及例如能適合水稻的育 苗箱用農藥粒劑的緩釋性農藥粒劑及其製造方法。作爲緩釋性 的育苗箱用農藥粒劑,它是施用在水稻育苗所使用的育苗箱 中,在其後插秧時,在同所插的秧苗一起移植到水田中後的一 段時間中,含在這種粒劑中的多種農藥活性成以各自的溶出速 度持續而緩慢地釋放出來。 背景技術 近年來,以種稻實現低成本爲目的迅速地推進水田的大規模 生産和機械化。與此相應有關農藥的施撒方法的技術革新也層 出不窮,研究出各種方便高效的製劑及施撒方法。作爲其中一 例,在插秧前的水稻育苗箱中施用農藥組合物的育苗箱處理法 的開發取得重大進展。這種水稻栽培的育苗箱處理法的最大優 點是對於秧苗可在插秧同時施加農藥。而且,農藥同秧苗一起 移植到水田後,由於在所使用的農藥製劑中所含有的農藥活性 成分的緩慢釋放,插秧後在一段長時間内可以達到以防治病蟲 害的目的。由於這個優點,育苗箱處理法,對在插秧期間必須 施撒的農藥而言是理想的方便高效的施用法。 另一方,近年來,同只含一種農藥活性成分的製劑相比,通 過將兩種以上的農藥活性成分,例如殺蟲劑和殺菌劑組合,進 行一次處理就能同時防治病蟲害的農藥製劑爲人們所追求。總 之,顯示不同作用的,兩種以上的農藥活性成分被緩慢釋放的 3 (請先閱讀背面之注意事項再填寫本頁) 錶1239807 A7 B7 V. Description of the invention (I) TECHNICAL FIELD The present invention relates to a slow-release pesticide granule containing two or more different kinds of pesticide active ingredients, and used to dissolve each of the pesticide active ingredients into an aqueous medium, and to use them The manufacturing method, more specifically, relates to, for example, a slow-release pesticide granule that is suitable for agrochemical granules for rice seedling boxes and a method for manufacturing the same. As a slow-release seedling box pesticide granule, it is applied to the seedling box used for rice seedlings. When the seedlings are subsequently transplanted, the seedlings are transplanted into the paddy field with the inserted seedlings for a period of time. The multiple pesticides in this granule are active and released slowly and continuously at their respective dissolution rates. Background Art In recent years, large-scale production and mechanization of paddy fields have been rapidly promoted with a view to achieving low cost by growing rice. Correspondingly, technological innovations in pesticide application methods have been continuously developed, and various convenient and efficient preparations and application methods have been developed. As an example, significant progress has been made in the development of a seedling box treatment method in which a pesticide composition is applied to a rice seedling box before transplanting. The biggest advantage of this rice cultivation nursery box treatment method is that pesticides can be applied to the seedlings at the same time as transplanting. In addition, after the pesticide is transplanted into the paddy field with the seedlings, due to the slow release of the pesticide active ingredients contained in the pesticide formulation used, the purpose of controlling pests and diseases can be achieved for a long time after transplanting the seedlings. Because of this advantage, the nursery box treatment method is an ideal convenient and efficient application method for pesticides that must be applied during transplanting. On the other hand, in recent years, compared with preparations containing only one pesticide active ingredient, by combining two or more pesticide active ingredients, such as pesticides and fungicides, pesticide preparations that can simultaneously control pests and diseases for one treatment are people. Pursued. In short, two or more pesticide active ingredients showing slow action are slowly released. 3 (Please read the precautions on the back before filling this page) Table

訂----;-----線丨I 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 1239807 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明(;►) 混合製劑,具體地,在水稻栽培期間中,在必須防治病蟲害的 30日一60日之間,或者根據情況在比60日更長的時間中,能 夠持續釋放農藥活性成分的混合製劑爲人們所追求。 作爲這樣的將兩種以上農藥活性成分緩慢釋放的例子,在特 開2000—44404號公報中,公開了一種混合製劑,其構造是, 對於含有緩慢釋放所必須的農藥活性成分的内核粒子,做成以 樹脂包覆其表面的包覆顆粒後,進一步在該樹脂被包覆顆粒的 外側設置含有別的農藥活性成分的外層部。此處所記載的混合 製劑的結構的重要特性是:1、其結構必須是以樹脂包覆内核粒 子的表面;2、外層部也可以不必做成緩慢釋放型;3、在内核 粒子和外層部各自所主要含有的兩種農藥活性成分的水溶解度 的差異不作爲特別要考慮的問題。 若更詳細地參照特開2000—44404號公報,關於以樹脂包覆 内核粒子的作用,在表示試驗例1 (溶出試驗)的結果的表4中, 當同實施例2—4和比較例2—4的結果比較時,可以明顯地看 出,以樹脂包覆内核粒子的實施例2—4與沒有包覆内核粒子的 比較例2—4相比,由於抑制了在内核粒子所含有的化合物的溶 出,設置樹脂被膜對内核粒子中所含有的農藥活性成分的緩慢 釋放具有顯著貢獻(控制溶出)。但是,由於在配製成内核粒子 後,另外設置了以樹脂包覆其表面的工序,當然的是,粒劑製 造的工序數則增多,伴隨而來的是作業成本也提高。 另外,關於不必使外層部也緩慢釋放這點,在試驗例1(溶 出試驗)中,其溶出特性被驗證的實施例1 一3是使用無機製固 體載體成形外層部,尤其是由於顯示的事實是沒有進行緩釋性 4 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) f請先閱讀背面之注音?事項再填寫本頁>>Order ----; ----- line 丨 I Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is printed in accordance with China National Standard (CNS) A4 (210 X 297 mm) 1239807 A7 B7 Intellectual Property of the Ministry of Economic Affairs Printed by the Bureau ’s Consumer Cooperatives V. Invention Description (; ►) Mixed preparations, specifically, during the rice cultivation period, between 30 days and 60 days that must be controlled by pests or diseases, or longer than 60 days depending on the situation In China, a mixed preparation capable of continuously releasing active ingredients of pesticides is sought after. As an example of such slow release of two or more pesticide active ingredients, Japanese Patent Application Laid-Open No. 2000-44404 discloses a mixed preparation having a structure in which core particles containing the pesticide active ingredient necessary for slow release are made After coating particles on the surface of the resin-coated particles are formed, an outer layer portion containing another pesticide active ingredient is further provided on the outside of the resin-coated particles. The important characteristics of the structure of the mixed preparation described here are: 1. Its structure must be coated with the surface of the core particles by resin; 2. The outer layer portion does not need to be made into a slow release type; 3. The core particles and the outer layer portion are each separate The difference in water solubility of the two main pesticide active ingredients is not a special consideration. Referring to Japanese Patent Application Laid-Open No. 2000-44404 for more details, regarding the effect of coating the core particles with a resin, Table 4 showing the results of Test Example 1 (dissolution test) is the same as that of Examples 2-4 and Comparative Example 2 When comparing the results of -4, it can be clearly seen that, in Example 2-4 in which the core particles were coated with resin, compared with Comparative Example 2-4 in which the core particles were not coated, the compounds contained in the core particles were suppressed. The dissolution of the resin film has a significant contribution to the slow release of the pesticide active ingredient contained in the core particles (controlling the dissolution). However, after preparing the core particles, a step of coating the surface with a resin is additionally provided. Of course, the number of steps for manufacturing the granules is increased, and the operation cost is also increased. In addition, regarding the point that it is not necessary to slowly release the outer layer portion, in Test Example 1 (dissolution test), Examples 1 to 3 whose dissolution characteristics were verified were formed by using an unstructured solid carrier to form the outer layer portion, especially due to the facts shown Is it slow-releasing? 4 This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm). F Please read the note on the back first? Matters refill this page > >

Man · I n —ϋ 1 i·— l n Γ 、· i n n mmaMm n ϋ Bmmmmm I · 言口 一 1239807 A7 B7 經濟部智慧財產局員工消費合作社印製 五、1墓造14有μ論的餘地。但是在表4中,顯示出在外層部所 含有的農藥活性成分的安可在水中慢慢溶出的結果。這種緩慢 的溶出,安可在20°C的水溶解度爲80ppm,由於安可本身是較 難溶於水的化合物,可以理解到,源於此反映出,在靜置狀態 其溶出速度也很低。而且,試驗時間同日相比又是較短的時 間,可以推測到在這種程度的時間内,僅是構成外層部的無機 固體載體成形層的破裂,而不必進行緩釋性處理也能抑制同水 介質的接觸。 , 關於内核粒子和外層部各自所含有的兩種農藥活性成分,在 該特開2000—44404號公報中對所使用的農藥活性成分的水溶 解度沒有特別考慮,至於兩者的水溶解度的差異則完全未予考 慮。順便說一下,對於在這些實施例中所示的混合製劑而言, 在外層部所含有的安可的水溶解度爲如上所述的80ppm,在内核 粒子中所含有的噻菌靈在20°C的水溶解度爲150ppm,其差異僅 爲70ppm,沒有大的差別。 另外,如特開2000—26206號公報中所示,水溶解度高的農 藥活性成分的緩慢釋放使用蠟已爲公衆所知。然而,採用使用 蠟這樣的疏水性物質的緩釋化方法,對於兩種以上的農藥活性 成分,尤其是對水的溶解具有極大差異的兩種農藥活性成分, 當使用同一種蠟使其緩釋化時,若選擇對一種農藥活性成分的 釋放速度爲最佳的蠟,則對另一種農藥活性成分的釋放速度或 者極快,或者相反極慢,要達到使兩者都具有適當的較緩慢的 釋放速度是困難的。即,限於本發明的發明人所知,作爲將水 溶解度具有極大差異的兩種以上的農藥活性成分包含在一種顆 5 ‘紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) J1 *—i l· I--------------^^------^ (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 1239807 A7 -__ B7 五、發明說明(令) 粒製劑中,使這兩種以上的農藥活性成分同時緩釋化的農藥製 劑,現仍不知道合適的劑型。另外,分別使用兩種以上的蠟於 各農樂活性成分的緩釋化的例子也未見報導。 如上所述,含有兩種以上農藥活性成分,至少有關其中一種 農藥活性成分使其緩釋化的農藥製劑的技術方案的,在至少含 有兩種水溶解度具有極大差異的農藥活性成分的農藥製劑中, 若能使兩者同時都能緩釋化從而使得各自.以不同的溶出速度釋 放,以製成例如適合用作水稻育苗箱處理法所使用的農藥粒 劑,至今尚未見到滿足這個要求的新劑型方案。 發明内容 本發明的目的就在於解決上述問題,提供一種例如人們所期 望的水稻的育苗箱處理法所使用的新型的劑型緩釋性農藥粒劑 及其高效的製造方法,它是在一種農藥製劑中,含有不同的兩 種或兩種以上的,水溶解度具有極大差異的農藥活性成分的情 況下,使得該水溶解度具有極大差異的農藥活性成分的每一個 都以各自所希望的溶出速度釋放而同時實現緩釋化。 本發明的發明人就上述要解決的問題進行深入研究後認 爲,當將兩種或兩種以上的,水溶解度具有極大差異的農藥活 性成分分別緩釋化時,可通過以下方法製成具有雙層結構的粒 劑,即,將水溶解度高的農藥活性成分分散在蠟黏黏合料中成 形爲製粒物而將其作爲内核,另一方面,將水溶解度低的農藥 活性成分,同比内核的蠟的熔點要低的另一種蠟一起混合再包 覆在内核的表面而形成外層部。 本發明的發明人通過採用這種結構,可以看到,内粒中的水 6 本紙張尺度適用中國國家標準(CNS)A4規格(210>< 297公釐) — hit U--------------^---Ϊ------^0 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 1239807 A7 _ B7 五、發明說) 溶解度局的農藥活性成分和外層中的水溶解度低的農藥活性成 分兩者都實現了緩釋化。 本發明的農藥粒劑更具體的如以下所述製作。 首先,將至少一種以上的水溶解度高的農藥活性成分,無機 系稀釋載體及作爲蠘成分所使用的難溶於水的第一熱塑性材料 加熱、混合,製粒,製作成具有各成分均勻分散的内核的製粒 物。 、 隨後,將至少一種以上的水溶解度低的農藥活性成分,無機 系稀釋載體及比第一熱塑性材料熔點低的、難溶於水的第二熱 塑性材料在下超過上述第一熱塑性材料的熔點的溫度下加熱, 混合而得到各成分均勻分散的混合物,將該混合物包覆在作爲 上述内核的製粒物的表面經冷卻後即製成本發明的具有二層結 構的粒劑。 經本發明的發明人研究證實,在本發明的粒劑中,通過採用 如上配製的雙層結構,在内核中所含有的農藥活性成分,不管 其水溶解度高與否,由於第一熱塑性材料的作用使其達到充分 的緩釋化,在外層部所含有的另外的農藥活性成分,加之農藥 活性成分本身難溶於水,由於第二熱塑性材料的作用使其充分 實現緩釋化,其結果,在一種粒劑中的兩種或兩種以上的水溶 解度不同的農藥活性成分都可以分別實現緩釋化。本發明的發 明人通過這些研究,探索根據親自得到的知識以至完成本發明。 艮P,本發明的緩釋性農藥粒劑是爲了將農藥的活性成分持續 地溶出供給給水介質的所使用緩釋性的農藥粒劑,上述粒劑具 有由内核和包覆在内核表面的外層部構成的包覆型粒劑的結 (請先閱讀背面之注意事項再填寫本頁)Man · I n —ϋ 1 i · — l n Γ, · i n n mmaMm n ϋ Bmmmmm I · Speech 1 1239807 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. There is room for μ in the tomb construction. However, Table 4 shows the results of the slow dissolution of encore of the pesticide active ingredient contained in the outer layer portion in water. This slow dissolution, the water solubility of Encore at 20 ° C is 80ppm. Since Encore is a relatively difficult water-soluble compound, it can be understood that this reflects that its dissolution rate is also very high in the standing state. low. In addition, the test time is shorter than that of the same day. It can be inferred that within this period of time, only the inorganic solid carrier forming layer constituting the outer layer portion is broken, and it is possible to suppress the same without the need for slow release treatment. Contact with aqueous media. Regarding the two kinds of pesticide active ingredients contained in the inner particle and the outer layer part, in Japanese Patent Application Laid-Open No. 2000-44404, there is no special consideration for the water solubility of the pesticide active ingredient used. As for the difference in water solubility between the two, Not considered at all. By the way, for the mixed preparations shown in these examples, the water solubility of Encore contained in the outer layer portion was 80 ppm as described above, and the thiabendazole contained in the core particles was at 20 ° C. Water solubility is 150ppm, the difference is only 70ppm, there is no big difference. In addition, as shown in Japanese Patent Application Laid-Open No. 2000-26206, waxes for slow release of agriculturally active ingredients having high water solubility have been known to the public. However, using a slow-release method using a hydrophobic substance such as wax, for two or more pesticide active ingredients, especially two pesticide active ingredients that have a great difference in water solubility, when the same wax is used for sustained release During chemical conversion, if the wax with the best release rate for one pesticide active ingredient is selected, the release rate for the other pesticide active ingredient is extremely fast, or the opposite is extremely slow. The speed of release is difficult. That is, it is limited to the present inventor's knowledge, and as a method of including two or more pesticide active ingredients having greatly different water solubility in one grain of 5 ′ paper, the Chinese National Standard (CNS) A4 specification (210 X 297 mm) is applicable. J1 * —il · I -------------- ^^ ------ ^ (Please read the precautions on the back before filling out this page) Employees ’Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs Printing 1239807 A7 -__ B7 V. Description of the Invention (Policy) In the granule formulation, the pesticide formulation which releases more than two kinds of pesticide active ingredients at the same time is still unknown. In addition, no examples of sustained release of two or more waxes for each of the agricultural active ingredients have been reported. As mentioned above, for a technical solution that contains at least two pesticide active ingredients and at least one of the pesticide active ingredients slows down the release of a pesticide formulation, in a pesticide formulation containing at least two pesticide active ingredients with greatly different water solubility If both can be slow-released at the same time so that they can be released at different dissolution rates to make, for example, pesticide granules suitable for use in rice seedling box treatment methods, so far no one that meets this requirement has been seen. New dosage form program. SUMMARY OF THE INVENTION The object of the present invention is to solve the above problems, and to provide a new type of slow-release pesticide granules used in a rice seedling box treatment method desired by people, and an efficient manufacturing method thereof. In the case of containing two or more different pesticide active ingredients having greatly different water solubility, each of the pesticide active ingredients having such a large difference in water solubility is released at a respective desired dissolution rate and At the same time, slow release is achieved. The inventors of the present invention conducted in-depth research on the problems to be solved, and thought that when two or more kinds of pesticide active ingredients with great differences in water solubility were sustained-released, they could be prepared by the following methods: Granules with a double-layer structure, that is, a pesticide active ingredient with high water solubility is dispersed in a wax binder to be formed into a granule and used as a core. On the other hand, a pesticide active ingredient with low water solubility is kerneled year-on-year. Another wax with a lower melting point is mixed with another wax and then coated on the surface of the inner core to form an outer layer portion. By adopting this structure, the inventor of the present invention can see that the paper size of the inner grains 6 is in accordance with the Chinese National Standard (CNS) A4 specification (210 > < 297 mm) — hit U ----- --------- ^ --- Ϊ ------ ^ 0 (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1239807 A7 _ B7 5 (Invention) Both the pesticide active ingredient in the solubility board and the pesticide active ingredient with low water solubility in the outer layer have been slow-released. The pesticide granules of the present invention are more specifically produced as described below. First, at least one or more water-soluble pesticide active ingredients, an inorganic dilution carrier, and a first water-insoluble thermoplastic material used as a rhenium component are heated, mixed, and granulated to produce a uniformly dispersed component. Kernel pellets. Then, at least one or more pesticide active ingredients having a low water solubility, an inorganic dilution carrier, and a second thermoplastic material that has a lower melting point than the first thermoplastic material and is difficult to dissolve in the water are lowered below the melting point of the first thermoplastic material. The mixture is heated under heating and mixed to obtain a uniformly dispersed mixture of the components. The mixture is coated on the surface of the granulated material as the core, and the granule having the two-layer structure of the present invention is prepared after cooling. The research by the inventors of the present invention has confirmed that in the granules of the present invention, by adopting the double-layer structure prepared as above, the pesticide active ingredient contained in the core, regardless of its high water solubility, is due to the effect of the first thermoplastic material It achieves a sufficient sustained release, and the additional pesticide active ingredient contained in the outer layer part, coupled with the pesticide active ingredient itself, is hardly soluble in water. Due to the action of the second thermoplastic material, it fully realizes sustained release. As a result, in Two or more kinds of pesticide active ingredients with different water solubility in one granule can realize sustained release respectively. Through these studies, the inventor of the present invention explored the knowledge obtained by himself and completed the present invention. That is, the slow-release pesticide granules of the present invention are sustained-release pesticide granules used to continuously dissolve the active ingredients of pesticides and supply them to an aqueous medium. The granules have an inner layer and an outer layer covering the inner surface of the inner core. Of the coated granules (please read the precautions on the back before filling this page)

本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 1239807 A7 B7 五、發明說明(k ) 構,上述内核是由20°C的水溶解度在10⑻ppm以上一 10%以下的 至少一種農藥活性成分,無機系稀釋性載體,難溶於水的第一 熱塑性材料構成的製粒物,上述外層部是由20°C的水溶解度爲 0.01—500ppm的至少一種農藥活性成分,無機系稀釋載體和比 上述内核中所含有的第一熱塑性材料的熔點低的而且屬不同材 料的難溶於水的第二熱塑材料組成的包覆層,使用這種包覆型 粒劑的結構,上述内核中所含有的農藥活性成分和外層部中所 含有的農藥活性成分分別都可控制地緩慢地釋放出來。 在這種本發明的緩釋性農藥粒劑中,該外層部也可以進一步 包含介面活性劑。另外,例如也可以做成如下結構,g卩:在内 核中所含的上述難溶於水的第一熱塑性材料是二十九烷酸蠟及 /或二十九烷酸酯蠟。另一方面,最好做成如下結構,g卩:在 外層部所含有的上述難溶於水的第二熱塑性材料是石蠟。 就本發明的緩釋性農藥粒劑而言,例如,在内核中所含有的 農藥活性成分可以是(RS) --1—甲基一2—硝基一3-(四氫化 基一3—呋喃基甲基)胍,在外層部所含有的農藥活性成分可以 選擇由噻菌靈構成。 另外,本發明的緩釋性農藥粒劑的製造方法是製造具有上述 結構的緩釋性農藥粒劑的方法。對於作爲内核的上述製粒物, 當將作爲外層部的包覆層形成在内核的表面時,將構成上述包 覆層的第二熱塑性材料加熱熔化,爲了實現向上述製粒物表面 的包覆,加熱溫度應低於在内核中所含有的第一熱塑性材料的 熔點。 再有,在本發明的緩釋性農藥粒劑的雙層結構中,將内核這 8 (請先閱讀背面之注意事項再填寫本頁) 訂——*------線· 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 經濟部智慧財產局員工消費合作社印製 1239807 A7 __ B7 五、發明說明(ί ) 個用語用於指粒劑内側中心的作爲農藥核心的部分,外層部這 個用語用來指粒劑表面,包覆上述内核的外周的部分。 具體實施方式 以下對本發明的緩釋性農藥粒劑作更詳細的說明。 本發明的緩釋性農藥粒劑,例如,在水稻的育苗箱處理中所 使用的育苗箱用粒劑中,當製作將至少具兩種作用的農藥活 性成分包含在一種粒劑中的混合製劑時,是能很好使用的劑 型。也就是說,作爲育苗箱用粒劑施撒之後,使其在相互不同 的時期慢慢地溶出並維持所希望的濃度,當供給所必須的這兩 種以上的,其作用相互不同的農藥活性成分時,通過利用具有 雙層結構的本發明的緩釋性農藥粒劑,在一定時期内可由外層 部持續地釋放出一種農藥活性成分,而在較長一段時間中可由 内核持續釋放出另外的農藥活性成分。因此,所謂用本發明的 緩釋性農藥粒劑所實現的溶出控制就是指在外層部和内核各自 所含有的不同種類的農藥活性成分同時而且慢慢地溶出。 在本發明緩釋性農藥粒劑中,採用由内核和外層部構成的雙 層結構,使兩種或兩種以上的,水溶解度具有極大差異的農藥 活性成分含在該雙層結構中,在内核中含有水溶解度高的農藥 活性成分,在外層部,含有水溶解度低的農藥活性成分,根據 農藥活性成分的水溶解度的變低以區分其在整個粒劑中所存在 的位置。具體的是,在内核中所含有的農藥活性成分,選擇20 °C的水溶解度在loooppm以上一10%以下者,相反,在外層部所 含有的農藥活性成分限定於20 °C的水溶解度限定爲 9 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) — »ΙΜ· - «J —u I I I I I - — — I! — — — 1 — — — — — — — — (請先閱讀背面之注意事項再填寫本頁) 1239807 五、發明說明(尽) 〇· 01—500ppm者,做成兩者的水溶解度具有顯著差異的組合。 這時,關於在内核中所含有的水溶解度非常高的農藥活性成 分,爲了控制其溶解釋放速度並使其具有充分的緩釋性,將其 做成分散在蠘黏黏合料中的形式,作爲該黏黏合料所用的蠟,| 使用難溶於水的第一熱塑性材料。將這種難溶於水的第一熱塑 性材料做成黏黏合料的結果抑制了農藥活性成分同水介質的接 觸。另外,其外層部也用另外的難溶於水的第二熱塑性材料組 成的,作爲將纟鼠冋樣作爲黏黏結劑的包覆層,其結果更進一步 增加了在内核中所含有的農藥活性成分的緩釋性。另一方面, 外層部所含有的,水溶解度低的農藥活性成分分散在使用上述 難溶於水的第二熱塑性材料的蠟黏黏合料中的同時並同其低的 水溶解度相結合,可控制其溶解釋放速度而得到所要求的緩釋 性。 這樣,在本發明的緩釋性農藥粒劑中,關於所含有的多種農 藥活性成分,根據其水溶解度的差異,選擇其在由内核和外層 部所構成的雙層結構中所在的位置,加之其水溶解度的作用, 有區別的選擇所用蠟的種類從而使得最佳的蠟黏合料實現所要 求的緩釋性。這時,釋放速度由於與粒劑的粒子直徑(表面積This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1239807 A7 B7 V. Description of the invention (k) structure, the core is made of at least 20⑻ppm and less than 10% water solubility at 20 ° C A pesticide active ingredient, an inorganic-based diluent carrier, a granulated product composed of a first thermoplastic material that is hardly soluble in water, and the outer layer part is at least one pesticide active ingredient having a water solubility of 20 ° C from 0.01 to 500 ppm. A coating layer composed of a diluent carrier and a second thermoplastic material that is lower in melting point than the first thermoplastic material contained in the core and is a different material and hardly soluble in water. Both the pesticide active ingredient contained in the inner core and the pesticide active ingredient contained in the outer layer portion can be slowly released in a controlled manner. In the sustained-release pesticide granule of the present invention, the outer layer portion may further contain a surfactant. In addition, for example, it is also possible to make the following structure: g 卩: The first water-insoluble first thermoplastic material contained in the inner core is a nonacosanoic acid wax and / or a nonacosanoic acid ester wax. On the other hand, it is preferable to have a structure in which the above-mentioned second water-insoluble thermoplastic material contained in the outer layer portion is paraffin. In the case of the sustained-release pesticide granules of the present invention, for example, the pesticide active ingredient contained in the inner core may be (RS) --1-methyl-2-nitro-3- (tetrahydro- 3-- Furylmethyl) guanidine, the active ingredient of the pesticide contained in the outer layer can be selected from thiabendazole. The method for producing a sustained-release pesticide granule of the present invention is a method for producing a sustained-release pesticide granule having the above-mentioned structure. For the granulated material as the inner core, when the coating layer as the outer layer portion is formed on the surface of the inner core, the second thermoplastic material constituting the coated layer is heated and melted, in order to achieve coating on the surface of the granulated material. The heating temperature should be lower than the melting point of the first thermoplastic material contained in the core. In addition, in the double-layer structure of the sustained-release pesticide granules of the present invention, the inner core 8 (please read the precautions on the back before filling this page) Order —— * ------ Line · Ministry of Economic Affairs Printed on the paper by the Intellectual Property Bureau employee consumer cooperatives. The paper size applies to the Chinese National Standard (CNS) A4 (210 X 297 mm). Printed by the Intellectual Property Bureau Employee Consumer Cooperatives of the Ministry of Economic Affairs. 1239807 A7 __ B7 V. Description of the invention (ί) The part used as the pesticide core for the inner center of the granule, and the term "outer part" is used to refer to the surface of the granule, covering the outer periphery of the inner core. BEST MODE FOR CARRYING OUT THE INVENTION The slow-release pesticide granules of the present invention will be described in more detail below. For the slow-release pesticide granules of the present invention, for example, in the granules for a nursery box used in the treatment of rice nursery boxes, a mixed preparation containing at least two pesticide active ingredients in one granule is prepared. Is a dosage form that works well. In other words, after being applied as a granule for a nursery box, it slowly dissolves at different times and maintains the desired concentration. When these two or more kinds are required, their effects are different from each other. In the case of ingredients, by using the sustained-release pesticide granules of the present invention having a double-layered structure, a pesticide active ingredient can be continuously released from the outer layer part in a certain period of time, and another core part can be continuously released for a longer period of time. Pesticide active ingredients. Therefore, the so-called dissolution control achieved by the slow-release pesticide granules of the present invention means that different kinds of pesticide active ingredients contained in the outer layer portion and the inner core are simultaneously and slowly dissolved. In the slow-release pesticide granules of the present invention, a double-layer structure composed of a core and an outer layer portion is used, so that two or more kinds of pesticide active ingredients having greatly different water solubility are contained in the double-layer structure. The inner core contains a highly water-soluble pesticide active ingredient, and the outer layer contains a low water-solubility pesticide active ingredient. The water-solubility of the pesticide active ingredient is reduced to distinguish its position in the entire granule. Specifically, the pesticide active ingredient contained in the inner core is selected to have a water solubility of 20 ° C above 10 ppm and 10% or less. Conversely, the pesticide active ingredient contained in the outer layer is limited to a water solubility limit of 20 ° C. For 9 paper sizes, the Chinese National Standard (CNS) A4 specification (210 X 297 mm) is applied — »ΙΜ ·-« J —u IIIII-— — I! — — — 1 — — — — — — — (Please (Read the precautions on the back before filling this page) 1239807 V. Description of the invention (exhaustive) 〇 · 01-500ppm, a combination with a significant difference in water solubility between the two is made. At this time, in order to control the rate of dissolution and release of the pesticide active ingredient with a very high water solubility contained in the inner core, and to make it have sufficient sustained release properties, it is made into a form dispersed in a concrete adhesive, as the Wax for adhesives, | use the first thermoplastic material that is hardly soluble in water. As a result of making this first water-insoluble thermoplastic material into a binder, contact between the pesticide active ingredient and the aqueous medium is suppressed. In addition, its outer layer is also made of another second thermoplastic material that is hardly soluble in water, as a coating layer using the mole-like compound as a bonding agent. As a result, the pesticide activity contained in the inner core is further increased. Slow release of ingredients. On the other hand, the low-water-soluble pesticide active ingredient contained in the outer layer is dispersed in the wax adhesive using the second water-insoluble second thermoplastic material and combined with its low water-solubility, which can be controlled. Its dissolution release rate achieves the required sustained release. In this way, in the sustained-release pesticide granules of the present invention, regarding the contained multiple kinds of pesticide active ingredients, the positions of them in the double-layer structure composed of the inner core and the outer layer portion are selected according to the difference in water solubility, plus The role of its water solubility, the type of wax used is selected differently so that the optimal wax binder can achieve the required sustained release. At this time, the release rate is due to the particle diameter (surface area

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製 和體積的比率)緊密相關,將所要求的内核的粒子直徑,包覆 外層部的整個粒子的直徑達到一定值爲目的,加在各自的農藥 活性成分中所加的無機系稀釋載體,使得農藥活性成分和無機 系稀釋載體以相互均勻混合的形式分散在由熱塑性材料構成的 蠟黏合料中並將每單位體積的農藥活性成分的含有量調整到適 當的範圍。 10 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 經濟部智慧財產局員工消費合作社印製 1239807 A7 B7 五、發明說明(分) 如上所述,本發明的緩釋性農藥粒劑爲由内核和外層部構成 的雙層結構,作爲適合於這種結構的製造方法是使用各自不同 的熱塑性材料作爲蠟黏合料而做成明確劃分爲内核和外層部的 形狀。爲了簡便地製作這種結構,作爲内核,使用第一熱塑性 材料,加熱混合後,配製成成型爲所要求粒子直徑的製粒物, 將作爲外層部的包覆用組合物包覆在製粒物的表面,在加熱的 情況下使第二熱塑性材料熔化成爲液態後、,包覆在上述製粒物 上。具體地,在包覆上述外層部的工序中,當將其置於加熱環 境中時,爲了避免保持作爲内核的製粒物的形狀的第一熱塑性 材料再熔化,在外層部所使用的第二熱塑性材料的熔點應選擇 比第一熱塑性材料的熔點更低。因此,包覆形成外層部的工序 的加熱條件選擇的溫度應不超過第一熱塑性材料的熔點,從而 使其在第二熱塑性材料的熔點上而又不引起上述第一熱塑性材 料的熔化。 這樣,在本發明的緩釋性農藥粒劑中,在内核和外層部中使 用不同的熱塑性材料進行緩釋的處理的結果,例如,在必須防 治相互不同的病害和蟲害期間,當含有對於病原體和病害蟲具 有防治作用的兩種以上農藥活性成分時,可以確保分別持續釋 放,這兩種或兩種以上的農藥活性成分的功能作用。 下面,進一步更具體的說明製造本發明的緩釋性農藥粒劑的 方法。首先,爲了使20°C的水溶解度在l(X)Oppm以上一 10%以下 的農藥活性成分的溶出緩釋化,使用該農藥活性成分,無機系 稀釋載體以及難溶於水的第一熱塑性材料,加熱到上述第一熱 塑性材料的熔點以上的溫度,將以上均勻混合的組合物成型爲 11 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) I U4 L I n 1 ϋ I n ϋ n —.1 --------訂---^------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 1239807 A7 B7 五、發明課明(v〇 ) 所要;^的形狀,粒子直徑,經冷卻而製得内核用的製粒物。隨 後,將20°C的水溶解度爲0.01—500ppm的農藥活性成分,無機 系稀釋載體,以及難溶於水的第二熱塑材料一起均勻地混合, 使用該混合得到的組合物通過一邊加熱到上述第二熱塑性材料 的熔點以上的溫度一邊將其包覆在上述内核用製粒物的表面, 從而可製得由内核和設置在其表面的外層部的雙層結構的粒 劑。這時,第二熱塑性材料的熔點應低於第一熱塑性材料的熔 點,預先選擇好這些材料,就可以做到使實施外層部的包覆時 的加熱溫度爲未達到第一熱塑性材料的熔點的溫度。再有,所 謂内核的農藥活性成分的溶出作到緩釋化的狀態是指通過將難 溶於水的第一熱塑性材料加熱熔化而做成黏合料從而製得可控 制農藥活性成分向水中的釋放的農藥製劑。 總之,本發明的緩釋性農藥粒劑具體地可以用以下的工序 製造。 工序1,首先,將20°C的水溶解度爲l〇〇〇ppm以上一1〇%以下的 範圍内的水溶解度高的農藥活性成分,無機稀釋載體,以及第 一熱塑性材料使用裝有加熱裝置的混合機(例如浮動式混合機) 等加熱混合。這時,加熱溫度應在第一熱塑性材料的熔點溫度 以上,而且其溫度未達到其中所含的農藥活性成分的熔點。 工序2,加熱混合後,將所得到的均勻混合物用裝有加熱裝置的 製粒機製粒。製粒機的種類可以考慮作爲目標産物的製粒物的 形狀和粒子直徑等適當選擇。具體的,要製得圓柱形的成型物 時,可選擇裝有同所要求粒徑相吻合的篩網的擠壓式成型機, 要製得球狀的成型物時,可選擇轉動製粒機等。製粒的溫度最 12 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) 訂——:------線- 1239807 A7 B7 五、發明說明(A ) 好在所使用的第一熱塑性材料的熔點溫度以上而在所含有的農 藥活性成分的熔點溫度以下。 工序3,所得到的製粒物往往有相互黏連的情況,須將其破碎並 按要求進行篩分,從而製得所要求形狀,粒子直徑的緩釋性製 粒物(内核)。 工序4,將同在内核中所含有的水溶解度高的農藥活性成分不同 的,20°C的水溶解度爲0· 01—500ppm範圍内的水溶解度低的農 藥活性成分,無機系稀釋載體,和同内核中所含有的第一熱塑 性材料不同而且其熔點比第一熱塑性低的,難溶於水的第二熱 塑性材料以及根據需要還有介面活性劑和補助劑一起用混合機 (例如浮動式混合機)等混合,製得外層部用的原料粉末。 工序5,將由工序3製得的内核加入裝有加熱裝置的混合機(例 如,浮動式混合機,轉動製粒機,庫拉(々-5-)混合機,滾筒 式混合機,馬魯麥拉紮5〗〒一)等),一邊加熱一邊混 合,將工序4準備的外層部原料定量地投入,使其包覆在内核 的表面而製得具有所要求的粒度分佈的粒子。這時,包覆的外 部層由於將加熱溫度定到所含有的第二熱塑性材料産生熔化的 溫度,熔化的第二熱塑性材料成爲黏結劑,使水溶解度低的農 藥活性成分和無機系稀釋載體形成均勻分散的包覆層,從而製 得本發明的包覆型緩釋性農藥粒劑。再有,在這個加熱,包覆 工序中,爲了防止因内核中的第一熱塑性材料的軟化、熔融産 生内核之間的附著,黏連,進一步爲防止内核同混合槽内壁的 附著,壓接等,加熱溫度應在外層部所使用的第二熱塑性材料 的熔化溫度以上而在内核所使用的第一熱塑性材料的熔點溫度 13 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) 訂——^------線 經濟部智慧財產局員工消費合作社印制农 經濟部智慧財產局員工消費合作社印製 1239807 A7 — B7 五、發明說明(\>) 以下。 在具有上述結構特徵的本發明的包覆型緩釋性農藥粒劑 中,構成其外層部和内核的各組合物的組成比沒有特別限定, 可以根據下述情況,考慮各農藥活性成分應維持的濃度範圍, 例如,達到防止效果的有效濃度範圍,另外,應維持該濃度的 延續時間等適當決定,g卩.·表層部和内核中各自所含有的一種 以上的農藥活性成分的各成分的溶出速度、,在相應植物體内分 能排出速度及吸收進植物體内的速度以及將植物體的苗移植到 田地中等。這時,通常,對每個粒劑,在其外層部和内核中各 自所含有的至少一種以上有的農藥活性成分的質量分別進行計 算,將其計算的質量比可控制在内核:外層部=1: 15—15: 1的 範圍内。另外,本發明的包覆型緩釋性農藥粒劑,或是由外層 部和内核構成的固態劑,其外形尺寸,劑型也沒有限定,例如, 可以是通常的粒劑型,丸藥型,藥片型等任何一種形狀。另外, 選取上述的劑型時,其尺寸大小可根據使用的形態適當選擇, 例如,圓柱狀或球狀的直徑可在0.1—3腿的範圍内,沒有特別 限定。具體的,在本發明的包覆型緩釋性農藥粒劑中,根據施 撒的形式可以適當地選擇其粒徑,例如,當使用水稻的育苗箱 用粒劑時,最好將用於調整控制粒徑,外形的篩網的網孔,選 擇在0.3—3mm範圍内。再有,圓柱形的長度,根據其直徑最好 選擇在不要過長的範圍内,例如,圓柱形的直徑在0.1—3画範 圍内時,其長度最好選擇在〇· 1—1〇眶範圍内。 另外,本發明的包覆型緩釋性農藥粒劑中,例如,當選取球 狀的形狀時,對其内核和外層部的直徑比沒有特別限定,通常 14 本紙張尺度適用中國國家標準(CNS)A4規格(210 x 297公釐) — Ίν — 1—x--------------^---:------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印^^ 1239807 A7 B7 五、發明說明(θ ) 可選擇在不超過1: 3的範圍内。通常,所含有的農藥活性成分 的溶出,粒劑的粒徑愈小,農藥活性成分的每單位含有量的粒 劑表面則增大,與此相應溶出加速,然而在本發明的包覆型緩 釋性農藥粒劑中,内核和外層部都各自採用不同的難溶於水的 熱塑性材料,通過獨立進行緩釋性的控制,將粒徑及内核和外 層部的直徑比限定在上述範圍内,都可以達到所要求的溶出特 性。 、 具體的,内核和外層部都各自加入了農藥活性成分,通過採 取含有無機系稀釋載體的結構,由於可將每單位體積所含有的 農藥活性成分量在較寬的範圍内進行調整,可將農藥活性成分 的每單位含有量的粒劑表面積控制在一定範圍内。這時,在内 核和外層部各層中,由於用無機系稀釋載體將各農藥活性成分 均勻地稀釋,最好採用將各農藥活性成分和無機系稀釋載體一 起製成粉末形狀再相互均勻混合的方法。 在本發明的包覆緩釋性農藥粒劑中,在其内核和外層部中所 分別含有的不同種類的農藥活性成分中,通常對於作爲物件的 植物體,例如對於水稻可以使用的農藥活性成分中,20°C的水 溶解度在lOOOppm以上一 10%以下範圍内的水溶解度高的農藥活 性成分至少一種以上,20°C的水溶解度在0· Olppm —500ppm範 圍内的水溶解度低的農藥活性成分至少一種以上,最好使用具 有任何一種殺生物活性的,農藝園藝用的化合物。例如,在上 述具有殺生物活性的化合物中,最好選擇殺蟲劑和殺菌劑的組 合,但也未將以下的組合排除在最佳組合之外,g卩:選擇其作 用機理相互不同的殺蟲劑之間的組合或者殺菌劑之間的組合 15 (請先閱讀背面之注意事項再填寫本頁) · n n n ϋ n n ϋ 5rJ* I n n n ϋ 1 n I , 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 經濟部智慧財產局員工消費合作社印製 1239807 Λ7 B7 五、發明說明(\Ao 等,也可以選擇在其有效防治期間具有差異的藥劑的組合。另 夕卜,包覆型緩釋性農藥粒劑中這些農藥活性成分的含有量,根 據其含有部位是内核或外層部沒有區別,在各部分中,通常可 選擇在0. 01質量%—50質量%範圍内,最好在0· 5質量%--30質 量%範圍内,沒有特別限定。即:對每個粒劑,所含有的各農藥 活性成分的含有量,根據該活性成分的性質,適用場合決定, 其施撒形式,例如,根據作爲育苗箱用粒劑的施撒形式,每1000 平方米所施撒的量可以選擇其含有量使其滿足每1000平方米所 必須的處理量。 在本發明的包覆型緩釋性農藥混合粒劑中,爲了製得水溶解 度格外不同的兩種以上農藥活性成分分別緩釋化的混合粒劑, 在内核中所含有的農藥活性成分的20°C的水溶解度比在外層部 中所含有的農藥活性成分的水溶解度必須明顯的高。總之,在 内核中所含有的農藥活性成分的20°C的水溶解度在至少在 lOOOppm以上一 10%以下,最好5000ppm以上一 10%以下,尤其好 lCK)00ppm以上一10%以下範圍内選擇,另一方面,在外層部所含 有的農藥活性成分的20 °C的水溶解度選擇在至少 〇· 〇1—500ppm,最好在 1 一300ppm,尤其好 0· 5—200ppm 範圍内 選擇,最好通過這種選擇使得兩者的水溶解度之間存在極懸殊 的差異。 另外,在内核中所含有的農藥活性成分的熔點同内核中所用 的第一熱塑性材料的熔點相同或更低時,在製造本發明的緩釋 性農藥粒劑的工序中,製造内核用的製粒物時,爲了熔化第一 熱塑性材料而加熱時,混合在其中的農藥活性成分也完全熔 16 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) — ,J ii 1-L--------------^---^------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 1239807 A7 B7 五、發明說明) 化。在這種情況下,存在以液體狀態相互不能均勻混合均勻的 可能性,另外,即使均勻混合了,在其後凝固時,也存在農藥 活性成分偏析,不能均勻分散的可能性。在這種情況下,在内 核中,農藥的活性成分同所添加的無機系稀釋載體一起不能形 成均勻地分散到第一熱塑性材料的蠟黏合料中的形態,從而存 在不能實現所期望的緩釋化這樣重大的問題。爲了解決這個問 題,在内核中所含有的農藥活性成分的焰^占定比所用的第一熱 塑性材料的熔點要高,最好使用熔點在100°C者。若這樣選擇, 在内核中所含有的農藥活性成分不熔化,這樣,加熱到第一熱 塑性材料軟化、熔化的溫度,例如,最好將粉末狀的農藥活性 成分和無機系稀釋載體形成均勻地混合,分散到第一熱塑性材 料中的形態。同樣地,在外層部所含有的農藥活性成分的熔點 在比外層部所使用的第二熱塑性材料的熔點相同或者更低時, 在將外層部包覆在内核表面的工序中,爲了熔化第二熱塑性材 料而加熱時,混合在其中的農藥活性成分也完全熔化。這時, 存在産生同樣不正常的問題。爲了預先防止這些問題,在外層 部所含有的農藥活性成分的熔點,至少應比所使用的第二熱塑 性材料的溶點高,若有可能,希望能比該溶點更高的第一熱塑 性材料的熔點還高,最好使用熔點在100°C以上者。 作爲滿足以上條件的農藥活性成分,具體的可例舉如下的物 質,作爲在内核中的含有的農藥活性成分,例如就殺蟲劑而言, 可例舉如下,熔點和20°C的水溶解度分別具有括弧内的值,殺 蟲環才〉夕7 A) (125—128Γ,約80%),阿塞他米普利多 (7七女S 卜、)(1〇1-1〇3· 3°C· 42〇0ppm),奇阿麥托克隆 17 — Jhlt -----------^------^ (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 經濟部智慧財產局員工消費合作社印製 1239807 A7 __B7 五、發明說明) / 卜今廿 Λ) (139· rC,4100ppm),或者特開平 7-179448 號中所示的化合物(KS) -1-甲基-2-硝基-3-(四氫化基—3一咲 喃基甲基)胍(約105°C,54(X)0ppm),另外,作爲殺菌劑可列 舉皮洛克隆(112°C,4000ppm,稻瘟素S (235°C,3%)等。 另一方面作爲在外層所含有的農藥流活性成分,例如就殺蟲 劑而言,可列舉如下,熔點和20°C的水溶解度具有表示在括弧 内的值。NAC (142°C,約lOOppm),並帶卡魯普> 夕、< 才力 少 ^ ),(124· 6-128· 7°C,40ppm);庫洛奇阿尼金(夕 口 ^ 7 二 夕 >),(176-178°C,270ppm),皮麥托洛金(匕。J 卜 α>), (234.4°C,270 ppm)菲普洛尼魯(7 4 7。口二几)(約 2〇〇°C, 1.9ppm),布普洛菲金(7、、7。口 7 工、y、>)(約 i〇5°C,0.9 ppm), 特布菲羅基多(于工乂>) (191°C,0.83 ppm),另外,作爲 殺菌劑,可例舉富美雙(155°C,30ppm),異菌脲(136°C,13ppm), 望加多(102°C,9.6ppm),奇弗魯紮米多寸、$ K)(約178 °C,1· 59 ppm),卡魯普洛帕米多(力口〜S卜、)(147-149 °C,3.6 ppm),氧化偶氮斯托洛賓(r、/今i 7卜π匕、>)(約118 °C,lOppm),普洛別鈉佐魯(文 口 〜于、/一;〇 (約 138°C,150ppm), 基庫洛希麥托σ y卜)(約150。(:,5口?111),萘四酮酸(才 今:^」二7々酸)(310。〇,3.2口口111),特庫洛弗他拉姆(亍々口7 夕 3 a)(198°C,14 ppm),菲利木宗a、/>)(175°C,162 ppm),基庫洛麥金(^ 々 π J) (250-253· 5 °C,〇· 74 ppm),克 菌丹(178°C,3· 3 ppm),其中,將殺蟲劑的(RS) — 1 一甲基一2—硝 基一3—(四氫化基一3—呋喃基甲基)胍,用於内核,將殺菌劑的 噻菌靈用於外層部的組合是將本發明的緩釋性農藥粒劑製成育 18 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) — „J h I, -----------^-----1 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 1239807 A7 __ B7 五、發明說明〇〇 ) 苗箱用粒劑時的最佳組合之一. 本發明的緩釋性農藥粉劑中所使用的内核用的第一熱塑性 材料中,最好使用20°C的水溶解度不足0.5%的,不溶於水或難 溶於水的在常溫下爲固體的有機物,其熔點在70°C-110°C,最 好在72°C-W0°C,尤其好的在74°C-98°C範圍内。例好可列舉 小燭樹蠟,主加原(i二力、一^ > )蠟,拉斯(57 )蠟, 等植系蠟,二十九烷酸蠟,地蠟,白地獵等礦物系蠟微晶蠟礦 酯得便感石油系蠟,弗歇爾-特羅普歇蠟等合成烴,二十九烷酸 蠟的衍生物,石蠟的衍生物,微晶蠟的衍生物等的改性蠟,硬 化蔑麻油,硬化蔑麻油衍生物的氫化蠟,12-羥基硬脂酸,硬脂 酸胺,鄰苯二甲酸酐亞胺,還有具有氯化烴基的脂肪酸,醯胺, 酯,酮等。其中,按照ASTMD1386標準規定的試驗法,使用鹼 進行滴定求定得的酸值最好在10mgkoH/g以上。例如,主加原 p二力、一^ 蠟(熔點:75Ό,酸值:約21mgk〇H/g)或二 十九烷酸蠟(BASF公司製,商品名Luwax S,熔點:75-85°C, 酸值:135-160mgkoH/g)二十九焼酸酯赠(BASF公司製,商品 名 LuwaxE,熔點:75-85°C,酸值·· 10-25mgkoH/g)等既可以 付與緩釋性,又可使在内核中所含有的農藥溶劑性成分近乎 100%地釋放出來,特別適合。再有,這些蠟作爲熱塑性材料既 可以僅使用一種,也可以將兩種以上混合使用,第一熱塑性材 料的合計使用量相對於構成本發明的緩釋性農藥粒劑的内核的 組合物的總質量通常在5質量%以上最好在1〇質量%以上選擇, 可以考慮所添加的農藥活性成分的量,無機系稀釋載體的性質 及其量適當決定。最好從經濟的覲點來看,第一熱塑性材料的 19 度適用中國國家標準(CNS)A4規格(210 X 297公^ — .J V^ I 1-L-------------^---:------^ (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 1239807 A7 _____ B7 五、發明說明(\?) 添加量的上限可選擇在20質量%。 在本發明的緩釋性農藥粒劑中所使用的内核用的無機系稀 釋載體至少應限於幾乎未顯示水溶性,沒有特別的限定,例如, 可列舉黏土、石英、矽藻土、碳酸鈣、浮石、膨潤土、蛭石、 珍珠岩、綠坡縷石及非質含水矽酸、俗名白炭黑等,通常將一 種或一種以上同使用在農藥粉劑或粒劑中使用的所謂增量劑或 載體並用。 、 另外,在本發明的緩釋性農藥粒劑中,在内核中,除了上述 無機系稀釋載體以外,在不損害本發明的目的和效果的範圍 内,還可以做成粉劑添加抗氧化劑紫外線吸收劑,抗靜電干擾 劑等各種添加劑。例如,作爲抗氧化劑,可列舉辛達多(t >夕' 一 K)酚系抗氧化劑,硫系抗氧化劑,磷系抗氧化劑,氨系抗氧 化劑,内酯系抗氧化劑,維生素E系抗氧化劑等。另外作爲紫 外線吸收劑,可列舉二氧化鈷等無機化合物系紫外線吸收劑, 苯並三唑或二苯甲酮,三嗪苯甲酸酯,水揚酸酯等有機化合物 系紫外線吸收劑等。這時,這些抗氧化劑或紫外線吸收劑可以 根據在内核中所含有的農藥活性成分的物理化學性質選擇,或 者可以添加能確認其效果的量。 再有,作爲抗靜電干擾劑,可列舉氧化鈷、氧化鋅、氧化錳 等,無機化合物,磷酸鈣系化合物等。另外,聚氧乙烯烷基醚 磷酸酯等磷酸酯系介面活性劑也可以作爲抗靜電干擾劑使用。 再有,抗靜電干擾劑可根據需要使用,其使用量在不損害本發 明的目的和效果的範圍内,可以使用可確認抗靜電效果的量。 另一方面,在本發明的緩釋性農藥粒劑中,作爲外層部的難 20 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公爱) 丨 n i 丨 --------------訂---^------線 (請先閱讀背面之注意事項再填寫本頁) A7 1239807 五、發明說明(A) 溶於水的第d熱塑性材料同在内核中所使用的熱塑性材料大體 上是相同的材料,也可以將兩種以上混合使用,同在内核中所 含有的第一熱塑性材料相比其熔點必須更低,具體的第二熱塑 性材料的溶點最好在以下範圍内選ί幸,通常爲40 C-70 C, 最好在50°C-69°C,尤其好在60°C-68°C。再有第二熱塑性材料 在包覆工序中,由於使其熔化而成黏結劑,若熔融黏度低,則 包覆時顆粒之間的附著則少,是合適的。作爲滿足上述各種條 件的第二熱塑性材料的各合適的具體例子,列舉小燭樹蠟、日 本蠟等植物系蠟,蜂蠟、月桂精、鯨蠟,牛脂等動物系蠟、石 蠟、礦脂等石油系蠟、弗歇爾-特羅普歇蠟等全成烴,石蠟的衍 生物等改性蠟等。其中,尤其是石蠟(日本精蠟公司製,商品 名:石蠟140,熔點:61°C,或商品名·· SP-0145,熔點:63°C, 石螺150,溶點66°C)更好。其使用量根據在外層部所含有的 農藥活性成分的量,無機系稀釋載體的性質決定,但在本發明 的緩釋性農藥粒劑中,對其外層部組合物的總質量可在以下範 圍内選擇,即:通常爲1質量%-20質量%,最好1質量%-15質 量%,再有第二熱塑性材料的含有量需設定在這種外層部組合物 的總吸油量以下。 本發明的緩釋性農藥粒劑中所使用的外層部用的無機系稀 釋載體至少限於幾乎未顯示具有水溶性,沒有特別的限定。若 使用同在前所述的内核用的無機系稀釋載體大體相同的材料就 可充分地達到目的。因此,例如可列舉黏土,石英,滑石,膨 潤土,碳酸鈣,浮石,矽藻土,蛭石,珍珠岩,綠坡縷石及非 品質含水矽酸,俗稱白炭黑等,通常,將其一種或一種以上同 21 以再尺/f翻中酬家標準(CNS)A4規格(210x 297公髮) "": — .J. V Ί- --------^---\------^ (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 A7 1239807 五、發明說明(>°) 在農藥粉劑或粒劑中所使用的所謂增量劑或載體並用。 另外,在本發明的緩釋性農藥粒劑中,在外層部,除了無機 系稀釋載體以外,在不損害本發明的目的和效果的範圍内,還 可含有介面活性劑和補助劑。 在本發明的緩釋性農藥粒劑中,作爲可添加在外層部的介面 活性劑,可以列舉在農藥製劑中通常使用的非離子性介面活性 劑,陰離子性介面活性劑,陽離子性介面性劑以及兩性介面 活性劑,例如,烷基醚,聚氧乙烯烷基芳基醚,聚氧乙烯苯二 烯基苯基醚,聚氧乙烯烷基酯,聚氧乙烯山梨糖醇酐芳基烷基 化物,聚氧乙烯苯基醚聚合體,聚氧二烯亞烷基苯基芳基醚, 聚氧乙烯亞烷基乙二醇,聚氧乙烯聚氧丙烯嵌段共聚物等非離 子性介面活性劑,木質磺酸鹽,烷基芳基磺酸鹽,磺基琥珀酸 二烷基酯,聚氧乙烯烷基芳基醚硫酸鹽,烷基磺酸萘,聚氧乙 烯苯乙烯基苯基硫酸鹽等陰離子性介面活性劑,烷基胺鹽,季 銨鹽,烷基甜菜鹼,氧化胺等陽離子性介面活性劑及兩性介面 活性劑等。添加這些介面活性劑時,既可以使用一種,也可將 同種的或不同種的並用。 除介面活性劑以外,作爲可添加到外層部的補助劑可列舉芳 香族竣酸,多元羧酸,糖衍生物羧酸等固體狀的有機酸或水溶 性高分子等。具體的作爲有機酸可列舉草酸、丙二酸、琥拍酸、 馬來酸、富馬酸等二元酸,或者蘋果酸、酒石酸、等羥基置換 二元酸、抗壞血酸、檸檬酸等糖衍生型羧酸。另外,作爲水溶 性高分子,可列舉,聚乙烯醇,羧甲基纖維素,糊精羥乙基纖 維素,甲基纖維素,藻酸鹽,明膠,果膠,普魯郎 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) —•"7 *-------------------訂---·------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作社印製 1239807 A7 ________________ B7 五、發明說明 (>\) 聚乙烯吡咯烷酮,聚丙酸鹽,聚環氧乙烷等。介面活性劑及這 些補助劑的添加量兩者合計相對外層部組合物的總質量最好保 持在以下範圍内,即一般爲0· 01質量%-20質量%,最好0.01質 量-10質量%。 以上說明的結構的本發明的緩釋性農藥黏劑,可以實現緩釋 化,使得不同的兩種或兩種以上的,尤其是能使水溶解度具有 極大差異的農藥活性成分以各自的溶出速釋放,可以作爲特 別適用於水稻的育苗箱用粒劑的農藥粒劑。通過使用本發明的 緩釋性農藥粒劑,能夠得到水稻的育苗箱用粒劑,在從插秧開 始的水稻栽培期間必須防治病蟲害的30-60日中,根據不同情 況也在比60日長的時間中持續地釋放農藥活性成分並可大體上 完全釋放出來。另外,本發明的緩釋性農藥粒劑,在製造時, 由於可省去以特開2000-44404號公報所記載的方法所必須的乾 燥工序,其優點是可降低製造成本。本發明的緩釋性農藥粒劑, 例如,當作水稻的育苗箱用粒劑時,可以在插秧前施放到水稻 育苗箱中。另外,當作成育苗箱用粒劑時,其施用量大致在每 個水稻育苗箱(約30cmX60cm) 10g-100g,一般爲50左右,沒 有特別的限定,製劑中農藥活性成分的含有量,在必須防止病 蟲害期間,可根據每10公畝中所使用的育苗箱個數決來定。 另外,本發明的農藥粒劑,例如,當施用到水稻育苗箱中時, 將粒劑均勻地撒布到整個育苗箱再將秧苗移植到水田時,每株 秧苗周圍的農藥粒劑的個數最好不要産生大的差別。爲此目 的,粒劑的粒徑,具體的是決定該粒徑分佈的篩分等所使用篩 網孔徑不要過大,所以防止相應於一定使用量的農藥粒劑的個 23 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ϋ ΜΙ» b— I Ji -ΊΙ n I n ϋ I ϋ · ϋ n n I I n ϋ 一^J« n I ml n n ϋ ϋ I \ (請先閱讀背面之注意事項再填寫本頁) ^___ 經濟部智慧財產局員工消費合作社印製 1239807 發明說明(>>) 數不要過少。即,作爲水稻的育苗箱用粒劑所使用者,每lg農 藥粒劑的個數在300個以上,最好在400個以上,據此選擇上 述的篩網孔徑。但是,由於所含有的無機稀釋載體的含有率, 其松裝比重等的不同,粒劑的粒徑也不要過小,必須防止因過 小而呈現浮游在水中的狀態。在外層部,添加介面活性劑,增 加對水的表面的親和性,可防止出現上述的一些不正常狀態, 這樣每lg農藥粒劑的個數希望保持在不超過2000個的範圍内。 具體實施方式 i 下面通過實施例,對本發明作進一步詳細的說明。 尤其是將本發明的緩釋性農藥粒劑作爲水稻的育苗箱用粒 劑的具體例子,但本發明不受這種育苗箱用粒劑的製造方法及 所得到的製劑配方的任何限定。 例如,作爲内核的農藥活性成分所使用的(KS) -1-甲基-2-硝基-3-(四氫化基-3-呋喃基甲基)胍,作爲外層部的農藥活 性成分所使用的噻菌靈都可用上述的各種農藥活性成分代替, 或者在實施例中所表示的内核和外層部中所使用的各熱塑性材 料,無機系稀釋載體也可用上述的其他的物質代替等,使用本 發明的緩釋性農藥粒劑,可以製得水稻的育苗箱用粒劑。 再有,在下述的具體例子中所表不的組成比例,除了特殊指 定的情況外,都用産量%比。 參考例1-6以表1所示的組成比例,按照以下所述的製作方 法得到參考例1-6的内核。 24 I J >--Ίν--------------訂---^------線 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) A7 1239807 B7 五、發明說明(y>) [表1] 製粒物(内核)的組成 組成内容(質量邰) 製造條件 化合 Luwax Luwax 白碳 滑石 碳酸 加熱 網孔 物1 S E 里 J > 鈣 溫度 尺寸 參考 例1 3· 0 18.0 5.0 10.0 64.0 90 °C 0.8 mm 參考 例2 3.0 18.0 3.8 10.0 65. 3 83 °C 0.8 mm 參考 例3 3.0 3.6 14.4 5.0 10.0 64·〇 83 °C 0.8 mm 參考 例4 5.0 18.0 5.0 10.0 62. 0 90 °C 0.7 mm 參考 例5 5.0 18.0 3.8 10.0 63· 3 83〇C 0.7 mm 參考 例6 5.0 3.6 14.4 5.0 10.0 62. 0 83 °C 0.7 mm J—ί 雙------- — 訂---^------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 作爲在内核中所含有的農藥活性成分使用根據特開平7-179448 號公報中記載的法合成的(KS)-l-甲基-2-硝基-3-(四氫化基 -3-呋喃基甲基)胍(以下簡稱:化合物1),作爲無機系稀釋載體 使用白炭黑,滑石,碳酸鈣,作爲第一熱塑性材料使用二十九烷 酸蠟(BASF公司製,商品名Luwax S,熔點:75-85°C,酸值: 135-160 mgkoH/g)及/或二十九烷酸酯蠟(BASF公司製,商品名 LuwaxE,熔點·· 75-85°C,酸值:10-25mgkoH/g),將以上材料 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 經濟部智慧財產局員工消費合作社印製 1239807 A7 _____ B7 五、發明說明( 一起放進裝有加熱裝置的浮動式混合機中,加熱到83°C-90°C混 合使用該混合物用加熱裝置保持在90°C的臥式擠壓製粒機(網 孔尺寸爲0· 7mm或者0· 8mm篩網)進行擠壓製粒,將用表丨分別 表示的組成配分,製造條件得到的製粒物,粉碎,篩分後製得 的參考例1-6的製粒物(内核) 實驗例1:内核的溶出實驗。 用以下方法測定由參考例1-6製得的内核所釋放出的農藥 活性成分(化學物1)的溶出率^ 即,將參考例1-6可得的内核放入裝有25ml核准3度的硬 水的熔量爲50 ml的帶密封塞的試管中,分別將可所有的農藥 活性成分全量溶出時,可放如的量相應於使農藥活性成分(化 合物)的濃度達到920ppm的量,不溶物沈澱於水中,在這種狀 態,25°C下靜量一定時間後,將全量過濾,用HPCC測定濾液中 所溶解的農藥活性成分量(化合物1)。根據測定值。按下式計 算溶出率,將結果匯總於表2。 溶出率=(濾液中的農藥活性成分量/粒劑中的農藥活性成 分量)X 100。如表2所示所表明的,在本發明的緩釋性農藥粒 劑中與該内核相當的參考例1-6的製粒物中(内核)可在一周 到二個月的範圍内在任何時候都緩慢釋放所含有的農藥活性成 分(化合物1),同時大體上可完全釋放。 26 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公爱) n n —1 1— ϋ n n I n ϋ · -Ϊ n 1 .1 II «I I I ϋ I n ϋ ϋ n I I (請先閱讀背面之注意事項再填寫本頁) 1239807 A7 五、發明說明(/) [表2] 由製粒物(内核)釋放出的化合物1的溶出率 化合物1的溶出率(%) 1曰後 3日後 7曰後 14曰 後 —--—— 30日 後 60日 後 參考例1 59.2 77. 7 98. 5 ιαι· 1 參考例2 17.6 26.8 40. 1 53.2 72.6 97.7 參考例3 31.8 44. 7 59. 2 75.6 95.4 100.2 參考例4 51.6 75.0 97.6 100.2 參考例5 20.6 32. 3 44· 5 58.4 75.8 94.8 參考例6 35.5 50.0 65.0 82· 2 98.4 100.0 n -i^i n J— «n n I n ! I— 1— · mu n n· 1 n (請先閱讀背面之注意事項再填寫本頁) 訂 實施例1 -12 以表3所示的組成所比,在作爲内核的參考例1—6的製粒物上, 用以下所述的方法包覆形成外部層,從而製得實施例1-12的水 稻育苗箱用粒劑。 [表3] 皇Mgl 1-12的水稻育苗箱用粒劑的紺成 線 經濟部智慧財產局員工消費合作社印製 内核 (質量部) 67. 5 (參考例1) 原體粉 碎末 石蠘The ratio of system and volume) is closely related. The required particle diameter of the inner core and the diameter of the entire particle covering the outer layer portion are brought to a certain value. The inorganic dilution carriers added to the respective active ingredients of pesticides make The pesticide active ingredient and the inorganic-based diluted carrier are dispersed in a wax binder made of a thermoplastic material in a uniformly mixed manner, and the content of the pesticide active ingredient per unit volume is adjusted to an appropriate range. 10 This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1239807 A7 B7 V. Description of the invention (minutes) As mentioned above, the slow-release properties of the present invention Pesticide granules have a double-layer structure composed of a core and an outer layer. As a manufacturing method suitable for this structure, different thermoplastic materials are used as wax binders, and the shapes are clearly divided into core and outer layers. In order to easily produce such a structure, a first thermoplastic material is used as the core, and after heating and mixing, it is formulated into a granulate having a desired particle diameter, and the coating composition as an outer layer portion is coated on the granule. The surface of the object is coated with the granulated object after the second thermoplastic material is melted into a liquid state when heated. Specifically, in the step of covering the outer layer portion, when the first layer is placed in a heating environment, in order to avoid remelting the first thermoplastic material that maintains the shape of the pellets as the inner core, the second used in the outer layer portion The melting point of the thermoplastic material should be selected to be lower than the melting point of the first thermoplastic material. Therefore, the heating conditions of the step of forming the outer layer portion should be selected at a temperature not exceeding the melting point of the first thermoplastic material so as to be above the melting point of the second thermoplastic material without causing the above-mentioned first thermoplastic material to melt. In this way, in the sustained-release pesticide granules of the present invention, as a result of the sustained-release treatment using different thermoplastic materials in the inner core and the outer layer portion, for example, when it is necessary to control mutually different diseases and insect pests, When two or more kinds of pesticide active ingredients which have a controlling effect on diseases and pests can be ensured to be continuously released respectively, the functional effects of these two or more kinds of pesticide active ingredients. Hereinafter, the method for producing the sustained-release pesticide granules of the present invention will be described more specifically. First, in order to slow the release of a pesticide active ingredient with a water solubility of 20 ° C from 1 (X) Oppm to 10%, the pesticide active ingredient, an inorganic dilution carrier, and a first thermoplastic which is hardly soluble in water are used. The material is heated to a temperature above the melting point of the first thermoplastic material, and the above uniformly mixed composition is formed into 11 papers. The size of the paper is applicable to China National Standard (CNS) A4 (210 X 297 mm) I U4 LI n 1 ϋ I n ϋ n —.1 -------- Order --- ^ ------ line (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1239807 A7 B7 Fifth, the invention course (v) required; the shape of ^, the diameter of the particles, after cooling to obtain the pellets for the core. Subsequently, the pesticide active ingredient having a water solubility of 0.01-500 ppm at 20 ° C, an inorganic-based diluted carrier, and a second thermoplastic material which is hardly soluble in water are uniformly mixed together, and the composition obtained by using the mixture is heated to the The second thermoplastic material is coated on the surface of the pellets for the inner core at a temperature higher than the melting point of the second thermoplastic material, so that granules having a double-layer structure composed of the inner core and an outer layer portion provided on the surface can be obtained. At this time, the melting point of the second thermoplastic material should be lower than the melting point of the first thermoplastic material. By selecting these materials in advance, the heating temperature during the coating of the outer layer portion can be a temperature that does not reach the melting point of the first thermoplastic material. . In addition, the so-called dissolution of the active ingredient of the inner core to a sustained release means that the first thermoplastic material that is hardly soluble in water is heated and melted to form a binder, so that the release of the active ingredient of the pesticide into water can be controlled. Pesticide formulation. In short, the sustained-release pesticide granules of the present invention can be specifically produced by the following steps. Step 1. First, a 20 ° C water-soluble pesticide active ingredient having a high water solubility in the range of 1000 ppm to 10% is used, an inorganic dilution carrier, and a first thermoplastic material are equipped with a heating device. Heating mixer (such as a floating mixer). At this time, the heating temperature should be above the melting point of the first thermoplastic material, and its temperature does not reach the melting point of the pesticide active ingredient contained therein. Step 2. After heating and mixing, the obtained homogeneous mixture is granulated with a granulation mechanism equipped with a heating device. The type of the granulator can be appropriately selected in consideration of the shape and particle diameter of the granulated product as the target product. Specifically, when a cylindrical shaped article is to be obtained, an extrusion type molding machine equipped with a screen matching the required particle size may be selected. When a spherical shaped article is to be obtained, a rotary granulator may be selected. Wait. Granulation temperature is up to 12 This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page) Order——: ------ Line- 1239807 A7 B7 5. Description of the invention (A) It is preferable that the melting point temperature of the first thermoplastic material used is higher than the melting point temperature of the contained pesticide active ingredient. In Step 3, the obtained granules often adhere to each other, and they must be crushed and sieved as required to obtain the slow-release granules (cores) of the required shape and particle diameter. Step 4, the same as the pesticide active ingredient with high water solubility contained in the core, the pesticide active ingredient with low water solubility in the range of 0.01-500ppm at 20 ° C, the inorganic dilution carrier, and The second thermoplastic material, which is different from the first thermoplastic material contained in the core and has a lower melting point than the first thermoplastic material, is difficult to dissolve in the second thermoplastic material, and if necessary, also has a surfactant and an auxiliary agent, such as a floating mixer Machine), etc., to obtain raw material powder for the outer layer portion. Step 5, adding the core prepared in Step 3 to a mixer equipped with a heating device (for example, a floating mixer, a rotary granulator, a Kura (々-5-) mixer, a drum mixer, Marumai Laza 5〗 (i) and so on), mix while heating, and quantitatively add the outer layer raw materials prepared in step 4 to cover the surface of the inner core to produce particles with the required particle size distribution. At this time, the heating temperature of the coated outer layer is set to the melting temperature of the contained second thermoplastic material, and the molten second thermoplastic material becomes a binder, so that the pesticide active ingredients with low water solubility and the inorganic dilution carrier are uniformly formed. The dispersed coating layer is used to prepare the coated sustained-release pesticide granules of the present invention. In addition, in this heating and coating step, in order to prevent the adhesion and adhesion between the cores due to the softening and melting of the first thermoplastic material in the core, and to prevent the cores from adhering to the inner wall of the mixing tank, crimping, etc. The heating temperature should be higher than the melting temperature of the second thermoplastic material used in the outer layer and the melting temperature of the first thermoplastic material used in the core. 13 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ) (Please read the precautions on the back before filling out this page) Order —— ^ ------ Printed by the Consumers' Cooperatives of the Intellectual Property Bureau of the Ministry of Economics Printed by the Consumers ’Cooperatives of the Intellectual Property Bureau of the Ministry of Agriculture and Economy 1239807 A7 — B7 5. Description of the invention (\ >) The following. In the coated sustained-release pesticide granules of the present invention having the above-mentioned structural characteristics, the composition ratio of each composition constituting the outer layer portion and the inner core thereof is not particularly limited, and it may be considered that the active ingredients of each pesticide should be maintained according to the following circumstances The concentration range, for example, the effective concentration range to achieve the preventive effect, and the duration of the concentration should be maintained appropriately. G 卩. · The components of one or more pesticide active ingredients contained in the surface layer portion and the inner core, respectively. Dissolution rate, speed of energy dissipation and absorption in the corresponding plant body, and transplantation of plant seedlings to the field. At this time, in general, for each granule, the mass of at least one or more pesticide active ingredients contained in the outer layer portion and the inner core of each granule is separately calculated, and the calculated mass ratio can be controlled in the inner core: outer layer portion = 1 : 15-15: 1 range. In addition, the coated sustained-release pesticide granules of the present invention or a solid agent composed of an outer layer portion and a core are not limited in shape and dosage form, and may be, for example, ordinary granules, pills, or tablets. Wait for any shape. In addition, when selecting the above dosage form, its size can be appropriately selected according to the use form. For example, the diameter of a cylindrical or spherical shape can be in the range of 0.1 to 3 legs, which is not particularly limited. Specifically, in the coated sustained-release pesticide granules of the present invention, the particle size can be appropriately selected according to the application form. For example, when using granules for rice nursery boxes, it is best to adjust the particle size. Control the particle size and shape of the mesh of the sieve, select within the range of 0.3-3mm. In addition, the length of the cylinder is preferably selected within a range that is not too long according to its diameter. For example, when the diameter of the cylinder is within the range of 0.1 to 3 strokes, the length is preferably selected to be between 0.1 and 10. Within range. In addition, in the coated sustained-release pesticide granules of the present invention, for example, when the spherical shape is selected, the diameter ratio of the inner core and the outer layer portion is not particularly limited. Generally, 14 paper sizes are applicable to the Chinese National Standard (CNS ) A4 size (210 x 297 mm) — Ίν — 1—x -------------- ^ --- :: -------- (Please read the precautions on the back first Refill this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ^^ 1239807 A7 B7 V. Description of the invention (θ) can be selected within the range of 1: 3. In general, the dissolution of the contained pesticide active ingredients, the smaller the particle size of the granules, the larger the granule surface per unit content of the pesticide active ingredients, and the dissolution is accelerated accordingly. However, in the coating type of the present invention, In the release pesticide granules, the inner core and the outer layer are each made of different hardly water-soluble thermoplastic materials. Through independent control of slow release, the particle size and the diameter ratio of the inner core and the outer layer are limited to the above ranges. Can achieve the required dissolution characteristics. Specifically, both the inner core and the outer layer are each added with a pesticide active ingredient. By adopting a structure containing an inorganic dilution carrier, since the amount of the pesticide active ingredient per unit volume can be adjusted within a wide range, the The granule surface area per unit content of the pesticide active ingredient is controlled within a certain range. At this time, since the pesticide active ingredients are uniformly diluted with an inorganic-based dilution carrier in each of the inner core and outer layer portions, it is preferable to adopt a method in which each of the pesticide active ingredients and the inorganic-based dilution carrier are powdered together and uniformly mixed with each other. In the coated sustained-release pesticide granules of the present invention, among the different types of pesticide active ingredients contained in the inner core portion and the outer layer portion of the granular sustained-release pesticide granules, usually, the pesticide active ingredient that can be used for a plant body as an object, for example, rice At least one or more pesticide active ingredients with high water solubility in the range of 1000 ° C to 10% in water at 20 ° C and pesticide activity with low water solubility in the range of 0 · Olppm to 500ppm at 20 ° C At least one kind of ingredients, and it is preferable to use any kind of biocidal compound for agricultural and horticultural purposes. For example, among the above compounds having biocidal activity, it is best to select a combination of insecticide and fungicide, but the following combinations are not excluded from the optimal combination. Combination of insecticides or fungicides 15 (Please read the precautions on the back before filling out this page) · nnn ϋ nn ϋ 5rJ * I nnn ϋ 1 n I, this paper size applies Chinese National Standard (CNS ) A4 size (210 X 297 mm) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1239807 Λ7 B7 V. Invention description (\ Ao, etc., can also choose a combination of drugs that have differences during their effective control period. 01 质量 % —50 质量 % 范围 , The content of these pesticide active ingredients in the coated sustained-release pesticide granules is not different according to whether the contained part is the core or the outer part. In each part, it is usually selected in the range of 0.01% by mass to 50% by mass. It is preferably within the range of 0.5 to 30% by mass, and is not particularly limited. That is, for each granule, the content of each pesticide active ingredient contained, according to the nature of the active ingredient, applicable field According to the decision, the application form is, for example, according to the application form as a granule for a nursery box, the amount to be applied per 1,000 square meters can be selected so that its content meets the necessary treatment amount per 1,000 square meters. In the coated sustained-release pesticide mixed granules of the present invention, in order to obtain mixed granules in which two or more pesticide active ingredients with particularly different water solubility are sustained-released, 20 ° of the pesticide active ingredients contained in the kernel The water solubility of C must be significantly higher than the water solubility of the pesticide active ingredient contained in the outer layer. In short, the water solubility of the pesticide active ingredient contained in the core at 20 ° C is at least 1,000 ppm to 10%. (Preferably 5000 ppm to 10%, particularly preferably lCK) 00 ppm to 10%, and on the other hand, the water solubility of the pesticide active ingredient contained in the outer layer at 20 ° C is selected to be at least 〇 · 〇 1-500ppm, preferably in the range of 1-300ppm, particularly preferably 0.5-200ppm, it is best to use this selection to make a very disparity in water solubility between the two. In addition, when the melting point of the pesticide active ingredient contained in the inner core is the same as or lower than the melting point of the first thermoplastic material used in the inner core, in the step of manufacturing the sustained-release pesticide granules of the present invention, the manufacturing system for the inner core is manufactured. In the case of particulate matter, when heated to melt the first thermoplastic material, the pesticide active ingredients mixed therein are also completely melted. 16 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) —, J ii 1- L -------------- ^ --- ^ ------ line (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1239807 A7 B7 V. Description of the invention). In this case, there is a possibility that they cannot be uniformly mixed with each other in a liquid state, and even if they are uniformly mixed, there is a possibility that the pesticide active ingredient segregates and cannot be uniformly dispersed when it is solidified thereafter. In this case, in the inner core, the active ingredients of the pesticide cannot form a form uniformly dispersed in the wax binder of the first thermoplastic material together with the added inorganic-based diluent carrier, so that the desired sustained release cannot be achieved Such a major issue. In order to solve this problem, the flame content of the pesticide active ingredient contained in the core is higher than the melting point of the first thermoplastic material used, and it is best to use a melting point of 100 ° C. If selected in this way, the pesticide active ingredient contained in the inner core does not melt. In this way, it is heated to a temperature at which the first thermoplastic material softens and melts. For example, it is best to form a powdery pesticide active ingredient and an inorganic dilution carrier to form a uniform mixture. , Dispersed in the first thermoplastic material. Similarly, when the melting point of the pesticide active ingredient contained in the outer layer portion is the same as or lower than the melting point of the second thermoplastic material used in the outer layer portion, in the step of coating the outer layer portion on the surface of the inner core in order to melt the second When the thermoplastic material is heated, the pesticide active ingredient mixed therein is also completely melted. At this time, there is a problem that the same abnormality occurs. In order to prevent these problems in advance, the melting point of the pesticide active ingredient contained in the outer layer should be at least higher than the melting point of the second thermoplastic material used. If possible, it is desirable that the first thermoplastic material has a higher melting point. The melting point is also high, it is best to use one with a melting point above 100 ° C. As the pesticide active ingredient that satisfies the above conditions, the following can be specifically exemplified. As the pesticide active ingredient contained in the core, for example, in the case of pesticides, the following can be exemplified. Melting point and water solubility at 20 ° C Have values in parentheses, respectively, insecticidal ring> evening 7 A) (125-128Γ, about 80%), Acetamipril (7 Seven Women S Bu,) (101-10-1 3 · 3 ° C · 42.0 ppm), Kiamato clone 17 — Jhlt ----------- ^ ------ ^ (Please read the precautions on the back before filling this page) The standard is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 1239807 A7 __B7 V. Description of the invention) / Bu Jin 廿 Λ) (139 · rC, 4100ppm), or The compound (KS) shown in Japanese Patent Application Laid-Open No. 7-178448 (1-methyl-2-nitro-3- (tetrahydro-3-pyranylmethyl) guanidine (about 105 ° C, 54 (X ) 0ppm). Examples of fungicides include pilocon (112 ° C, 4000ppm, blastin S (235 ° C, 3%), etc.) On the other hand, as the active ingredient of the pesticide stream contained in the outer layer, for example, Kill insects Examples include the following, melting point and solubility in water at 20 ° C with the value .NAC (142 ° C, about lOOppm) shown in brackets, and with Karup > Xi, < Less talented ^), (124 · 6-128 · 7 ° C, 40ppm); Kuloch Anijin (Xikou ^ 7 Erxue >), (176-178 ° C, 270ppm), leather Metoprolin (dagger. J bu α >), (234.4 ° C, 270 ppm) Fipronil (7 4 7. Mouth and mouth) (approximately 200 ° C, 1.9 ppm), Bupron Philippine (7, 7, 7. Port 7 y, y, >) (approximately i0 ° C, 0.9 ppm), Tebuferroquito (at 乂 >) (191 ° C, 0.83 ppm) In addition, as the bactericide, Fumeishuang (155 ° C, 30ppm), isocarbazone (136 ° C, 13ppm), Wang Jiaduo (102 ° C, 9.6ppm), Chifuzamido , $ K) (approximately 178 ° C, 1.59 ppm), Caruplopamide (Likou ~ Sb,) (147-149 ° C, 3.6 ppm), azostoropine oxide ( r, / now i 7 π π, >) (approximately 118 ° C, 10 ppm), Probezina Zulu (Wenkou ~ Yu, / a; 0 (approximately 138 ° C, 150 ppm), Kikulo Hemetor σ y) (approximately 150. (:, 5 mouth? 111), naphthalene tetraketonic acid (now today: ^ "di 7 acetic acid) (310. 0, 3.2 mouth 111), Tekulov Talam (7 Mouth and 3 A) (198 ° C, 14 ppm), Philly Zong a, / >) (175 ° C, 162 ppm), Kikulomakin (^ 々π J) (250-253 · 5 ° C, 0.74 ppm), Clotridone (178 ° C, (3 · 3 ppm), in which the pesticide (RS) — 1 —methyl — 2 —nitro — 3 — (tetrahydro — 3 —furylmethyl) guanidine is used as a core, and the fungicide is used The combination of Thicarbin for the outer layer is made from the sustained-release pesticide granules of the present invention to produce 18 paper sizes. The paper size applies the Chinese National Standard (CNS) A4 (210 X 297 mm) — „J h I, ----------- ^ ----- 1 (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 1239807 A7 __ B7 V. Description of the invention. 〇) One of the best combinations when used in seed box granules. Among the first thermoplastic materials for the core used in the slow-release pesticide powder of the present invention, it is best to use water with a solubility of less than 0.5% at 20 ° C. Organic matter that is insoluble or hardly soluble in water at room temperature and has a melting point of 70 ° C-110 ° C, preferably 72 ° C-W0 ° C, particularly preferably 74 ° C-98 ° C Within the range. For example, candelilla wax, the main plus original (i Erli, ^ &);) wax, Russ (57) wax, other plant-based waxes, nonacosanoic acid wax, ceresin wax, white ground hunting and other mineral waxes microcrystalline wax wax esters to get a feeling of petroleum-based wax, Fuchsal- Tropsch wax and other synthetic hydrocarbons, derivatives of icosanoic acid waxes, paraffin derivatives, microcrystalline wax derivatives, modified waxes, hardened sesame oil, hardened sesame oil derivatives, hydrogenated waxes, 12 -Hydroxystearic acid, amine stearate, imine phthalic anhydride, and fatty acids having chlorinated hydrocarbon groups, amidines, esters, ketones, and the like. Among them, the acid value determined by titration with an alkali according to the test method specified in the ASTM D1386 standard is preferably 10 mgkoH / g or more. For example, the main addition of the original p Erli, wax (melting point: 75 Ό, acid value: about 21mgkOH / g) or docosanoic acid wax (manufactured by BASF, trade name Luwax S, melting point: 75-85 °) C, acid value: 135-160mgkoH / g) icosanoic acid ester (made by BASF company, trade name LuwaxE, melting point: 75-85 ° C, acid value ·· 10-25mgkoH / g), etc. can be paid Sustained release, and can make the pesticide solvent components contained in the kernel release nearly 100%, especially suitable. These waxes may be used alone or as a mixture of two or more of them as a thermoplastic material. The total amount of the first thermoplastic material used is relative to the total amount of the composition constituting the inner core of the slow-release pesticide granules of the present invention. The mass is usually selected from 5 mass% or more and preferably 10 mass% or more. The amount of the pesticide active ingredient to be added, the nature of the inorganic diluent carrier and the amount thereof may be appropriately determined. It is best to look at it from an economic point of view. The 19 degree of the first thermoplastic material is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm ^ — .JV ^ I 1-L ---------- --- ^ ---: ------ ^ (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1239807 A7 _____ B7 V. Description of Invention (\?) The upper limit of the amount of addition can be selected to be 20% by mass. The inorganic-based diluent carrier for the core used in the sustained-release pesticide granules of the present invention is at least limited to show little water solubility and is not particularly limited. For example, examples include Clay, quartz, diatomaceous earth, calcium carbonate, pumice, bentonite, vermiculite, perlite, green palygorskite and non-aqueous hydrous silicic acid, commonly known as white carbon black, etc., usually one or more of them are used in pesticide powder or The so-called bulking agents or carriers used in the granules are used in combination. In addition, in the sustained-release pesticide granules of the present invention, in addition to the above-mentioned inorganic diluent carrier in the core, the objects and effects of the present invention are not impaired. Within the range, it can also be made into powders and added with antioxidant UV absorption Various additives such as antistatic interference agents. For example, as the antioxidant, syndado (t > Xi'K) phenol-based antioxidant, sulfur-based antioxidant, phosphorus-based antioxidant, ammonia-based antioxidant, internal Ester-based antioxidants, vitamin E-based antioxidants, etc. Examples of the ultraviolet absorber include inorganic compound-based ultraviolet absorbers such as cobalt dioxide, benzotriazole or benzophenone, triazine benzoate, and water-based Organic compounds such as acid esters are UV absorbers, etc. At this time, these antioxidants or UV absorbers can be selected based on the physicochemical properties of the active ingredient of the pesticide contained in the core, or an amount can be added to confirm the effect. Examples of the antistatic interference agent include cobalt oxide, zinc oxide, manganese oxide, etc., inorganic compounds, calcium phosphate-based compounds, etc. In addition, phosphate-based surfactants such as polyoxyethylene alkyl ether phosphate can also be used as antistatic interference. In addition, the antistatic interference agent can be used as needed, and the amount used is within a range that does not impair the object and effect of the present invention. An amount capable of confirming the antistatic effect may be used. On the other hand, in the sustained-release pesticide granules of the present invention, it is difficult to be used as the outer layer. This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297). ) Ni 丨 -------------- Order --- ^ ------ line (please read the precautions on the back before filling this page) A7 1239807 V. Description of the invention ( A) The d-th thermoplastic material that is soluble in water is substantially the same as the thermoplastic material used in the core. It can also be used in combination of two or more. Its melting point is compared with the first thermoplastic material contained in the core. Must be lower, the melting point of the specific second thermoplastic material is best selected within the following range, usually 40 C-70 C, preferably 50 ° C-69 ° C, especially 60 ° C-68 ° C. There is a second thermoplastic material. In the coating step, since it is melted to form an adhesive, if the melt viscosity is low, there is less adhesion between particles during coating, which is suitable. As suitable specific examples of the second thermoplastic material satisfying the above-mentioned various conditions, botanical waxes such as candelilla wax and Japanese wax, beeswax, laurel, whale wax, animal waxes such as tallow, petroleum oils such as paraffin, petrolatum, and the like are listed. Fully hydrocarbon-forming waxes such as system waxes, Fuchscher-Tropsch waxes, and modified waxes such as paraffin derivatives. Among them, paraffin wax (made by Nippon Seiki Wax Co., Ltd., trade name: paraffin 140, melting point: 61 ° C, or trade name · SP-0145, melting point: 63 ° C, stone snail 150, melting point 66 ° C) and more it is good. The amount used is determined by the amount of the pesticide active ingredient contained in the outer layer portion and the nature of the inorganic diluent carrier. However, in the sustained-release pesticide granules of the present invention, the total mass of the composition of the outer layer portion can be in the following range Internal selection, that is, usually 1% to 20% by mass, preferably 1% to 15% by mass, and the content of the second thermoplastic material needs to be set below the total oil absorption of the outer layer composition. The inorganic diluent carrier for the outer layer portion used in the sustained-release pesticide granule of the present invention is at least limited to show no water solubility and is not particularly limited. The use of substantially the same material as the aforementioned inorganic diluent carrier for the inner core can sufficiently achieve the purpose. Therefore, for example, clay, quartz, talc, bentonite, calcium carbonate, pumice, diatomaceous earth, vermiculite, perlite, green palygorskite and non-quality hydrous silicic acid, commonly known as silica, etc. Or one or more of the same as 21 to re-size / f CNS A4 specifications (210x 297 public) " ": — .J. V Ί- -------- ^ --- \ ------ ^ (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 1239807 V. Description of the invention (> °) in pesticide powder or granules The so-called bulking agents or carriers are used in combination. Further, in the sustained-release pesticide granules of the present invention, in addition to the inorganic-based diluent carrier, the surface layer may further contain a surfactant and a supplementary agent within a range that does not impair the object and effect of the present invention. Among the sustained-release pesticide granules of the present invention, examples of the surface active agent that can be added to the outer layer include nonionic surface active agents, anionic surface active agents, and cationic surface active agents commonly used in pesticide formulations. And amphoteric surfactants, such as alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene phenadienyl phenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan aryl alkyl Compounds, polyoxyethylene phenyl ether polymers, polyoxydiene alkylene phenyl aryl ethers, polyoxyethylene alkylene glycols, polyoxyethylene polyoxypropylene block copolymers and other nonionic interface activities Agent, lignosulfonate, alkylarylsulfonate, dialkylsulfosuccinate, polyoxyethylene alkylaryl ether sulfate, naphthalene alkylsulfonate, polyoxyethylene styrylphenyl sulfate Anionic surfactants such as salts, cationic surfactants such as alkylamine salts, quaternary ammonium salts, alkylbetaines, and amine oxides, and amphoteric surfactants. When these surfactants are added, one kind may be used, or the same kind or different kinds may be used in combination. In addition to the surfactant, examples of the auxiliary agent that can be added to the outer layer include solid organic acids such as aromatic aromatic acids, polycarboxylic acids, sugar derivative carboxylic acids, and water-soluble polymers. Specific examples of the organic acid include dibasic acids such as oxalic acid, malonic acid, succinic acid, maleic acid, and fumaric acid, or sugar-derived types such as malic acid, tartaric acid, and other hydroxyl-substituted dibasic acids, ascorbic acid, and citric acid. carboxylic acid. Examples of water-soluble polymers include polyvinyl alcohol, carboxymethyl cellulose, dextrin hydroxyethyl cellulose, methyl cellulose, alginate, gelatin, pectin, and pullulan paper. China National Standard (CNS) A4 Specification (210 X 297 mm) — • " 7 * ------------------- Order --- · ----- -Line (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Consumer Cooperatives of the Ministry of Economic Affairs and Intellectual Property Bureau printed 1239807 A7 ________________ B7 V. Description of the Invention (> \) Polyethylene Pyrrolidone, polypropionate, polyethylene oxide, etc. The total amount of the surface active agent and these supplements relative to the total mass of the outer layer composition is preferably kept in the following range, which is generally 0.01 mass% to 20 mass%, and preferably 0.01 mass to 10 mass%. . The slow-release pesticide adhesive of the present invention having the structure described above can realize slow-release, so that two or more different pesticide active ingredients that can greatly differ in water solubility have their respective dissolution rates. Release, can be used as pesticide granules especially suitable for rice seedling box granules. By using the slow-release pesticide granules of the present invention, granules for rice nursery boxes can be obtained. Among the 30-60 days that must be prevented from pests and diseases during the rice cultivation period from rice transplanting, depending on the situation, it is also longer than 60 days. The pesticide active ingredient is continuously released over time and can be released substantially completely. In addition, the slow-release pesticide granules of the present invention can reduce the manufacturing cost because the drying process necessary for the method described in JP-A-2000-44404 can be omitted. For example, when the slow-release pesticide granules of the present invention are used as granules for a rice seedling nursery, they can be put into the rice seedling nursery before transplanting. In addition, when used as a granule for a nursery box, its application amount is approximately 10g-100g per rice nursery box (approximately 30cmX60cm), generally 50 or so, which is not particularly limited. The content of pesticide active ingredients in the preparation is necessary. The period of preventing pests and diseases can be determined according to the number of nursery boxes used in every 10 ares. In addition, when the pesticide granules of the present invention are applied to a rice nursery box, for example, when the granules are evenly spread throughout the nursery box and then the seedlings are transplanted to the paddy field, the number of pesticide granules around each seedling is the largest. Don't make a big difference. For this purpose, the particle size of the granules, specifically the size of the sieve used to determine the particle size distribution, etc. should not be too large, so prevent the use of pesticide granules corresponding to a certain amount of use. Standard (CNS) A4 (210 X 297 mm) Μ ΜΙ »b— I Ji -ΊΙ n I n ϋ I ϋ · ϋ nn II n ϋ 一 ^ J« n I ml nn ϋ \ I \ (Please read first Note on the back, please fill out this page again) ^ ___ Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1239807 Invention Description (> >) The number should not be too small. That is, as a user of rice seedling box granules, the number of agricultural granules per lg is 300 or more, preferably 400 or more, and the sieve mesh size is selected accordingly. However, due to differences in the content of the inorganic diluent carrier and its loose specific gravity, the particle size of the granules must not be too small, and it must be prevented from floating in water due to too small a particle size. Adding a surface active agent to the outer layer to increase the affinity to the surface of the water can prevent some of the above-mentioned abnormal conditions. In this way, the number of pesticide granules per lg is expected to remain within the range of no more than 2000. DETAILED DESCRIPTION i The present invention will be described in further detail through the following examples. In particular, the slow-release pesticide granules of the present invention are used as specific examples of rice seedling box granules. However, the present invention is not limited by the method for producing such a seedling box granules and the obtained formulation. For example, (KS) -1-methyl-2-nitro-3- (tetrahydro-3-furanylmethyl) guanidine used as a core pesticide active ingredient is used as a pesticide active ingredient in the outer layer The thiabendazole can be replaced by the above-mentioned various pesticide active ingredients, or each of the thermoplastic materials used in the inner and outer parts shown in the examples, and the inorganic dilution carrier can also be replaced by other materials mentioned above. The slow-release pesticide granules of the invention can be used to prepare granules for rice nursery boxes. It should be noted that the composition ratios shown in the following specific examples are all yield% ratios except for those specified. In Reference Example 1-6, the cores of Reference Example 1-6 were obtained at the composition ratios shown in Table 1 by the production method described below. 24 IJ >-Ίν -------------- Order --- ^ ------ line (Please read the precautions on the back before filling this page) This paper size is applicable China National Standard (CNS) A4 specification (210 X 297 mm) A7 1239807 B7 V. Description of the invention (y >) [Table 1] Composition of the granulated substance (core) (quality 邰) Manufacturing conditions Luwax Luwax white Carbon talc heating mesh 1 SE J > Calcium temperature dimension reference example 1 3 · 0 18.0 5.0 10.0 64.0 90 ° C 0.8 mm reference example 2 3.0 18.0 3.8 10.0 65. 3 83 ° C 0.8 mm reference example 3 3.0 3.6 14.4 5.0 10.0 64 · 〇83 ° C 0.8 mm Reference Example 4 5.0 18.0 5.0 10.0 62. 0 90 ° C 0.7 mm Reference Example 5 5.0 18.0 3.8 10.0 63 · 3 83 ° C 0.7 mm Reference Example 6 5.0 3.6 14.4 5.0 10.0 62. 0 83 ° C 0.7 mm J—ί double ------- — order --- ^ ------ line (please read the precautions on the back before filling this page) Bureau of Intellectual Property, Ministry of Economic Affairs Printed by an employee consumer cooperative as a pesticide active ingredient contained in the kernel. (KS) -l-methyl-2-nitro-3- (synthesized according to the method described in Japanese Patent Application Laid-Open No. 7-178448 Hydrogenated 3-furanylmethyl) guanidine (hereinafter abbreviated as: Compound 1). As the inorganic diluent carrier, white carbon black, talc, and calcium carbonate were used. As the first thermoplastic material, nonacosanoic acid wax (manufactured by BASF Corporation) was used. , Trade name Luwax S, melting point: 75-85 ° C, acid value: 135-160 mgkoH / g) and / or icosanoic acid ester wax (manufactured by BASF, trade name LuwaxE, melting point 75-85 ° C, acid value: 10-25mgkoH / g), the paper size of the above materials shall be in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm). Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 1239807 A7 _____ B7 V. Description of the invention (Put together into a floating mixer equipped with a heating device, heat to 83 ° C-90 ° C and mix and use the mixture. Horizontal extrusion granulator (mesh size) maintained by the heating device at 90 ° C. (0.7 mm or 0.8 mm sieve)), extruded and granulated, the composition shown in Table 丨 and the granules obtained under the manufacturing conditions are pulverized and sieved according to the preparation of Reference Example 1-6. Particulate matter (nucleus) Experimental example 1: Dissolution experiment of kernel. The following method was used to measure the dissolution rate of the pesticide active ingredient (chemical 1) released from the kernel prepared in Reference Examples 1-6 ^ That is, the kernel obtained in Reference Examples 1-6 was placed in a 25 degree approved 3 degree container In a test tube with a sealing plug with a melting capacity of 50 ml of hard water, when all the pesticide active ingredients are fully dissolved, the amount that can be released corresponds to the amount that makes the concentration of pesticide active ingredients (compounds) reach 920 ppm, which is insoluble. The material was precipitated in water. In this state, after a certain amount of static time at 25 ° C, the whole amount was filtered, and the amount of the pesticide active ingredient (compound 1) dissolved in the filtrate was measured by HPCC. According to the measured value. The dissolution rate was calculated by the following formula, and the results are summarized in Table 2. Dissolution rate = (amount of pesticide active ingredient in the filtrate / pesticide active ingredient in the granules) X 100. As shown in Table 2, in the sustained-release pesticide granules of the present invention, the granules (cores) of Reference Examples 1-6 equivalent to the cores may be in the range of one week to two months at any time. Both release the contained pesticide active ingredient (Compound 1) slowly, and at the same time can be released substantially completely. 26 This paper size applies to China National Standard (CNS) A4 (210 X 297 public love) nn —1 1— ϋ nn I n ϋ · -Ϊ n 1.1 .1 II «III ϋ I n ϋ ϋ n II (please first Read the notes on the back and fill in this page again) 1239807 A7 V. Description of the invention (/) [Table 2] Dissolution rate of compound 1 released from the granules (inner core) Dissolution rate (%) of compound 1 7 days later, 14 days later ------- 30 days and 60 days later Reference Example 1 59.2 77. 7 98. 5 ιαι · 1 Reference Example 2 17.6 26.8 40. 1 53.2 72.6 97.7 Reference Example 3 31.8 44. 7 59. 2 75.6 95.4 100.2 Reference Example 4 51.6 75.0 97.6 100.2 Reference Example 5 20.6 32. 3 44 · 5 58.4 75.8 94.8 Reference Example 6 35.5 50.0 65.0 82 · 2 98.4 100.0 n -i ^ in J— «nn I n! I— 1— · Mu nn · 1 n (Please read the precautions on the back before filling in this page) Ordering Examples 1 -12 With the composition ratio shown in Table 3, on the pellets of Reference Example 1-6 as the core, The outer layer was coated by the method described below to prepare the granules for rice seedling boxes of Examples 1-12. [Table 3] Production line for rice seedling box granules of King Mgl 1-12 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Kernel (Quality Department) 67.5 (Reference Example 1) Primitive powder Crushed stone

24. sorp〇l - 5〇5〇24. sorp〇l-5〇5〇

本紙張尺度適用中國國家標準(CNS)A4規格(21〇 x 297公釐)This paper size applies to China National Standard (CNS) A4 (21 × 297 mm)

1239807 A7 B7 經濟部智慧財產局員工消費合作社印製 五、 S __ 實施例 2 67. 5 (參考例2) 24.0 4. 5 4. 0 實施例 3 67. 5 (參考例2) 24.0 4. 5 1. 0 3.0 實施例 4 67. 5 (參考例3) 24· 0 4.5 4.0 實施例 5 67. 5 (參考例3) 24.0 4.5 • 1.0 3.0 實施例 6 40.0 (參考例4) 24.0 7.0 29.0 實施例 7 40.0 (參考例5) 24.0 7.0 29.0 實施例 8 40.0 (參考例5) 24. 0 7.0 6.0 23.0 實施例 9 40.0 (參考例5) 24.0 7.0 1.0 23.0 實施例 10 40.0 (參考例6) 24.0 7.0 29.0 實施例 11 40.0 (參考例6) 24.0 7.0 6.0 23.0 實施例 12 40.0 (參考例6) 24.0 7.0 1.0 23.0 首先,作爲外層部的原料粉末,將含有農藥活性成分的(7° 口 :/于'/一;u)原體,作爲無機系稀釋載體的黏土,作爲黏土 28 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 1239807 Λ7 B7 五、發明說明(V?) 熱塑性材料的石蠘(日本精蠟公司製,商品名:石蠟150熔點 66°C,以及根據需要作爲介面活性劑的磺基琥珀酸二烷基酯(東 邦化學工業公司製,_品名S0RP0L—5050),或者作爲補助劑的 檸檬酸一起裝入浮動或混合機混合。 其次,將由參考例1-6製得的製粒物(内核)的任何一種, 放入裝有加熱裝置的浮動式混合機中一邊加熱到70°C—邊混 合,定量的添加先前製得的外層部原料粉.末,進行包覆,從而 得到只有所要求的粒度分佈,相當於網孔尺寸爲1.0-2. 0mm的 粒徑和粒子,製得實施例1-12的水稻育苗箱用粒劑。再有,此 處可得到的粒劑,任何一種的每lg的粒子數大致是400個。 比較例1-2 將兩種農藥活性成分:化合物(殺蟲劑)和口 X于、/一;(殺 菌劑) 一起包含在製料物中,而且爲了得到不設置包覆層的粒劑,用 表4所示100組成配方,用同參考例1-6 (内核)相同製粒的方 法配製製粒物。將可得到的製粒物進行粉碎。篩分後,製得比 較例1、2的粒劑。 n -H ϋ J— i— n n - - I n · - - I in 1 - n f 一 t 1 I I i l I ϋ I (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 [表4] 比較例1、2的粒劑的組成和製造條件 比較例1、2的粒劑組成(質量分) 製造條件 化 合 物1 噻菌 靈原 體粉 碎末 Luwax S Luwax E 白炭 里 滑石 碳酸 鈣 加 熱 溫 度 網孔 尺寸 29 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 經濟部智慧財產局員工消費合作社印製 1239807 A7 B7 t匕 較 例1 2.0 24.0 18.0 3.8 10.0 42. 3 83 °C 0. 8mm t匕 較 例2 2.0 24.0 3.6 14.4 5.0 10.0 41.0 83 °C 0. 8mm 比較例3-5 ' 如表5所示將兩種農藥活性成分:化合物1 (殺蟲劑)和π夂 于'/一> (殺菌劑)一起混合,用同參考例1-6相同的製粒方 法製得製粒物(内核)。其後按同實施例1-12相同的順序,將 完全不含有農藥活性成分的外層部原料粉末進行包覆,製得比 較例3-5的粒劑。 I M -h I π Ί.--------------訂----1------線 (請先閱讀背面之注意事項再填寫本頁) [表5]比較例3-5的粒劑組成 内核的組成(質量部) 製造條件 化 合 物1 噻菌 靈原 體粉 碎末 Luwax S Luwax E 白 炭 里 滑 石 碳酸 鈣 加 埶 溫 度 網孔 尺寸 b匕 較 例3 2.0 24.0 12. 2 3.4 6.8 19. 1 90 °C 0. 8mm 30 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) A71239807 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy V. S __ Example 2 67. 5 (Reference Example 2) 24.0 4. 5 4. 0 Example 3 67.5 (Reference Example 2) 24.0 4. 5 1. 0 3.0 Example 4 67. 5 (Reference Example 3) 24 · 0 4.5 4.0 Example 5 67.5 (Reference Example 3) 24.0 4.5 • 1.0 3.0 Example 6 40.0 (Reference Example 4) 24.0 7.0 29.0 Example 7 40.0 (Reference Example 5) 24.0 7.0 29.0 Example 8 40.0 (Reference Example 5) 24. 0 7.0 6.0 23.0 Example 9 40.0 (Reference Example 5) 24.0 7.0 1.0 23.0 Example 10 40.0 (Reference Example 6) 24.0 7.0 29.0 Example 11 40.0 (Reference Example 6) 24.0 7.0 6.0 23.0 Example 12 40.0 (Reference Example 6) 24.0 7.0 1.0 23.0 First, as a raw material powder for the outer layer portion, (7 ° Mouth: / 于 '/ A; u) the original body, as the clay of the inorganic dilution carrier, as the clay 28 (please read the precautions on the back before filling this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1239807 Λ7 B7 V. Description of the invention (V?) Shizuo (Japanese refined wax) for thermoplastic materials Company name, trade name: paraffin 150 melting point 66 ° C, and dialkyl sulfosuccinate as surfactant (manufactured by Dongbang Chemical Industry Co., Ltd., S_RP0L-5050) as needed, or citric acid as a supplement Put them together in a floating or mixer to mix them. Next, put any of the granules (cores) prepared in Reference Examples 1-6 into a floating mixer equipped with a heating device and heat to 70 ° C. 0mm 的 的 粒 的 量 和 粒 , 被 实施 例。 Preparation, mixing, quantitative addition of the previously prepared outer layer of raw material powder. Finally, coating, so as to obtain only the required particle size distribution, equivalent to a mesh size of 1.0-2. 0mm particle size and particles, to obtain an example Granules for rice seedling boxes of 1-12. In addition, the number of granules per lg of any of the granules available here is approximately 400. Comparative Example 1-2 Two pesticide active ingredients: compounds (kill Insecticide) and mouth X Yu, / a; (fungicide) are included in the preparation together, and in order to obtain the granules without a coating layer, a composition of 100 is shown in Table 4, and the same reference example 1- 6 (Kernel) Prepare the granules by the same method of granulation. The obtained granulated product is pulverized. After sieving, granules of Comparative Examples 1 and 2 were prepared. n -H ϋ J— i— nn--I n ·--I in 1-nf a t 1 II il I ϋ I (Please read the precautions on the back before filling out this page) Intellectual Property Bureau Staff Consumer Cooperatives Printed [Table 4] Composition of granules and manufacturing conditions of Comparative Examples 1 and 2 Granule composition (mass fraction) of Comparative Examples 1 and 2 Production conditions Compound 1 Thiabendia pulverized powder Luwax S Luwax E white carbon talc Calcium carbonate heating temperature mesh size 29 This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1239807 A7 B7 tdk Comparative Example 1 2.0 24.0 18.0 3.8 10.0 42. 3 83 ° C 0. 8mm t Comparative Example 2 2.0 24.0 3.6 14.4 5.0 10.0 41.0 83 ° C 0. 8mm Comparative Example 3-5 'As shown in Table 5, two pesticide active ingredients: Compound 1 (insecticide Agent) and π 夂 '/ a> (fungicide) were mixed together, and granulated material (inner core) was obtained by the same granulation method as in Reference Examples 1-6. Thereafter, in the same procedure as in Example 1-12, the raw material powder of the outer layer portion containing no pesticide active ingredient was completely coated to obtain granules of Comparative Example 3-5. IM -h I π Ί .-------------- Order ---- 1 ------ line (Please read the precautions on the back before filling this page) [Table 5 ] Comparative Example 3-5 Granule composition Core composition (mass part) Production conditions Compound 1 Thiabendia pulverized powder Luwax S Luwax E white carbon talc calcium carbonate temperature temperature mesh size b dagger comparative example 3 2.0 24.0 12. 2 3.4 6.8 19. 1 90 ° C 0. 8mm 30 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) A7

6.8 20. 83 °C ----〜 90 °C 〇· 經濟部智慧財產局員工消費合作社印制π 1239807 ΐ匕 較 例4 2.0 ;-1— 24.0 12.2 2.5 [:匕 較 2.0 24.0 7.2 2.0 例5 4. 外層部原料粉末的組成(質量分^^ 石蠟 黏土 ^---. S〇rp〇l、5 050 比較例3 4.5 27.0 1·0 比較例4 4. 5 27.0 --- 1.0 比較例5 7.0 52.0 1.0 比較例6-8 如表6所示,將7 π X于、/一;U (殺菌劑)加入到内核料中 用同參考例1-6同樣的製粒方法得到製粒物(内核)隨後,加 入化合物1 (殺蟲劑),將混合得到的外層原料粉末。 按同實施例1-12相同的順序包覆是在製粒物(内核)的表 面上,製得比較例6-8的粒劑。 31 f請先閱讀背面之>i音?事項再填寫本頁)6.8 20. 83 ° C ---- ~ 90 ° C 〇 · Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economy π 1239807 Comparative example 4 2.0; -1—24.0 12.2 2.5 [: comparative example 2.0 24.0 7.2 2.0 Example 5 4. Composition of the raw material powder in the outer layer (mass fraction ^^ Paraffin clay ^ ---. Sorpoll, 5 050 Comparative example 3 4.5 27.0 1 · 0 Comparative example 4 4. 5 27.0 --- 1.0 Comparative example 5 7.0 52.0 1.0 Comparative Examples 6-8 As shown in Table 6, 7 π X in / /; U (fungicide) was added to the core material and granulated by the same granulation method as in Reference Examples 1-6. (Inner core) Subsequently, compound 1 (insecticide) is added, and the outer raw material powder obtained by mixing is coated in the same order as in Example 1-12. The surface of the granulated product (inner core) is coated to obtain a comparative example. Granules 6-8. 31 f Please read the > i sound on the back? Matters before filling out this page)

本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 1239807 五、發明說明(V9) A7 表六 比較例6-8的粒劑的組成 内核的組成 (質量分) 製造條件 噻菌 Luw- Luw- 白炭 滑 碳酸 加熱 網孔 靈原 ax S ax E 里 石 鈣 溫度 尺寸 體粉 碎末 ·* 比較例 24.0 12.2 3. 4' 6.8 21. 1 90 V 〇· 8 6 mm 比較例 24.0 12.2 2· 5 6.8 22.0 83 V 0.8 7 mm 比較例 8 24.0 7.2 2.0 4.0 2.8 90 °C 0.7 mm (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 外層部的原料粉末的組成(質量 分) 化合物 1 石蠟 黏土 比較例6 2.0 4. 5 26·〇 比較例7 2.0 4.5 26.0 比較例8 2.0 7.0 51.0 比較例9 如表7所示的組成,將予先把化合物1(殺蟲劑)溶解的甲 醇溶液吹附在球狀固體載體(東海工業公司製,商品名:伊豆 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 經濟部智慧財產局員工消費合作社印製 1239807 a? B7 五、發明說明(Μ) 石英砂,粒徑〇·3-lmm)的表面後,在50°C的乾燥器中靜置3 小時以除去甲醇,製得不能緩釋化的内核。隨後,加入表7所 示組成的 (殺菌劑),將混合得到的外層部原料粉末用同 實施例1-2相同的方法包覆在上述内核的表面,製得比較例9 的粒劑。 表7比較例9的粒劑的組成 内核(質量分) 外屬部原料粉末的組 成(質量分) 化合物1 球狀固體載體 (伊豆石英砂) 噻菌 靈原 體 石蠟 黏土 比較例 9 2.0 38.0 24.0 12.0 24.0 試驗例2,水稻的育苗箱用粒劑溶出試驗 對於由上述實施例1-12和比較例1-9得到的粒劑,測定由 各粒劑釋放出的農藥活性成分的溶出率。 ①化合1 (殺蟲劑)的溶出率。 在由實施例1-12和比較例1-9製得的粒劑中所含有的兩種 農藥活性成份中,用以下所述的方法測定由各粒劑中釋放出的 化合物1 (殺蟲劑)的溶出率。 艮P,將由實施例和比較例製得的各粒劑放入裝有25ml標準 3度硬水的容量爲50ml的帶密封塞的試管中,加入的量相當於 使化合物1 (殺蟲劑)的濃度達到920ppm的量,當所含有的化 合物1 (殺蟲劑)分別全部溶出時,不溶物沈澱於水中。在這種 (請先閱讀背面之注意事項再填寫本頁) .¾ 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) A7 1239807 五、發明說明(β 狀態,25°C下靜置一定時間,全量過濾,用HPLC法測定溶解在 濾液中的化合物1 (殺蟲劑)的量。根據測定值按下式計算溶出 率,將結果匯總於表8。 溶出率=(濾液中的殺蟲劑量/粒劑中的殺蟲劑量)X 100 I Ί ^ Ί . --------訂----:------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 表8 由各粒劑釋放出的化合物1 (殺蟲劑λ的溶出率 化合物的溶出率(%) 1日後 3日後 7曰 後 14日 後 30日 後 60日 後 90日 後 實施例 1 3.3 9.7 22. 1 44· 9 100. 1 實施例 2 0. 7 2. 7 6.6 15.7 33. 3 77.8 97.8 實施例 3 10.2 22.7 41.9 59.6 81.2 99. 1 實施例 4 5. 5 11. 2 21.9 41. 6 87.2 101.0 實施例 5 27.8 42. 7 59. 1 77.0 94.4 100. 5 實施例 6 2. 7 8.8 19.8 40.9 92.6 實施例 7 0.4 2. 1 5. 7 12.8 30. 1 66. 6 94.6 34 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 1239807 B7 A7 經濟部智慧財產局員工消費合作社印製 五、名 tn口 士公口、______ "mm 8 9. 8 18. 7 33.6 52.8 78. 1 100.4 實施例 9 8. 5 23. 1 39. 7 56.6 78. 3 97.8 實施例 10 5. 7 11· 1 22.2 41. 3 85.3 99. 9 實施例 11 28. 1 44.0 64. 1 81.4 98.9 實施例 12 31.3 44.2 60.0 77. 1 96.2 比較例 1 82.6 96.8 100· 1 比較例 2 95. 7 99.4 99. 3 比較例 6 97.3 100.8 101.0 比較例 7 94. 1 99.2 99.8 比較例 8 95. 5 97.6 99. 3 比較例 9 79. 3 92.8 98.8 如表8所示所表明的,就實施例的粒劑而言,在内粒中所 含有的殺蟲活性成分可在約1個月一3個月的時間中持續地釋放 35 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 1239807 A7 B7 五、發明說明(々今) 出來,而且,所含有的殺蟲活性成分的全部大致可完全釋放出 來。與此相反,對於沒有設置包覆層的比較例1,2,另外對沒 有内核,在外層部中含有化合物1的比較例6-8;或者對沒有使 用解釋化技術的内核中含有化合物1的比較例9而言,任何一 種都不能緩釋化,在大致1-3日中就達到近乎100%的溶出率。 ②d 口 f于、/一> (殺菌齊ij)的溶出率。 在由實施例1-2和比較例1-9所得到的粒劑中所含有的二 種農藥活性成分中由各粒劑釋放出的d 口 {于/一;l (殺菌劑) 的溶出率用以下所提到的方法進行測定。 艮P,將由實施例和比較例製得的各粒劑放入裝有1000ml, 離子交換水的容量爲l〇〇〇ml帶密封的三角燒瓶中,加入的量相 當於使d α {于'/一;(殺菌劑)的濃度達到30ρρπι的量,當所 含有的d 口 '/一;u (殺菌劑)全部溶出時,不溶物沈澱於水 中,在這種狀態25°C下靜置,隨後,每隔一定時間,由水深5cm 深度處,採樣lml用HPLC法測定該採樣中的殺菌活性成分的濃 度,實驗條件是供試驗的粒劑中殺菌劑的全量在三角燒瓶中的 1⑻0ml的水中溶出時的濃度爲30ppm,將所測定的殺菌劑的濃 度值以30ppm去除即得溶出率。將結果匯總於表9。 I M -h U ----------------訂---^------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印制π 36 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 1239807 λ7 Β7 五、發明說明(^) [表9]由各粒劑釋放出的^一>)殺菌劑的溶出率 經濟部智慧財產局員工消費合作社印制衣 (7。口^:于y 一;殺菌劑的溶出率(0/〇) 1曰 後 3日後 7日後 14日 後 30日後 60曰 後 90曰 後 實施例 1 〇· 7 5. 1 9.2 18.4 40.0 82. 1 101. 0 實施例 2 1. 1 2.9 7.3 15.9 35.6 77. 7 96.2 實施例 3 2.0 5. 7 12.4 22· 6 52· 1 97· 2 98.0 實施例 4 0.2 3.1 7.9 17.7 39.3 84.8 93. 5 實施例 5 2.9 6.2 14.5 28.9 55.6 100.0 實施例 6 0.4 6. 1 10.0 22.2 44. 2 84.6 102.0 實施例 7 3.0 6.9 15. 1 27· 1 46.2 88. 1 97. 7 實施例 8 3. 3 7· 1 13.2 25.9 54.4 100.6 實施例 9 2. 7 5. 5 13. 1 24.9 55.6 98. 9 實施例 10 3.6 6·〇 13. 3 28.0 47.0 84. 0 96.8 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) 1239807 B7 }- 5.8 實施例 11 2.2 13. 7 26.8 58.8 99.0 實施例 12 3.0 5.7 17.2 31.6 57.3 100. 7 比較例 3 0.2 1. 1 3.2 6· 6 14.9 28.8 38. 1 比較例 4 ND ND 0.8 2.4 7.5、 18.2 26.9 比較例 5 0.2 0.8 2.4 5· 1 12.0 24.7 33. 3 比較例 6 ND 0.4 1.7 3.7 7.4 13.6 22.8 比較例 7 ND 0· 1 0.4 2· 1 5.0 11· 1 22. 7 比較例 8 ND ND 0.4 1. 1 3.6 9.9 16.3 如表9所示的結果表明的,實施例的各粒劑可在大約3個 月的時間中將殺菌劑逐漸釋放出來,而且在外層部所需有的全 部殺菌劑大致能完全釋放出來,與此相反,就内核中所有殺菌 劑的比較例3-8的粒劑而言,即使經過約2個月,也只有含有 量的一部分溶出,其溶出率極低。 在本發明的包覆型緩釋性農藥粒劑中,當含有水溶解度具 有極大差異的兩種以上的農藥活性成分時,大體是其中一種的 水溶解度在lOOOppm以上時,可以將這兩種以上的濃度活性成 38 本紙張尺度適用中國國家標準(CNS)A4規格(210 x 297公釐) (請先閱讀背面之注意事項再填寫本頁) «衣 訂- ------線 經濟部智慧財產局員工消費合作社印製 1239807 A7 B7 五、發明說明(7文) 分分別實現緩釋化,例如,可以製得適於水稻的育苗箱用粒劑 的農藥混合粒劑,另外,就本發明的包覆型緩釋性農藥粒劑而 言,由於可以將所含有的兩種以上的農藥活性成分含有的量大 致全部一起釋放出來,在所要求的時期中可將應慢慢散佈在田 地中的農藥活性成分不斷溶出,不必擔心有一部分殘留在粒劑 中,再有,本發明的包覆型緩釋性農藥粒劑在製造時,不必用 樹脂包覆内核的表面而生成包覆粒子,由於可以省去設置在樹 脂包覆後的乾燥工序,節省了多餘的工序,這樣其優黏是既採 用雙層結構的劑型,又可降低其製造成本。 (請先閱讀背面之注意事項再填寫本頁) •罐衣 訂i — T-----線- 經濟部智慧財產局員工消費合作社印制农 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐)This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1239807 V. Description of the invention (V9) A7 Table 6 Composition of the granules of Comparative Examples 6-8 Composition of the core (mass fraction) Manufacturing conditions Bacteria Luw- Luw- White carbon slip carbonic acid heating mesh Lingyuan ax S ax E Lithium calcium temperature dimensional body crushing powder * Comparative Example 24.0 12.2 3. 4 '6.8 21. 1 90 V 〇 · 8 6 mm Comparative Example 24.0 12.2 2 · 5 6.8 22.0 83 V 0.8 7 mm Comparative Example 8 24.0 7.2 2.0 4.0 2.8 90 ° C 0.7 mm (Please read the precautions on the back before filling out this page) Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives Printed materials for the outer layer Powder composition (mass fraction) Compound 1 Paraffin Clay Comparative Example 6 2.0 4. 5 26 · 〇 Comparative Example 7 2.0 4.5 26.0 Comparative Example 8 2.0 7.0 51.0 Comparative Example 9 The composition shown in Table 7 will be given first. (Insecticide) The dissolved methanol solution is blown onto a spherical solid carrier (manufactured by Tokai Industries Co., Ltd., trade name: Izu paper size applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy 1239807 a? B7 V. Description of the invention (M) Surface of quartz sand (particle size: 0.3-lmm), and then left in a desiccator at 50 ° C for 3 hours to remove Methanol produced a core that could not be slow-released. Subsequently, (bactericide) having the composition shown in Table 7 was added, and the raw material powder of the outer layer portion obtained by mixing was coated on the surface of the inner core in the same manner as in Example 1-2 to obtain a granule of Comparative Example 9. Table 7 Composition core (mass fraction) of the granules of Comparative Example 9 Composition (mass fraction) of raw material powder of the external part Compound 1 Spherical solid support (Izu quartz sand) Thiazethrin paraffin clay comparative example 9 2.0 38.0 24.0 12.0 24.0 Test Example 2, Granule Dissolution Test for Rice Nursery Box For granules obtained in the above Examples 1-12 and Comparative Examples 1-9, the dissolution rate of the pesticide active ingredient released from each granule was measured. ① Dissolution rate of compound 1 (insecticide). Among the two pesticide active ingredients contained in the granules prepared in Examples 1-12 and Comparative Examples 1-9, the compound 1 (insecticide) released from each granule was measured by the method described below. ) Dissolution rate. That is, each of the granules prepared in the examples and comparative examples was placed in a test tube with a stopper capacity of 50 ml containing 25 ml of standard 3 degree hard water in an amount equivalent to that of compound 1 (insecticide). When the concentration reached 920 ppm, when all the contained Compound 1 (insecticide) were dissolved out, insoluble matter was precipitated in water. In this case (please read the precautions on the back before filling this page). ¾ This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) A7 1239807 V. Description of invention (β state, 25 ° C Let it stand for a certain period of time, filter the whole amount, and measure the amount of Compound 1 (insecticide) dissolved in the filtrate by HPLC method. Based on the measured value, calculate the dissolution rate according to the following formula, and summarize the results in Table 8. Dissolution rate = (filtrate Insecticide dose / Insecticide dose in granules) X 100 I Ί ^ Ί. -------- Order ----: ------ line (Please read the precautions on the back first Refill this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy Table 8 Compound 1 released from each granule (dissolution rate of pesticide λ (%) Dissolution rate of compound 1 day 3 days 7 days 14 days later Example 30 after 60 days and 90 days after Example 1 3.3 9.7 22. 1 44 · 9 100. 1 Example 2 0. 7 2. 7 6.6 15.7 33. 3 77.8 97.8 Example 3 10.2 22.7 41.9 59.6 81.2 99. 1 Example 4 5. 5 11. 2 21.9 41.6 87.2 101.0 Example 5 27.8 42. 7 59. 1 77.0 94.4 100. 5 Example 6 2. 7 8.8 19.8 4 0.9 92.6 Example 7 0.4 2. 1 5. 7 12.8 30. 1 66. 6 94.6 34 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 1239807 B7 A7 Intellectual Property Bureau, Ministry of Economic Affairs, employee consumption Cooperative printed five, name tn spokesperson public mouth, ______ " mm 8 9. 8 18. 7 33.6 52.8 78. 1 100.4 Example 9 8. 5 23. 1 39. 7 56.6 78. 3 97.8 Example 10 5 7 11 · 1 22.2 41.3 85.3 99. 9 Example 11 28. 1 44.0 64. 1 81.4 98.9 Example 12 31.3 44.2 60.0 77. 1 96.2 Comparative Example 1 82.6 96.8 100 · 1 Comparative Example 2 95. 7 99.4 99.3 Comparative Example 6 97.3 100.8 101.0 Comparative Example 7 94. 1 99.2 99.8 Comparative Example 8 95. 5 97.6 99.3 Comparative Example 9 79. 3 92.8 98.8 As shown in Table 8, the granules of the examples In other words, the insecticidal active ingredients contained in the inner grains can be continuously released for about 1 month to 3 months (please read the precautions on the back before filling this page) This paper size applies to China Standard (CNS) A4 specification (210 X 297 mm) 1239807 A7 B7 V. Description of invention (today ), And almost all of the insecticidal active ingredients contained can be completely released. In contrast, for Comparative Examples 1, 2 without a cladding layer, and Comparative Examples 6 to 8 containing compound 1 in the outer layer portion without a core; or for compounds containing Compound 1 in a core without using an interpretation technique In Comparative Example 9, neither release was sustained, and the dissolution rate reached almost 100% in approximately 1-3 days. ② Dissolution rate of d-port f and / a> (sterilization ij). The dissolution rate of the d-portion {于 / 一; l (bactericide)) released from each of the two pesticide active ingredients contained in the granules obtained in Examples 1-2 and Comparative Examples 1-9 The measurement was performed by the method mentioned below. That is, each of the granules prepared in the examples and comparative examples was placed in a sealed Erlenmeyer flask containing 1000 ml of ion-exchanged water with a capacity of 1,000 ml, and the amount added was equivalent to d α {于 ' (一); (fungicide) concentration reaches 30ρρπι, when the contained d '' / a; u (fungicide) all dissolves, insoluble matter precipitates in water, and left to stand at 25 ° C in this state, Then, at a certain time interval, a sample of 1 ml was taken from a water depth of 5 cm to determine the concentration of the bactericidal active ingredient in the sample by HPLC. The experimental condition was that the entire amount of the bactericidal agent in the granules to be tested was in 1.0 ml of water in a conical flask. The concentration at the time of dissolution was 30 ppm, and the concentration value of the measured bactericide was removed at 30 ppm to obtain the dissolution rate. The results are summarized in Table 9. IM -h U ---------------- Order --- ^ ------ line (Please read the notes on the back before filling this page) Intellectual Property Bureau of the Ministry of Economic Affairs Printed by Employee Consumer Cooperatives π 36 This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 1239807 λ7 B7 V. Description of the invention (^) [Table 9] ^ 一 released by each granule >) Dissolution rate of fungicides Printed clothing of employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (7. Mouth ^: Yu y a; Dissolution rate of fungicides (0 / 〇) 1 after 3 days 7 days after 14 days 30 days after 60 days 60 After the 90th day, Example 1 0 · 7 5. 1 9.2 18.4 40.0 82.1 1101. 0 Example 2 1. 1 2.9 7.3 15.9 35.6 77. 7 96.2 Example 3 2.0 5. 7 12.4 22 · 6 52 · 1 97 · 2 98.0 Example 4 0.2 3.1 7.9 17.7 39.3 84.8 93.5 Example 5 2.9 6.2 14.5 28.9 55.6 100.0 Example 6 0.4 6. 1 10.0 22.2 44. 2 84.6 102.0 Example 7 3.0 6.9 15. 1 27 · 1 46.2 88. 1 97.7 Example 8 3. 3 7 · 1 13.2 25.9 54.4 100.6 Example 9 2. 7 5. 5 13. 1 24.9 55.6 98. 9 Example 10 3.6 6 · 13. 3 28.0 47.0 84. 0 96.8 paper ruler Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page) 1239807 B7}-5.8 Example 11 2.2 13. 7 26.8 58.8 99.0 Example 12 3.0 5.7 17.2 31.6 57.3 100. 7 Comparative Example 3 0.2 1. 1 3.2 6 · 6 14.9 28.8 38.1 Comparative Example 4 ND ND 0.8 2.4 7.5, 18.2 26.9 Comparative Example 5 0.2 0.8 2.4 5 · 1 12.0 24.7 33. 3 Comparative Example 6 ND 0.4 1.7 3.7 7.4 13.6 22.8 Comparative Example 7 ND 0 · 1 0.4 2 · 1 5.0 11 · 1 22. 7 Comparative Example 8 ND ND 0.4 1. 1 3.6 9.9 16.3 As the results shown in Table 9 show, each of the examples The granules can gradually release the fungicide in about 3 months, and almost all the fungicides required in the outer layer can be completely released. On the contrary, as for Comparative Example 3 of all fungicides in the inner core, 3- For the granules of 8, even after about 2 months, only a part of the content was dissolved out, and the dissolution rate was extremely low. In the coated sustained-release pesticide granules of the present invention, when two or more pesticide active ingredients having greatly different water solubility are contained, generally one of them may have a water solubility of 1,000 ppm or more. Concentration activity of 38 This paper size is applicable to China National Standard (CNS) A4 (210 x 297 mm) (Please read the precautions on the back before filling this page) Printed by the Consumer Property Cooperative of the Intellectual Property Bureau 1239807 A7 B7 V. Description of the Invention (7 texts) The sustained release can be realized separately. For example, pesticide mixed granules suitable for rice seedling box granules can be prepared. The coated sustained-release pesticide granules of the present invention can release substantially all of the contained contents of two or more pesticide active ingredients, and can be slowly dispersed in the field in a required period. The pesticide active ingredients in the solution are continuously dissolved, and there is no need to worry about a part remaining in the granules. Furthermore, the coated sustained-release pesticide granules of the present invention do not need to cover the surface of the inner core with a resin during manufacture. In the production of coated particles, the drying process after the resin coating can be omitted, and redundant processes are saved. In this way, its superior viscosity is achieved by using a double-layered dosage form and reducing its manufacturing cost. (Please read the precautions on the back before filling out this page) • Canned clothing set i — T ----- line-Printed agricultural paper size for employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs applies Chinese National Standard (CNS) A4 specifications (210 X 297 mm)

1239807 申請曰期 案 號 類 別 (1239807 Application date category (

修A A4 C4 補充 :名稱 群《"型專利説明書 中文 被覆型緩釋性農藥粒劑 英 文 姓 名 國 籍 •岸大輔 •長島宏一 .运邊孝 •接井慎司 •上野滋 b乂日本Revision A A4 C4 Supplement: Name Group "" Type Patent Specification Chinese Covered Slow Release Pesticide Granules English Name First Name Nationality • Kishi Daisuke • Nagashima Koichi .Yunbei Takahashi • Receiving Shinji • Ueno Shibuki Japan

Daisuke KISHI Koichi NAGASHIMA Takashi WATANABE Shinji SAKURAI Shigeru UENO 裝 發明 住、居所 1·曰本國千葉縣茂原市東鄉1144(三井化學股份有限公司内) •曰本國千葉縣茂原市東鄉1144(三井化學股份有限公司内) 曰本國千葉縣茂原市東鄉H44(三井化學股份有限兔?内) 4·灵子i 3奈川縣责濱市港北區師岡町760號(明治製杲股份有限 5.日港北區師岡町760號(明治製窠股份有限 .公司藥品綜合研究所内) ___ 訂 姓 名 (名稱) .三井化學股份有限公司MITSUI CHEMICALS,INC· 2.明治製窠股份有限公司MEIJISEIKAKAISHA., LTD. 經濟部皙慧57/|.^$工;/]^合作社印製 三、申請人 國 籍 住、居所 事務所) 代表人 姓 名 1.曰本2· B本 1·日本東京都千代田區霞加關3 丁目2之5號 2·曰本國東京中央區京橋2丁目4之16號 I·中西宏幸2·北里一即 線 本紙張尺度適用中國國家榡準(CNS) Α4说格(210Χ297公釐)Daisuke KISHI Koichi NAGASHIMA Takashi WATANABE Shinji SAKURAI Shigeru UENO Pretends to live and live in 1 · Toyo 1144, Togo, Mobara, Chiba Prefecture, Japan (inside Mitsui Chemicals Co., Ltd.) H44, Togo, Mobara, Chiba Prefecture, Japan (Mitsui Chemical Co., Ltd. Rabbit?) 4. Lingzi i 3, No. 760, Shioka-cho, Kohoku-ku, Obama-shi, Naikawa Prefecture (Meiji Corporation Limited, No. 760, Shioka-cho, Kita-ku, Japan Meiji Chemical Industry Co., Ltd. (Inside the Company's Pharmaceutical Research Institute) ___ Name (name). Mitsui Chemicals Co., Ltd. MITSUI CHEMICALS, INC. 2. Meiji Chemical Industry Co., Ltd. MEIJISEIKAKAISHA., LTD. Ministry of Economy Xihui 57 / |. ^ $ 工; /] ^ Printed by a cooperative 3. The applicant's nationality resides and resides in the office) Name of representative 1. Japanese version 2. Japanese version 1. Japanese version 2. Kasumigaru 3, Chiyoda-ku, Tokyo, Japan 2-5, No. 2 · Said in the home country, Tokyo, Chuo-ku, Tokyo 2nd, No. 16 No. 16 I. Nakasushi Hiroshi 2 North Kitaichi immediate line paper size applicable to China National Standards (CNS) Α4 grid (210 × 297 mm)

Claims (1)

1239807 本 £ 0 | 更 ,rv A 月 /PAj 8 88 8 ABCD 輕濟部中央橾準局負工消費合咋汪中装 申請鐘1釋性農藥粒劑, 是爲了將農藥活性成分持續地溶 出供給水介質所使用的緩釋性農藥粒劑,其特徵在於: 上述粒劑具有由内核和包覆在内核表面的外層部組成的包 覆型粒劑的結構 上述内核是由20°c的水溶解度在lOOOppm以上一 10%以下的 至少一種農藥活性成分,無機系稀釋載體及難溶於水的第一熱 塑性材料組成的製粒物; 上述外層部是由20°C的水溶解度在0· Olppm—500ppm的至 少一種農藥活性成分,無機系稀釋載體及與上述内核中所含有 的第一熱塑性材料相比熔點更低,而且是不同材料的,難溶於 水的第二熱塑性材料組成的包覆層; 由於這種包覆型粒劑的結構,上述内核中所含有的農藥活 性成分和外層部所含有的農藥活性成分可以分別控制使其緩慢 的溶出。 2、 如申請專利範圍第1項所述之緩釋性農藥粒劑,其特徵 在於,外層部還含有介面活性劑。 3、 如申請專利範圍第1或2項所述之緩釋性農藥粒劑, 共特徵在於,内核中所含有的上述難溶於水的第一熱塑性材半^ 是二十九烷酸蠟,及/或二十九烷酸酯蠟。 4、 如申請專利範圍第Γ或2項所述之緩釋性農藥粒劑, 共特徵在於:外層部中所含有的上述難溶於水的第二熱璧 性材料是石蠘。 5、 如申請專利範圍第1或2項所述之緩釋性農藥粒劑,其 特徵在於:内核中所含有的農藥活性成分爲(RS) —1 一2甲 1:- i g --- <請先M讀背面之注意事項再填寫本頁} i Awn ^------ -訂----- 線----Γ:--- 本纸張尺度逍用中國國家播準( CNS ) A4规格(210Χ297公釐) 12398071239807 this £ 0 | more, rv A month / PAj 8 88 8 ABCD Ministry of Economic Affairs Central Bureau of Standards and Technology Bureau of Work and Consumption Coordinator Wang Zhongzhuang applied for 1-release pesticide granules to continuously dissolve and supply pesticide active ingredients The sustained-release pesticide granules used in an aqueous medium are characterized in that: the granules have a structure of a coated granule composed of a core and an outer layer portion coated on the surface of the core; the core has a water solubility of 20 ° C; Granules composed of at least one pesticide active ingredient above 1000 ppm and below 10%, an inorganic dilution carrier and a first thermoplastic material which is hardly soluble in water; the outer layer portion is made of water with a solubility of 20 ° C at 0 · Olppm— 500 ppm of at least one pesticide active ingredient, an inorganic dilution carrier, and a coating layer composed of a second thermoplastic material that is of a different material and hardly soluble in water compared to the first thermoplastic material contained in the core described above Because of the structure of such coated granules, the pesticide active ingredient contained in the inner core and the pesticide active ingredient contained in the outer layer part can be controlled to make it slowly dissolve separately. 2. The sustained-release pesticide granule according to item 1 of the scope of the patent application, characterized in that the outer layer part further contains a surfactant. 3. The slow-release pesticide granules described in item 1 or 2 of the scope of the patent application, which are characterized in that the first hardly water-soluble first thermoplastic material contained in the inner core is a nonacosanoic acid wax, And / or icosanoate wax. 4. The sustained-release pesticide granules described in item Γ or 2 of the scope of the patent application, which are characterized in that the second heat-resistant material which is hardly soluble in water and contained in the outer layer portion is stone mortar. 5. The slow-release pesticide granules described in item 1 or 2 of the scope of the patent application, characterized in that the pesticide active ingredient contained in the kernel is (RS) —1 — 2A 1:-ig --- < Please read the notes on the back before filling in this page} i Awn ^ ------ -Order ----- Line ---- Γ: --- This paper size is free to use Chinese national broadcast standards (CNS) A4 specification (210 × 297 mm) 1239807 六、申請專利範圍 S~3~·硝基一3——(四氫化基一3一呋喃基甲基)胍、外層部中 所含有的農藥活性成分爲噻菌靈。 6、一種製造如申請專利範圍第丨項所述之緩釋性農藥粒劑 的方法,其特徵在於包含以下(1)-(3)之步驟: (1) 一獲得製粒物的步驟,將2(TC的水溶解度在lOOOppm以 上10%以下的至少一種農藥活性成分、無機系稀釋載體、難溶 於水的第一熱塑性材料,加以混合進行造粒以形成作為内核的 製粒物; (2) —獲得被覆用組成物的步驟,作為外層部分的該被覆型 組成物是由20°C的水溶解度為〇· 〇i-500ppm的至少一-農藥活 性成分、無機系稀釋載體、和較該内核中所含有的該第一熱塑 性材料溶點低且屬不同材料並難溶於水的第二熱塑性材料所組 成; (3) —被覆步驟,即對於步驟(1)中所獲得之作為該内核的 該製粒物,於其表面將步驟(2)中所獲得之該被覆用組成物,以 該第二熱塑性材料之熔點以上而未達包含在該内核中之該第一 熱塑性材料之烙點的溫度進行加熱,而使該第二熱塑性材料加 熱溶解,而實現被覆於該製粒物上。 (請先H讀背面之注意事項再填寫本頁) 裝 ^ Ψ · Hah— —>ni —.Hi nn .τ L· 線 經濟部中央揉準局Λ工消費合作杜印U 41 本纸張尺渡逍用中國國家揉率(CNS ) A4洗格(210X297公潑)6. Scope of patent application S ~ 3 ~ · Nitro-3 ~ (tetrahydro-3 ~ furylmethyl) guanidine, the active ingredient of pesticide contained in the outer part is thiabendazim. 6. A method for manufacturing a sustained-release pesticide granule according to item 丨 of the patent application scope, characterized by comprising the following steps (1)-(3): (1) A step of obtaining a granulated product, 2 (TC has at least one pesticide active ingredient with a water solubility of 10,000 ppm or more and 10% or less, an inorganic dilution carrier, and a first thermoplastic material that is hardly soluble in water, mixed and granulated to form a granulated substance as a core; (2 ) — A step of obtaining a coating composition, the coating composition as an outer layer part is composed of at least one of a water solubility of 20 ° C. and i-500 ppm, a pesticide active ingredient, an inorganic dilution carrier, and The first thermoplastic material contained in the inner core is composed of a second thermoplastic material having a low melting point, which is a different material and is hardly soluble in water; (3)-a coating step, that is, the core obtained in step (1) is used as the inner core; On the surface of the granulated product, the coating composition obtained in step (2) is above the melting point of the second thermoplastic material and does not reach the melting point of the first thermoplastic material contained in the core on the surface thereof. The temperature of The second thermoplastic material is dissolved by heating to cover the granulated material. (Please read the precautions on the back before filling this page) Ψ · Hah— — > ni —.Hi nn .τ L · Line Central Government Bureau of the Ministry of Economic Affairs, Λ Industrial Consumption Cooperation, Du Yin U 41 This paper ruler is used in China's National Kneading Rate (CNS) A4 Washing (210X297)
TW090130661A 2000-12-12 2001-12-11 Covered type controlled release of agrochemical granular agent TWI239807B (en)

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CN1358433A (en) 2002-07-17

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