TWI283256B - The biodegradable, floating foaming element having high oil absorption, the preparation and the composition containing thereof - Google Patents

The biodegradable, floating foaming element having high oil absorption, the preparation and the composition containing thereof Download PDF

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TWI283256B
TWI283256B TW090110107A TW90110107A TWI283256B TW I283256 B TWI283256 B TW I283256B TW 090110107 A TW090110107 A TW 090110107A TW 90110107 A TW90110107 A TW 90110107A TW I283256 B TWI283256 B TW I283256B
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Taiwan
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starch
parts
pesticide
mass
foam
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TW090110107A
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Chinese (zh)
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Hitoshi Hosoda
Takeshi Hirata
Kinji Tanizawa
Norio Hishiki
Hiroshi Wadamori
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Sankyo Agro Co Ltd
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/16—Foams
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/12—Powders or granules
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/22—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A01N65/40—Liliopsida [monocotyledons]
    • A01N65/44—Poaceae or Gramineae [Grass family], e.g. bamboo, lemon grass or citronella grass
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N2300/00—Combinations or mixtures of active ingredients covered by classes A01N27/00 - A01N65/48 with other active or formulation relevant ingredients, e.g. specific carrier materials or surfactants, covered by classes A01N25/00 - A01N65/48
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2003/00—Use of starch or derivatives as moulding material

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

Abstract

The foaming element floating completely on the water is adding and mixing 95.0 to 99.0 the parts of mass of starch with 0.1 to 5 the parts of mass of cross-linking agent. And it has that the diameter obtained by processing with extruder is 1 to 5 times as large as the diameter of die, the bulk specific volume is 1 to 20 ml/g, and the ability of oil absorption is 0.3 to 5 times then its weight.

Description

1283256 五、發明説明（1 ) 技術領域 本發明係關於以澱粉爲主成份，經擠壓機處理，具有高 度吸油能力之生物分解性水面懸浮發泡體及其製法，含有 此生物分解性水面懸浮發泡體之農藥組成物，其製法，及 其使用方法。向來油脂類或有機溶劑等油性液狀物質，視 用途加以粉末化往往較爲方便，以食品、飼料、醫藥、農 藥爲開始，而在各種領域也嘗試將液狀物製成粉末。由於 本發明發泡體可含有油性液狀物質，故可應用於上述領域 ，其中可在發泡體含有農藥，而在提供具有優良特性之農 藥組成物。 背景技術 向來有關含澱粉之物質經擠壓機處理成發泡體之技術， 載於日本專利特開平7-32441和9-296076號公報。 其中特開平7-32441號揭示利用澱粉爲原料之可食性生 物解性緩衝材料及其製法，具有優良柔軟性、彈性，可食 性且生物分解性，作爲發泡體乙烯代替品之緩衝材料。另 外，特開平9-296076號揭示生物分解性澱粉樹脂及其製 法。然而，因其含有澱粉，呈生物分解性之特徵，具有吸 油性且不能浮在水面，又因未添加本發明所添加交聯劑， 無法經由膨脹處理而具有微細氣泡。 再者，有關含農藥之澱粉發泡體技術，載於特表平 5-502437號，日本專利2785490號公報。其中特表平 5-502437號公報揭示使用交聯澱粉或在擠壓機處理時加以 交聯之技術，惟此案顯示澱粉不溶化，不像本發明藉控制1283256 V. INSTRUCTION DESCRIPTION OF THE INVENTION (1) Field of the Invention The present invention relates to a biodegradable water-surface suspension foam which is mainly composed of starch and which is treated by an extruder and has a high oil absorption capacity, and a method for preparing the same, comprising the biodegradable water surface suspension The pesticide composition of the foam, the preparation method thereof, and the method of using the same. It is often convenient to pulverize oily liquid materials such as oils and fats or organic solvents, depending on the application, starting with foods, feeds, medicines, and agricultural chemicals, and attempts to make liquids into powders in various fields. Since the foam of the present invention can contain an oily liquid substance, it can be applied to the above-mentioned field, in which a foam can contain a pesticide, and a pharmaceutical composition having excellent characteristics can be provided. Background Art A technique for treating a starch-containing material into a foam by an extruder is disclosed in Japanese Laid-Open Patent Publication No. Hei 7-32441 and No. 9-296076. Japanese Laid-Open Patent Publication No. Hei 7-32441 discloses an edible biodegradable cushioning material using starch as a raw material and a method for producing the same, which has excellent flexibility, elasticity, edibleness and biodegradability, and is used as a cushioning material for a foamed vinyl substitute. Further, Japanese Laid-Open Patent Publication No. Hei 9-296076 discloses a biodegradable starch resin and a process for producing the same. However, since it contains starch, it is biodegradable, has oil absorption, and cannot float on the surface of the water, and since it does not add the crosslinking agent added by this invention, it cannot have the microbubble by expansion processing. Further, the technique of the starch-containing foam containing the pesticide is disclosed in Japanese Patent Publication No. Hei 5-502437, and Japanese Patent No. 2785490. Japanese Patent Publication No. 5-502437 discloses a technique of crosslinking using a crosslinked starch or a treatment in an extruder, but the case shows that the starch is insolubilized, unlike the present invention.

1283256 五、發明説明（2 ) 發泡提高水懸浮性或吸油性。另外，專利2785490號公報 中同樣把農藥成份、油性成分和澱粉成份混合加以擠壓處 理，由於油性成分之助使比重減輕而得以懸浮水面，但因 添加油性成分會抑制澱粉粒的糊化，成爲不易溶於水的成 型物，內部含有農藥等之油性成兮很難放出水中，以致降 低農藥的早期效果。 相對地，按照本發明農藥組成物，發泡體和農藥混合後 ，在發泡體表面和氣泡部份會吸附農藥，投入水中時，表 面附著之油性成分容易從發泡體脫離（油分離性佳），被水 取代，徐徐滲透的水使發泡體膨潤，滲透吸附到內部之油 性成分，也在短期間內釋放到外部，早期即顯現藥效。 再者，於此揭示之技術，農藥本身在擠壓機內受到高壓 高溫處理，分解之揮發成份有發散的可能性，而發生環境 污染的問題。尤其是混有交聯劑時，更爲提高接受改質之 可能性。 向來，澱粉經擠壓處理所得澱粉發泡體呈具有大氣泡之 多孔性組織，吸水性優良，但澱粉發泡體本身有溶於水的 課題，即使添加懸浮水面之撥水性物質，亦得不到吸油能 力高的發泡體，故尙未有具備高度吸油能力的生物分解性 ，且懸浮水面之發泡體。 發明槪沭 本發明人等爲解決此等課題，潛心硏究結果，發現可製 造於含澱粉物95.0〜99.0質量份，添加混合交聯劑0.1〜5 質量份，經擠壓機處理所得發泡體，其直徑爲模徑的1〜5 -4- 1283256 五、發明説明（3 ) 倍，體積比容爲1〜20ml/g，具有本身重量0.3〜5倍的吸 '油能力，可充分懸浮於水，另於含澱粉物質和澱粉類（含 澱粉物質：澱粉類=0〜80:1 00〜20)45〜95質量份，添加混 合熱凝固物質1〜30質量份和交聯劑0.1〜5質量份，經 擠壓機處理所得發泡體，其直徑爲模徑的1〜5倍，體積 比容爲1〜20ml/g，具有本身重量0.3〜5倍之吸油能力， 可充分懸浮於水，也發現此發泡體可將油性液狀物質製成 粉末，又發現於本發明的發泡體吸收農藥或油狀物質，視 情形再被覆製成粉末狀的固體農藥或其預混物或固體載體 之微粉末，即可得具有水面懸浮性。且油狀有效成份在短 時間內即容易釋出之粒劑，而完成本發明。 本發明所用含澱粉物質，包含玉蜀黍、玉米粉、玉米渣 、米、米粉、米糠、乾樹薯、乾番薯、馬鈴薯、甘薯、大 豆、綠豆、麥糠、小麥、小麥粉、粟、稗等糊化後可形成 皮膜之澱粉。澱粉類有未加工澱粉和加工澱粉，具體例有 馬鈴薯澱粉、玉米澱粉、高溶膠澱粉之玉米澱粉、番薯澱 粉、樹薯澱粉、西米澱粉、米澱粉、莧菜澱粉等未加工澱 粉，及其加工澱粉（酸解澱粉）、氧化澱粉、二醛化澱粉、 醚化澱粉（羧甲基澱粉、羥烷基澱粉、陽離子澱粉、羥甲 基化澱粉等），酯化澱粉（乙酸澱粉、磷酸澱粉、丁二酸澱 粉、辛二烯基丁二酸澱粉、順丁烯二酸澱粉、高級脂肪酸 酯化澱粉等），交聯澱粉、接枝澱粉、及濕熱處理澱粉等 。以氧化澱粉、酸處理澱粉、和輕度交聯澱粉等皮膜性弱 的軟質系澱粉爲佳。強度交聯之澱粉’有在擠壓機不易發 .........产一 . 1283256 五、發明説明（4 ) 的傾向。其中更好的是小麥粉、玉米渣、玉米粉。小麥粉 分成強力粉、中力粉、薄力粉，以薄力粉最好。 本發明經擠壓機加壓擠出處理前之混合物，可添加脂質 。本發明所用脂質，有中性脂質（包含脂肪酸之甘油酯， 常溫爲液體之脂肪油和固體脂肪），鱲（包含脂肪酸和高級 醇之酯，石蠘脂、石蠘等石油蠘），還有固醇或維生素A 、0之酯等單純脂質，亦可含氮之磷脂質、具有糖爲構成 成份之糖脂質，及其中具有硫酸根或磺基之硫脂質，還有 具有C-10鏈等之複合脂質，視爲屬於以上二者的前驅體 或代謝產物之脂肪酸、高級醇、固醇、烴類之類胡蘿蔔素 或鯊烯等，以及脂溶性維生素等之衍生脂質。其中以脂肪 酸甘油酯之油酯（豬油、半脂、棕櫚校仁油、椰子油、大 豆油、橄欖油、紅花油、花生油、菜籽油、白絞油、玉米 油、棉籽油、米油、芝麻油、葵花油、蓖麻油、可可油、 亞麻仁油、桐油、蘇子油、海產動物油），或凡士林、石 蠘等蠘爲適用。 爲了利用擠壓機擠出，必須要熱塑性。爲使澱粉具有熱 塑性，非加水糊化不可。可是澱粉加水糊化所得發泡體， 含許多水份，爲提高本發明目的之吸油能力，發泡體必須 再進行乾燥。若添加少量脂質，可將水量減至最少或不加 ，水份少的發泡體可圓滑壓出。再者，在發泡體表面形成 薄脂質膜時，可大爲改善發泡體之吸油能力，並增加在水 面的懸浮能力。 脂質添加量爲〇·1〜8質量份，但使用含本來脂質的玉 -6- 1283256 五、發明説明（5 ) 米粉、玉米渣、小麥粉等含澱粉物質：或辛二烯基丁二酸 澱粉、高級脂肪酸酯化澱粉等加工澱粉等，添加量可不受 此限。 本發明以擠壓機加壓擠出處理前之混合物，可添加乳化 劑。本發明所用乳化劑，可用具有適當HLB値的非離子 界面活性劑、肥皂等陰離子界面活性劑、蛋白等高分子物 質等，惟以甘油脂肪酸酯、蔗糖脂肪酸酯、山梨糖醇脂肪 酸酯、丙二醇脂肪酸酯、卵磷脂、硬脂醯乳酸鈣、油酸鈉 、嗎啉脂肪酸鹽、聚氧乙烯高級脂肪醇等食品添加劑爲佳。 本發明中乳化劑可視爲提高含澱粉物質或澱粉類和脂質 之乳化性，結果可增大內部和表面之氣泡，有益於提高吸 油能力和水面懸浮性。 乳化劑添加量爲0.1〜5質量份。 本發明所用熱凝固物質有大豆蛋白、麩質等小麥蛋白、 酪蛋白等乳蛋白等之蛋白系，以及凝乳素或甲基纖維素般 熱凝固性多糖類。熱凝固物質溶解時成爲網目狀高分子構 造，因加熱而凝固，以擠壓機處理時，形成具有細氣泡的 發泡體。藉添加交聯劑，形成具有硬度之發泡體。 熱凝固物質之添加量爲1〜30質量份。 本發明所用交聯劑，可用三聚磷酸鈉、三焦磷酸鈉、氧 氯化磷等磷酸鹽類，表氯烷、末端具有二環氧基之聚環氧 化合物，甲醛、乙二醛等醛類，與其他澱粉等多糖類所含 羥基，蛋白等所含胺基、羧基反應所得含二官能基之物質 (己二酸、丙烯醛、雙乙烯尿素、二異氰酸酯、蜜胺系樹 -7- 1283256 五、發明説明（6 ) 脂、密胺-甲醛水系樹脂、胺基樹脂、多胺·表氯烷基系 樹脂、水溶性烷化胺基樹脂、水溶性甲基化密胺樹脂等） ’焦銻酸鉀、鈣鹽、鎂鹽等多價陽離子性鹽類。以食品添 加劑等無毒性者爲佳。此等交聯劑均不必用到任何觸媒 (只要加熱），惟交聯反應所必要的觸媒，可添加一般所用 者（通常爲得最適pH，可添加鹼性觸媒或酸性觸媒）。添加 量爲0.1〜5質量份。 本發明中的交聯劑，有助於發泡時調節發泡體直徑，並 具有益於水面懸浮性。 在上述種種材料中，其混配質量分別如下。含澱粉物質 95.0〜99.0質量份，交聯劑0.1〜5質量份，和交聯所必要 量的觸媒。含澱粉物質和澱粉類（含澱粉物質：澱粉類=0〜 80:1 00〜20)45〜95質量份，必要時脂質0.1〜8質量份， 必要時乳化劑0.1〜5質量份，熱凝固物質1〜30質量份 ’交聯劑〇· 1〜5質量份，以及交聯所必要量之觸媒。 本發明中的含澱粉物質，包含其他天然物或其衍生物， 例如有纖維素系、蛋白質系和天然膠系般之天然物，或其 衍生物。 纖維素系的天然物或其衍生物，有例如羧甲基纖維素及 其鹽，甲基纖維素、羥乙基纖維素、羥丙基纖維素、羥丙 基甲基纖維素等纖維素衍生物。 蛋白質系之天然物或其衍生物，有例如動物骨等所得明 膠、牛乳所得酪蛋白及其鹽，小麥所得麩質等。 天然膠系之天然物或其衍生物，有例如果膠、藻膠酸及 1283256 五、發明説明（7 ) 其鹽或酯等之衍生物，黏稠性多糖、漢生膠、韋勒膠、瓜 耳膠、凝乳素等。 茲就本發明處理裝置的擠壓機說明如下。 一般擠壓機係由斜槽、加料器、螺桿、筒部、模、加熱 盤管、冷卻夾套、驅動馬達所構成，有單軸和雙軸，以雙 軸爲佳。製成本發明發泡體，係在筒部溫度60〜250°C , 以80〜160°C爲佳，螺桿轉數50〜3 00i:pm，以70〜200 rpm爲佳，模溫90〜200°C，以1〇〇〜15 0°C爲隹，模出料 口徑〇·5〜10mm，以1〜5mm零佳之條件下擠出。發泡體 以模口徑10倍以下爲佳，1〜5倍時小氣泡多，可得比重 大的發泡體。 筒部溫度與澱粉糊化和交聯劑反應性有關。螺桿轉數影 響擠出壓力，同時可控制擠壓前乳化粒之大小。模溫影響 發泡力，與內部水份排出量有關。模擠出口徑可視用途適 當調節，惟發泡體在模口徑1 0倍以下爲佳，必須選在1〜 5倍時，可得小氣泡多而比重大的發泡體。 本發明發泡體爲模口徑1〜5倍，可製成小連續氣泡多 、比重大的發泡體。此發泡體之體積比容爲1〜20ml/g， 以1〜12.5ml/g爲佳，具有本身重量〇·3〜5倍，更好1倍 以上的吸油能力，懸浮水面1 0分鐘以上，以1小時以上 爲佳。 體積比容的測量方法，取樣品20克（輕者爲5克），放 入500毫升（輕者爲1公升）容量之量筒內，度量筒刻度（毫 升）(高、低値之平均値）。由下式求出體積比容乂 -9- 1283256 五、發明説明（8 ) 體積比容（ml/g) =刻度値/20(或5) 吸油倍數測定法：於200毫升容量的廣口玻璃瓶，放入 試料1 〇克，滴加少量白紋油。滴加後，把瓶加蓋，用手 搖瓶，使白絞油均混於試料。俟瓶內壁不再附著白絞油， 在試料表面已無白絞油亮光時，開蓋再添加適量白絞油， 重複上述操作。最後滴加到搖動混合5分鐘，在瓶內壁也 不再附著白絞油，試料表面已消失白絞油光亮之狀態，即 告結束，由下式求出吸油能力。 吸油能力（％) = [{滴加白絞油重量（§)} + {試料重量（10g)}]xl00 如此所得澱粉發泡體，分裝於水溶性膜，投入水田處理 ，即所謂巨劑或包劑，亦可不分裝，用作在水面圍兜處理 的水面懸浮性農藥粒劑之載體。此等劑型在近年農務背景 下，可用作強烈需求的省力型農藥，尤其是可調製成含高 濃度液狀原體之粒劑，得以減少每單位面積之藥量，然而 所含液狀原體吸藏於載體原狀下會沉沒，在短時間內釋出 水中，無藥害或效力不足之虞，爲其特徵。 本發明所用農藥有效成份，有在水田以水面施用之除草 劑、殺蟲劑、殺菌劑、植物調節劑等，其本身物理性狀無 特別限制，除草活性成份有例如比西拂隆美索、亞濟莫速 拂隆、依速隆、百速隆、亞朵索拂隆、亞諾速拂隆、西庫 隆發莫隆、濟米比列妥、米飛那西妥、普拉草、稻得牡、 比利普濟卡普、太尼庫隆、亞速普隆卡普、普多米活速、 普隆普濟朵、汰草隆、卡非速妥隆、洽隆活普索、比佐非 那普、必拉佐列妥、必拉佐克西非、比福列西妥、殺丹、 -10- 1283256 五、發明説明（9 ) 西美妥林、濟美他美妥林、陪妥克散佐、亞朵必散林朵、 濟齊歐必、丁基拉草、歐克散濟阿奇、那普隆阿尼林、西 美齊林、2,4-D及其烷基酯或鹽，MCPA、MCPB及其烷基 酯或鹽，歐克散庫隆美活、非妥拉散米朵、比佐必西庫隆 、伊塔諾發、庫米隆、必拉佐散、阿尼隆活速、必芬諾、 必隆活速、散諾庫接米、必林米諾巴庫美西、庫隆美庫隆 普及本達隆等。 殺蟲活性成份可用具有浸透移動性之殺蟲劑，以及水稻 象鼻蟲、稻負泥蟲等在水面生息的害蟲有效之殺蟲劑，例 如西拉拂歐非、西庫隆比隆妥林、亞妥非普隆庫速，益達 胺、尼他必拉母、亞西塔米普林，加福松、亞濟齊歐美妥 、大利松、硫賜妥、歐殺松、以及免扶克等。 殺菌活性成份可用具有對浸透移動性之稻熱病或紋枯病 等有效之殺菌劑，例如他庫隆福他拉、歐林普拉伊妥、阿 佐克西速妥隆必、米普隆巴米朵、百快隆、亞賜圃、普隆 比那佐、西拂散米朵、西美克那佐、丙基善樂松、三賽唑 、芬普尼、福多寧、福拉美妥必滅普寧、免賴得，以及7-氟-1，2,5,6-四氫-4H-吡咯并[3.2.1-i，j]睦啉-4-酮等。 植物調節劑有例如順丁烯二醯肼及其鹽，阿伯西斯酸、 過氧化鈣、伊那陪福朵巴克素、屋尼克那佐、妥林阿陪塔 諾及散伊克西等。 本發明所用農藥有效成份，可用上述除草劑、殺蟲劑、 殺菌劑、植物調節劑之一種或二種以上，除草劑當中，當 然可將作用機制或對象不同的二種以上有效成份加以混配 -11- 1283256 五、發明説明（1G ) ’惟例如除草劑和殺菌劑或殺蟲劑，亦可混配對象完全不 同的二種以上。 其中以丁基拉草、普拉草、阿尼隆活速、比福列西妥、 洽隆活普索、濟美他美妥林等液狀原體，比西拂隆美索、 百速隆、亞濟莫速拂隆、亞朵索拂隆、依速隆、西諾速拂 隆、西庫隆發莫隆等亞磺醯基尿素系除草劑（SU劑），卡非 速妥隆、歐克散濟阿奇、汰草隆、歐克散庫隆美活、非妥 拉散米朵、比佐必西庫隆、伊塔諾發、必林米諾巴庫美西 、必拉佐散、必拉佐列妥、比佐必西庫隆等除草劑，西拉 拂歐非、西庫隆比隆妥林、依芬寧、益達胺、尼他必拉母 、亞西塔卡普林、加福松等殺蟲劑，他庫隆福他拉，歐林 普拉伊妥，阿佐克西速妥隆必、卡普隆巴米朵、百快隆、 亞賜圃、普隆比那佐、西拂散米朵、西美克那佐等殺菌劑 宜，尤以上述液狀原體或SU系除草劑最適用。 此等農藥有效成份大多在投入水田時可懸浮於水面，在 水面廣大範圍擴大後，容易在水中分散、乳化、溶解，或 不進入水中而懸浮水面，必須盡快擴散於水田全體，以難 溶於水的化合物而言，有效成份長期間懸浮於水面時，會 被風吹離，加速有效成份之局部化，宜混配適當潤濕分散 劑或乳化劑，使有效成分在水中分散、乳化、溶解。因此 ，必要時要混配適當增量劑或補助劑，形成有效成分受水 潤濕時容易乳化、分散之粒劑。 本發明所用農藥有效成份之混配比例，雖無特別限制， 但考慮到經濟性和省力，在不妨礙處理的範圍內，愈高愈 -12- 1283256 五、發明説明（11 ) 好。通常在農藥粒劑中爲0」〜80%，以0.3〜70%爲佳， 0.5〜60%更好。 本發明在水面具上懸浮性之黏狀農藥組成物，宜在水面 擴展後，農藥有效成份即快速在水中分散、乳化、溶解， 可在投入水中時崩解或不崩解均可，即使不崩解，亦以在 短時間內溶出農藥有效成份者爲宜。爲使黏狀農藥組成物 具有崩解性，本發明在水面具有懸浮性之粒狀農藥組成物 ，可含有對含澱粉物質或澱粉類發生作用的酵素。 本發明所用酵素有澱粉葡萄糖苷酵素、α-澱粉酵素、 泠-澱粉酵素、異澱粉酵素。 澱粉葡萄糖苷酵素係利用細菌或絲狀菌生產之澱粉分解 酵素，對澱粉之α -1，4鍵和α -1，6鍵作用，從葡萄糖鏈的 非還原性末端，將葡萄糖分子逐一加以分離之外型（exo)酵 素。 α -澱粉酵素係利用細菌或絲狀菌生產之澱粉分解酵素 ，具耐熱性，當pH安定性。可將具有三個以上α -1，4鍵 的葡萄糖多糖類的α-1，4鍵水解之酵素，把最少5個以上 寡糖加以分解生成葡萄糖、麥芽糖、和寡糖之內壁（endo) 酵素。可將澱粉或其衍生物隨機切斷，一下子分解到寡糖 爲止，故黏度降低能力優異。 澱粉酵素係由麥芽所得之澱粉分解酵素，亦即麥芽 澱粉酵素。最近亦有由細菌、絲狀菌製得。從澱粉、動物 澱粉肝醣、糊精等α-1，4葡聚糖之葡萄糖類非還原性末端 ，依次生成麥芽糖之外型酵素。由麥芽生產者係與α- -13- 1283256 五、發明説明（12 ) 澱粉酵素之混合物。 異澱粉酵素存在於酵母、稻、馬鈴薯、豌豆、麥芽等。 對凝膠澱粉、動物澱粉肝醣等澱粉系多糖類中的α -1，6-醣 苷鍵作用，產生純由a -1，4鍵形成的澱粉酵素般多糖類之 內型酵素。 本發明在水面具有懸浮性之粒狀農藥組成物，含有纖維 素系天然物或其衍生物時，對其作用之酵素有纖維素酵素 。此酵素係至少三種酵素組成的複合酵素，大多具有對五 碳糖的多醣類之纖維素產生作用的半纖維素酵素活性。纖 維素酵素可將纖維素中的/3-1,4-葡萄糖鏈水解，生成可溶 性聚合物和右旋葡萄糖。纖維素酵素爲複合酵素，具有下 述活性。 C!活性：破壞天然纖維素之酵素。1283256 V. INSTRUCTIONS (2) Foaming improves water suspension or oil absorption. Further, in the Japanese Patent No. 2785490, the pesticide component, the oil component, and the starch component are mixed and extruded, and the oil component is suspended in the water surface due to the reduction of the specific gravity, but the addition of the oil component suppresses the gelatinization of the starch granule. A molded product that is not easily soluble in water, and an oily sputum containing a pesticide or the like inside is difficult to release into water, so that the early effects of the pesticide are lowered. In contrast, according to the pesticide composition of the present invention, after the foam and the pesticide are mixed, the pesticide is adsorbed on the surface of the foam and the bubble portion, and when the water is poured into the water, the oily component adhering to the surface is easily detached from the foam (oil separation property) Good), replaced by water, the water that permeates slowly swells the foam, and the oily component that is infiltrated and adsorbed into the interior is also released to the outside in a short period of time, and the effect is manifested in the early stage. Further, in the technique disclosed herein, the pesticide itself is subjected to high-pressure high-temperature treatment in the extruder, and the volatile components decomposed have a possibility of divergence, and environmental pollution occurs. In particular, when a cross-linking agent is mixed, the possibility of accepting the reform is further enhanced. In the past, the starch foam obtained by extrusion treatment of the starch has a porous structure having large bubbles, and the water absorption property is excellent, but the starch foam itself has a problem of being soluble in water, and even if the water-repellent substance of the suspended water surface is added, it is not In the case of a foam having a high oil absorption capacity, there is no biodegradability which has a high oil absorption ability, and the foam of the suspended surface is suspended. In order to solve these problems, the present inventors have found that they can be produced in a starch-containing material of 95.0 to 99.0 parts by mass, and a mixed crosslinking agent is added in an amount of 0.1 to 5 parts by mass, and the resulting foam is obtained by an extruder. The body has a diameter of 1~5 -4- 1283256. 5. Description of the invention (3) times, the volume specific volume is 1~20ml/g, and has a suction capacity of 0.3~5 times its own weight, which can be fully suspended. In water, another 45-95 parts by mass of starch-containing material and starch (containing starch: starch = 0 to 80:1 00~20), adding 1 to 30 parts by mass of mixed heat-solidified substance and 0.1~ 5 parts by mass, the obtained foam is treated by an extruder, the diameter of which is 1 to 5 times the diameter of the mold, the volume specific volume is 1 to 20 ml/g, and has an oil absorption capacity of 0.3 to 5 times its own weight, and can be fully suspended in Water, it has also been found that the foam can be made into a powdery oily liquid substance, and it is found that the foam of the present invention absorbs pesticides or oily substances, and is optionally coated into a powdery solid pesticide or a premix thereof. Or a fine powder of a solid carrier, that is, having a water surface suspension property. Further, the present invention is completed by the granules which are easily released in an oily active ingredient in a short period of time. The starch-containing material used in the invention comprises corn, corn flour, corn slag, rice, rice flour, rice bran, dried cassava, dried sweet potato, potato, sweet potato, soybean, mung bean, wheat bran, wheat, wheat flour, millet, alfalfa and the like. The starch of the film can be formed after the formation. Starch has unprocessed starch and processed starch, and specific examples include potato starch, corn starch, high sol starch corn starch, sweet potato starch, tapioca starch, sago starch, rice starch, amaranth starch and other unprocessed starch, and processing thereof. Starch (acidified starch), oxidized starch, dialdehydeized starch, etherified starch (carboxymethyl starch, hydroxyalkyl starch, cationic starch, methylolated starch, etc.), esterified starch (starch acetate, starch phosphate, Succinic acid starch, octadienyl succinate starch, maleic acid starch, higher fatty acid esterified starch, etc., crosslinked starch, grafted starch, and heat-treated starch. It is preferred to use soft starch which is weak in film such as oxidized starch, acid-treated starch, and lightly crosslinked starch. The strength-crosslinked starch ‘has not been easily produced in an extruder....1. 1283256 V. The tendency of the invention (4). Among them, wheat flour, corn slag, and corn flour are better. Wheat flour is divided into strong powder, medium strength powder and thin force powder. The present invention can be added with a lipid by pressurizing the mixture before extrusion treatment. The lipid used in the present invention comprises a neutral lipid (a glyceride comprising a fatty acid, a liquid fat and a solid fat at a normal temperature), a bismuth (including an ester of a fatty acid and a higher alcohol, a petroleum hydrazine such as a stone enamel, a sarcophagus, etc.), and A simple lipid such as a sterol or a vitamin A or an ester of 0, or a phospholipid containing nitrogen, a glycolipid having a sugar as a constituent component, a sulfur lipid having a sulfate or a sulfo group therein, and a C-10 chain. The composite lipid is regarded as a fatty acid of a precursor or a metabolite of the above two, a carotenoid of a higher alcohol, a sterol, a hydrocarbon, or a squalene, and a derivative lipid such as a fat-soluble vitamin. Among them, the oil ester of fatty acid glyceride (lard, half fat, palm school oil, coconut oil, soybean oil, olive oil, safflower oil, peanut oil, rapeseed oil, white skein oil, corn oil, cottonseed oil, rice oil) , sesame oil, sunflower oil, castor oil, cocoa butter, linseed oil, tung oil, sage oil, marine animal oil), or petrolatum, sarcophagus, etc. are applicable. In order to use an extruder to extrude, thermoplasticity is required. In order to make the starch thermoplastic, non-aqueous gelatinization is not possible. However, the foam obtained by adding starch to water paste contains a large amount of water, and the foam must be dried in order to improve the oil absorbing ability of the object of the present invention. If a small amount of lipid is added, the amount of water can be minimized or not added, and the foam with less moisture can be smoothly pressed out. Further, when a thin lipid film is formed on the surface of the foam, the oil absorbing ability of the foam can be greatly improved, and the ability to suspend on the water surface can be increased. The amount of lipid added is 〜·1 to 8 parts by mass, but jute-6-1283256 containing the original lipid is used. 5. Description of the invention (5) Starch containing rice flour, corn slag, wheat flour, etc.: or octadienyl succinic acid Processing starch such as starch, higher fatty acid esterified starch, etc., the amount of addition may not be limited. The present invention employs an extruder to pressurize the mixture before the extrusion treatment, and an emulsifier can be added. The emulsifier used in the present invention may be a nonionic surfactant having an appropriate HLB enthalpy, an anionic surfactant such as soap, a polymer such as a protein, or the like, but a glycerin fatty acid ester, a sucrose fatty acid ester, or a sorbitan fatty acid ester. Food additives such as propylene glycol fatty acid ester, lecithin, stearic acid calcium lactate, sodium oleate, morpholine fatty acid salt, and polyoxyethylene higher fatty alcohol are preferred. The emulsifier in the present invention can be regarded as improving the emulsifying property of the starch-containing substance or starch and the lipid, and as a result, the bubbles inside and on the surface can be increased, which is advantageous for improving the oil absorbing ability and the surface suspensibility. The amount of the emulsifier added is 0.1 to 5 parts by mass. The thermosetting substance used in the present invention includes protein proteins such as wheat protein such as soybean protein and gluten, milk proteins such as casein, and thermocoagulated polysaccharides such as curd or methyl cellulose. When the thermally solidified material is dissolved, it becomes a mesh-like polymer structure, and is solidified by heating, and when it is treated by an extruder, a foam having fine bubbles is formed. A foam having hardness is formed by adding a crosslinking agent. The amount of the thermally solidified substance added is 1 to 30 parts by mass. The crosslinking agent used in the present invention may be a phosphate such as sodium tripolyphosphate, sodium triphosphate or phosphorus oxychloride, epichlorohydrin, polyepoxy compound having a terminal epoxy group at the terminal, aldehyde such as formaldehyde or glyoxal. a difunctional group-containing substance (adipate, acrolein, diethylene urea, diisocyanate, melamine tree-7- 1283256) obtained by reacting an amino group or a carboxyl group contained in a polysaccharide such as other starches V. INSTRUCTIONS (6) Fat, melamine-formaldehyde water-based resin, amine-based resin, polyamine/epichloroalkyl-based resin, water-soluble alkylated amine-based resin, water-soluble methylated melamine resin, etc.) A polyvalent cationic salt such as potassium citrate, calcium salt or magnesium salt. It is preferred that non-toxic substances such as food additives are used. These cross-linking agents do not need to use any catalyst (as long as heating), but the catalyst necessary for the cross-linking reaction can be added to the general user (usually the optimum pH, alkaline or acid catalyst can be added) . The amount added is 0.1 to 5 parts by mass. The crosslinking agent in the present invention contributes to the adjustment of the diameter of the foam upon foaming and has a surface suspension property. Among the above various materials, the compounding qualities thereof are as follows. The starch-containing substance is 95.0 to 99.0 parts by mass, the crosslinking agent is 0.1 to 5 parts by mass, and the necessary amount of the catalyst is crosslinked. Starch-containing substance and starch (starch-containing substance: starch type = 0 to 80: 1 00 to 20) 45 to 95 parts by mass, if necessary, 0.1 to 8 parts by mass of the lipid, if necessary, emulsifier 0.1 to 5 parts by mass, thermally coagulated 1 to 30 parts by mass of the substance 'crosslinking agent 〇 · 1 to 5 parts by mass, and the necessary amount of catalyst for crosslinking. The starch-containing substance in the present invention contains other natural substances or derivatives thereof, for example, a natural substance such as a cellulose type, a protein type, and a natural rubber type, or a derivative thereof. Cellulose natural products or derivatives thereof, such as carboxymethyl cellulose and salts thereof, cellulose derivatives such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose Things. The natural product of the protein system or a derivative thereof may be, for example, gelatin obtained from animal bone or the like, casein obtained from cow's milk and a salt thereof, and gluten obtained from wheat. Natural rubber or natural derivatives or derivatives thereof, such as rubber, alginate and 1283256, invention instructions (7) derivatives of salts or esters, viscous polysaccharides, xanthan gum, weiler gum, guar Gum, curd, etc. The extruder of the treatment apparatus of the present invention is explained below. Generally, the extruder is composed of a chute, a feeder, a screw, a cylinder, a mold, a heating coil, a cooling jacket, and a drive motor, and has a single shaft and a double shaft, preferably a double shaft. The foam of the invention is made up of a tube temperature of 60 to 250 ° C, preferably 80 to 160 ° C, a screw rotation number of 50 to 3 00i: pm, preferably 70 to 200 rpm, and a mold temperature of 90 to 200. °C, with 1〇〇~15 0°C as the crucible, the die discharge diameter is 5·5~10mm, and extruded under the condition of 1~5mm. The foam is preferably 10 times or less in the die diameter, and has a small number of small bubbles at 1 to 5 times, and a foam having a large specific gravity can be obtained. The barrel temperature is related to starch gelatinization and crosslinker reactivity. The number of revolutions of the screw affects the extrusion pressure and controls the size of the emulsified particles before extrusion. The mold temperature affects the foaming power and is related to the internal moisture discharge. The die extrusion diameter can be appropriately adjusted according to the use, but the foam is preferably 10 or less times of the die diameter, and must be selected at 1 to 5 times to obtain a foam having a large number of small bubbles and a large specific gravity. The foam of the present invention has a die diameter of 1 to 5 times, and can be made into a foam having a small number of small continuous bubbles and a large specific gravity. The foam has a volume specific volume of 1 to 20 ml/g, preferably 1 to 12.5 ml/g, and has an oil absorption capacity of 3 to 5 times, more preferably 1 time or more, and a suspended water surface of 10 minutes or more. More than 1 hour is preferred. For the volumetric volume measurement method, take 20 grams of the sample (5 grams for light) and put it into a measuring cylinder of 500 ml (light 1 liter) capacity, and measure the cylinder scale (ml) (average 高 of high and low 値) . The volume specific volume is obtained by the following formula: -9- 1283256 V. Description of the invention (8) Volumetric specific volume (ml/g) = scale 値 / 20 (or 5) Oil absorption multiple measurement method: wide-mouth glass in a capacity of 200 ml Bottle, put 1 sample of sample, add a small amount of white oil. After the dropwise addition, the bottle was capped and the bottle was shaken by hand to mix the white skein oil with the sample. The inner wall of the bottle is no longer attached with white skein. When there is no white skein on the surface of the sample, open the cover and add a proper amount of white skein. Repeat the above operation. Finally, the mixture was added to the shaking mixture for 5 minutes, and the white skein oil was no longer attached to the inner wall of the bottle. The surface of the sample had disappeared and the white skein oil was bright. At the end, the oil absorbing ability was determined by the following formula. Oil absorption capacity (%) = [{ dripping white skein weight (§)} + {sample weight (10g)}] xl00 The starch foam thus obtained is divided into a water-soluble film and put into a paddy field treatment, that is, a so-called giant agent Or a package, or a package, may be used as a carrier for the surface suspended pesticide granules treated in the water surface bib. In recent years, these dosage forms can be used as labor-saving pesticides with strong demand, especially granules with high concentration of liquid prologues, which can reduce the amount of drug per unit area. The body absorbing in the original state will sink, and it will be released in a short time, without any phytotoxicity or insufficient efficacy. The active ingredients of the pesticide used in the present invention include herbicides, insecticides, fungicides, plant regulators and the like which are applied on the surface of the paddy field, and the physical properties thereof are not particularly limited, and the herbicidal active ingredients are, for example, Bixilong Mesozoic, Yazi. Moxuan Qianlong, Yishanglong, Baishoulong, Adoluo Qianlong, Yanuo Suolong, Xikulongfa Molong, Zimibituo, Mifa Nasit, Prasap, Rice Mu, Billipzik, Tuni Kullo, Azov Promup, Pudomi, Sulong Pujidu, Ticalon, Kafate, Perron, Bizo Napu, Birazzoluto, Bilazox West, Bifulrex, Dan, -10- 1283256 V. Description of invention (9) West American tolin, Jimmy Tatline, Acquatic散佐, 阿朵必散林朵, 齐齐欧必, 乙拉拉草, 欧克散齐阿奇, Naplon Anilin, similine, 2,4-D and its alkyl esters or Salt, MCPA, MCPB and its alkyl esters or salts, Ouke San Kulongmei, Non-Tolamisu, Bizobisikul, Itanof, Kumiron, Birazzo, Anilon Live speed, Fenno, will long live speed, then scattered Connaught library meters, the library will Linminuoba America West, US Kulon Kulon popular version of Talon and so on. Insecticidal active ingredients can be used as insecticides that are saturated with mobility, as well as insects that are effective in water-borne pests such as rice weevil, rice worms, such as Syrah, Occidental, and Sikron. , Yoshitoprolong, Idahim, Nitrobamine, Yasitamipine, Jiafusong, Yaziqi Occidental, Daisy, Sulfur, Oxen, and Fuk, etc. . The bactericidal active ingredient can be used as an effective bactericide such as rice fever or sheath blight which is soaking and mobilizing, for example, he is Kulong Fota, Olin Prai, Azoxi, and Mplonbami. Duo, Bai Kuilong, Ya Ciyu, Plong Bi Nazuo, Xi Xi San Mi Duo, Xi Me Ke Na Zuo, Bu Xi Le Le Song, Trimethoprim, Fenpney, Fu Duoning, Fulametine Chlorpheniramine, ruthenium, and 7-fluoro-1,2,5,6-tetrahydro-4H-pyrrolo[3.2.1-i,j]porphyrin-4-one and the like. Plant regulators include, for example, maleic acid and its salts, albisic acid, calcium peroxide, inafufubaksu, house niknana, tolina, and sigma. The active ingredient of the pesticide used in the present invention may be one or more of the above herbicides, insecticides, fungicides, and plant conditioners, and among the herbicides, it is of course possible to mix two or more active ingredients having different action mechanisms or objects. -11- 1283256 V. INSTRUCTIONS (1G) 'However, for example, herbicides and fungicides or insecticides, it is also possible to mix two or more kinds of objects completely different. Among them, the liquid precursors such as butyl praline, praache, alonone, piracetox, valonolactone, and medamine tartrate are more common than ximulon and sagitar , Yaji Mosuo Qianlong, Adoluo Qianlong, Yishanglong, Sinovel, Qianlong, Xikulongfa Moron and other sulfoximine-based urea herbicides (SU agent), card non-speed, Oke Sanchi Aji, Tica Long, Ouke San Kulongmei, Non-Tula Laomi, Bizo Bisikul, Itanof, Bili Minobaku Mexi, Bila Zuo, Herbicides such as mustazolidine, biszolzulkulon, sirolius, sulco sulphate, sultanate, effluentine, edetamine, nitrozil, yasicapalin, plus Fusong and other insecticides, he is Kulong Fota, Olin Prai, Azoxi West, Tallon, Kaplan Bami, Bai Kuilong, Yassin, Plonbina, West It is preferred to use bactericidal agents such as mitochondria and simexa, especially the above liquid precursor or SU herbicide. Most of the active ingredients of these pesticides can be suspended in the water surface when they are put into the paddy field. After the water surface is widely expanded, it is easy to disperse, emulsify, dissolve in the water, or suspend the water surface without entering the water. It must be diffused in the paddy field as soon as possible to be insoluble. In the case of a water compound, when the active ingredient is suspended in the water surface for a long period of time, it is blown away by the wind to accelerate the localization of the active ingredient, and a suitable wetting and dispersing agent or emulsifier should be mixed to disperse, emulsify and dissolve the active ingredient in water. Therefore, if necessary, a suitable extender or auxiliary agent should be mixed to form a granule which is easily emulsified and dispersed when the active ingredient is wetted by water. The compounding ratio of the active ingredient of the agricultural chemical used in the present invention is not particularly limited, but in consideration of economy and labor saving, it is higher in the range which does not hinder the treatment. -12-1283256 V. The invention description (11) is good. Usually it is 0"~80% in the pesticide granules, preferably 0.3~70%, more preferably 0.5~60%. The viscous pesticide composition suspended on the water mask of the invention should be dispersed, emulsified and dissolved in the water quickly after being expanded on the water surface, and can be disintegrated or not disintegrated when it is put into water, even if it is not Disintegration is also suitable for dissolving the active ingredients of pesticides in a short period of time. In order to make the viscous pesticide composition disintegrable, the granular pesticide composition having a suspension property on the surface of the present invention may contain an enzyme which acts on a starch-containing substance or a starch. The enzymes used in the present invention include amyloglucosidase, α-amylase, 泠-amylase, and isoamylase. Amyloglucosidase is a kind of amylolytic enzyme produced by bacteria or filamentous bacteria, which acts on α-1,4 bond and α-1,6 bond of starch, and separates glucose molecules one by one from the non-reducing end of glucose chain. Exo (exo) enzyme. Alpha-amylase is an amylolytic enzyme produced by bacteria or filamentous bacteria, which has heat resistance and is pH stable. An enzyme which hydrolyzes the α-1,4 bond of a glucose polysaccharide having three or more α -1,4 bonds, and decomposes at least 5 or more oligosaccharides to form an inner wall of glucose, maltose, and oligosaccharide (endo) Enzyme. The starch or its derivative can be cut off at random and decomposed into oligosaccharides at once, so that the viscosity-reducing ability is excellent. Amylase is an amylolytic enzyme derived from malt, also known as malt amylase. Recently, it has also been made from bacteria and filamentous bacteria. From the glucose non-reducing end of α-1,4 glucan such as starch, animal starch glycogen, and dextrin, maltose exogenous enzymes are sequentially produced. From the malt producers and α--13-1283256 V. Invention description (12) A mixture of amylase. Isoamylase is present in yeast, rice, potato, pea, malt, and the like. The α-1,6-glycosidic bond in starch-based polysaccharides such as gelatin starch and animal starch glycogen produces an endogenous enzyme of an amylase-like polysaccharide formed by a-1,4 bond. In the present invention, when a particulate pesticide composition having a suspension property on a water surface is contained, and a cellulose natural product or a derivative thereof is contained, the enzyme which acts on it is a cellulose enzyme. This enzyme is a complex enzyme composed of at least three enzymes, most of which have hemicellulase activity on the cellulose of the polysaccharide of the five-carbon sugar. Cellulase enzyme hydrolyzes the /3-1,4-glucose chain in cellulose to form a soluble polymer and dextrose. Cellulase is a complex enzyme having the following activities. C! Activity: An enzyme that destroys natural cellulose.

Cxl活性··以生成纖維糊精、纖維三糖、纖維二糖之內型 葡萄糖酵素，由麹菌屬黴菌分離。The Cxl activity is formed by the formation of cellodextrin, cellotriose, and cellobiose, and is isolated from the fungus of the genus Fusarium.

Cx2活性：把Cxl生成的纖維糊精分解，生成葡萄糖。 本發明在水面具有懸浮性的黏狀農藥組成物，含有蛋白 質系天然物或其衍生物時，對其作用之酵素，有例如細菌 蛋白酵素、絲狀菌蛋白酵素、木瓜酵素、胃蛋白酵素。 細菌蛋白酵素係由枯草桿菌生產之酵素，按其作pH分 成中性蛋白酵素和鹼性蛋白酵素。對蛋白質和肽作用，可 用於製造麵包、乾洗劑、家庭用淸潔劑等。 絲狀菌蛋白酵素有麴菌屬起源、酒麴菌屬起源、鏈黴菌 屬起源等，性質因起源而異，日本自古利用在咪噌、醬油 -14- 1283256 五、發明説明（13 ) 製造中分解大豆蛋質。大多爲外型蛋白酵素和內型蛋白酵 素’澱粉酵素含量因菌株不同而異。又，因菌株而有纖維 素酵素、磷酸脂酵素、RNA酵素、果膠酵素等共存。 木瓜酵素係由木瓜水果製造，用於防止啤酒渾濁。特別 對肽、醯胺、酯等鹼性胺基酸、白胺酸、甘胺酸等結合部 份水解’以半熟木瓜爲原料。 胃蛋白酵素可將芳族或二羧酸系的左旋胺基酸殘基鄰接 的肽鍵水解。對酯或醯胺無作用。在pH 1.8〜2.5之極低 pH亦可作用。 此外’作爲消炎藥的蛋白質分解酵素，有胰蛋白酵素、 胰凝乳蛋白酵素、胞漿素、瑕普隆西、鯊油肽酵素、鳳梨酵 素等。 本發明在水面具有懸浮性的粒狀農藥組成物，含有果膠 時，對其作用之酵素有果膠酵素。可用作麻之醱酵精煉、 果汁或葡萄酒之澄淸劑。果膠分解酵素係可對果膠物質水 解的酵素群總稱，包含原果膠酵素、果膠酯酵素、果膠· 果膠水化酵素、多聚半乳糖醛酸酵素、果膠酵素等。凡此 均有內型和外型。 本發明在水面具有懸浮性的粒狀農藥組成物，含有海藻 酸及其鹽或酯等衍生物時，對其作用之酵素有海藻酸酵素 ，及海藻酸裂解酵素。海藻酸酵素存在於鮑魚、蠑螺、海 兔、武鯛等之消化液中，生成寡糖醛酸替苯胺、甘露糖醛 酸、二或三糖醛醯替苯胺。海藻酸裂解酵素存在於單孢菌 屬中，可將海藻酸脫離反應性分解，生成以具有不飽和鍵 的糖醛酸爲非還原末端之低聚糖。 -15- 1283256 五、發明説明（14) 本發明在水面具有懸浮性之粒狀農藥組成物，含有黏稠 性多糖時，對其作用之酵素有支鏈澱粉酵素、異支鏈澱粉 酵素、支鏈澱粉酵素對黏稠性多糖澱粉果膠、動物澱粉肝 醣之α-1，6鍵水解，生成麥芽三糖、溶膠澱粉等直鏈多糖 類。對黏稠性多糖以內型作用β異支鏈澱粉酵素係對黏性性 多的α-1，6葡萄糖苷鏈相鄰之還原末端側的α-1，4葡萄糖 苷鏈水解，生成異6-α-葡萄糖基麥芽糖。 本發明在水面具有懸浮性的粒狀農藥組成物，含有多糖 類·黏聚多糖類時，對其作用之酵素，有玻糖醛酸酵素。 如此對天然高分子物質或其衍生物作用之酵素，有對高 分子鏈之鍵部份無所作用，對任何低分子量的聚合物可分 解者（內型），和對高分子鏈的末端鍵部位有作用，可將構 成成份逐一分離者（外型）。在本案中以內型酵素爲宜。 外型酵素也無妨，但由於只對天然物或其衍生物的末端 有作用，其缺點爲作爲結合劑的天然物或其衍生物分解稍 微費時（製劑之崩解、分散費時）。 在本案中，此等含澱粉物質及澱粉類與所作用的酵素組 合當中，較佳例係含澱粉物質和澱粉類爲玉蜀黍粉、玉米 渣、或小麥粉，且酵素係內型α-澱粉酵素或異澱粉酵素 之組合，而更好是天然物或其衍生物爲小麥粉，且酵素爲 內型α -澱粉酵素或異澱粉酵素之組合。 澱粉混配量因含澱粉物質和澱粉類物質及其混配量和酵 素種類及力價而大異，惟在本發明水面懸浮擴散型農藥性 製劑中，通常爲0.001〜10質量份，以0.002〜5質量份爲 -16- 1283256 五、發明説明（15 ) 佳，而以0.01〜3質量份更好。藉調節酵素的混配量’可 調節農藥製劑在水中的溶解或崩解時間。 本發明粒狀農藥組成物形狀爲圓柱形，亦可爲不定形。 農藥有效成份爲固體時，爲發揮生物活性，要粉碎到充 分粒度。必要時可加其他粉碎助劑、潤濕劑、分散劑等， 宜利用鎚磨機或噴磨機以乾式粉碎，形成含有高濃度農藥 有效成份之預混物，亦可利用砂磨機、硏磨機、珠磨機等 以濕式粉碎。 濕式粉碎時，若使用油狀物質爲媒體，可原樣吸收於本 發明載體，但使用水時，可用例如噴霧乾燥機等適當乾燥 機加以乾燥，若利用鎚磨機或噴磨機等以乾式粉碎時，可 按上述乾式預混物同樣處理。 製造粒劑時，可於預先調製之本發明發泡體，使用適當 不揮發性液狀物質被覆農藥有效成份，或將農藥有效成份 溶於適當溶劑，吸收於預先調製之本發明發泡體，而得標 的懸浮性農藥粒劑。 利用被覆法時，例如將預先調製之本發明發泡體，充塡 於攪拌混合機，添加非揮發性液狀物質，使表面潤濕後， 添加固體農藥有效成份之粉碎品，或必要時，添加含有水 面擴展劑或其他助劑之粉末預混物，再加攪拌，而被覆於 粒表面。非揮發性液狀物質亦可改用液狀或調成液狀之農 藥。 利用吸收法時，一般是例如將預先調製的本發明發泡體 充塡於攪拌混合機，添加液狀或利用溶劑等液狀化之農藥 -17- 1283256 五、發明説明（16) 有效成份，或其濃厚油性預混物，加以吸收。在農藥有效 成份的粉末或油性預混物中，可混配水面擴展劑，必要時 加其他助劑。 以被覆法或吸收法調製粒劑時，爲使水面擴展劑發揮最 大效果，可在被覆或吸收農藥有效成份或其他助劑後，最 後才添加。如此，被覆或吸收步驟亦可分二階段以上進行。 所用攬拌混合機宜選用水泥混合機、史密斯混合機、托 托瓶、諾塔混合機、條帶混持器、旋轉式混拌器、V型混 合機等，以低速混合減少粒破碎之機種。 關於粒劑粒度，粒徑小則易沉水中，作爲撒佈用粒劑時 ，易受到風的阻力。反之，粒徑大多在20mm以上，除可 容易用風吹送外，吸收於中心部的液狀有效成份溶出時間 費時，在吹達位置沉降時，會造成農藥有效成份的偏位。 通常是90%以上進入0.71mm〜15mm區域，以40%以上進 入1 mm〜1 0mm區域爲佳。 欲得本發明水面懸浮擴展性良好之農藥粒劑，可將農藥 有效成份與本發明發泡體，在水面擴大範圍使用之水面擴 展劑，以及其他補助劑，加以混配調製。 本發明水面擴展劑係爲將農藥賦形劑在水面擴展廣大範 圍而混配，可用例如丙烯酸、順丁烯二酸等羧酸，或苯乙 烯磺酸，將乙烯基等聚合所得鈉鹽、鉀鹽、銨鹽等羧酸型 或磺酸型之聚皂；油酸鈉或硬脂酸鉀等肥皂類；單或二烷 基磺丁二酸鹽，及於此附加環氧烷之界面活性劑，十二烷 基苯磺酸鈉，烷基硫酸鹽，α-烯烴磺酸鹽，α-磺脂肪酸 -18- 1283256 五、發明説明（17 ) 鹽，α-烯烴脂肪酸鹽，油基甲基牛磺酸鹽等陰離性界面 活性劑；聚氧乙烯烷芳醚、聚氧乙烯烷醚、聚氧乙烯芳芳 醚、聚氧乙烯烷芳酯、聚氧乙烯山梨糖醇酐之酯，山梨糖 醇酐之烷酯，矽酮系界面活性劑、乙炔系界面活性劑、 pluronic型界面活性劑等各種非離子性界面活性劑；聚氧 乙烯烷芳醚、聚氧乙烯烷醚、聚氧乙烯芳芳醚、聚氧乙烯 烷酯、山梨糖醇酐之烷酯等磷酸或硫酸酯，視情形可以適 當鹼加以中和之界面活性劑；氟系界面活性劑；各種陽離 子界面活性劑；兩性離子性界面活性劑；乙二醇，丙二醇 ，丁二醇，及其聚合物等二醇類之各種酯和醚類；流動石 蠘或環烷系或芳族系高沸點溶劑；低黏度聚丁烯、矽光油 、機油等礦物油類；各種動植物油；松脂等各種樹脂類； 樟腦白α -苹烯；樟腦；萘；疏水性氧化矽等，較佳爲單 或二烷基丁二酸鹽及於此附加環氧烷之界面活性劑，α -烯烴磺酸鹽，α-磺脂肪酸鹽，α-烯烴脂肪酸鹽，油基甲 基牛磺酸鹽，烷基硫酸鹽，乙炔系界面活性劑，矽酮系界 面活性劑，氟系界面活性劑，二醇類之醚類或酯類，以及 羧酸之烷酯，更好是α-烯烴磺酸鹽，α-烯烴脂肪酸鹽， 乙炔系界面活性劑，二醇類之酯。此等水面擴展劑當中， 可用分散劑，結合劑，製粒增進劑或乳化劑。 單或二烷基磺丁二酸鹽及於此附加環氧烷之界面活性劑 ’不但農藥一般所用二烷基磺丁二酸鹽，亦可含有單烷基 磺丁二酸鹽，預先附加單聚環氧烷（C2〜C4)，調製烷醚， 磺丁二酸每分子與此一分子或二分子反應所得鹽。 -19- 1283256 五、發明説明（18) 凡此有例如以紐克29 1 PG(日本乳化劑公司製品），尼歐 克SWCE，尼歐克SWC，尼歐克YSK(第一工業製藥公司 製品），紐克給EP-70G(竹東油脂公司製品），GERODON SOS(鹽野義製藥公司製品），倍禮克斯〇Τ-Ρ(花王公司製 品），野隆CT-1 (東邦化學工業公司製品），給拿坡 SV1970J(赫斯特日本公司製品），林巴860K，林巴870E( 獅子公司製品）等（二辛基磺丁二酸鈉），倍禮克斯TR(花王 公司製品）（二（十三烷基）磺丁二酸鈉），倍禮克斯CS(花王 公司公司製品）（二環己基磺丁二酸鈉），林巴ΝΤΟ (獅子公 司製品）(牛脂醯胺磺丁二酸鈉），紐克292PG(日本乳化劑 公司製品）（二乙基己基乙氧基磺丁二酸鈉），階隆普 ACR/4(羅帝亞•濟羅那斯製品（磺可二酸之月桂基乙氧基半 酯之鈉鹽）等商品名銷售。 α-烯烴磺酸鹽有以原油（石油）爲原料的磺化物之鹽，生 物分解性優，對皮膚和眼非常安定，對酸鹼安定，耐硬水 性優，具有諸如此類人或環境均優之特性，有例如C12〜 c16之α -烯烴磺酸鹽。 α -烯烴磺酸鹽之鹽無特別限制，有例如鈉、鉀、鈣、 銨，及各種胺鹽，以鈉、銨或鈣鹽爲佳。 α -烯烴磺酸鹽之具體例，有例如林波拉LB-490、林波 拉LB-840，林波拉PJ-400、Κ林波拉PJ-400，林波拉ΡΒ-800，Dt-95(獅王公司製品），Μ-3801，M-3801 G(第一工業 製藥公司製品），活斯塔發OSB(赫斯特日本公司製品)等。 α-磺脂肪酸鹽係以天然油脂爲原料之磺化物，例如有 -20- 1283256 五、發明説明（19) C10〜C14之α-磺脂肪酸鹽。 α -磺脂肪酸鹽之鹽，雖無特別限制，有例如鈉、鉀、 鈣、銨，及各種胺鹽等，惟以鈉、銨、鈣鹽爲佳。 α ·磺脂肪酸鹽之具體例，有例如FA-6513、FA-616B、 FA-617B(獅王公司製品），山倍斯，山倍斯FM-2(曰本油 脂公司製品）等。 ^ -烯烴脂肪酸鹽係羧酸對α -烯烴反應所得，有例如 Cu之α -烯烴以3-氫硫基丙酸反應所得月桂基硫代丙酸之 鹽，以諾巴斯妥SA-66T、諾巴斯妥SA-66TE(日本油脂公 司製品）商品產銷。 油基甲基牛磺酸鹽係油醯氯與Ν -甲基牛磺酸反應所得 之鹽，其鹽無特別限制，有例如鈉、鈣、鉀、銨鹽等，以 鈉或鈣鹽爲佳。 油基甲基牛磺酸鹽具體例，有例如戴西普Τ粉劑（曰本 油脂公司製品），活斯塔普Τ粉劑（赫斯特日本公司製品）、 阿克普Τ粉劑（赫斯特日本公司製品）等。 烷基硫酸鹽有例如月桂基硫酸鹽，以亞瑪10粉劑（花王 公司製品），莫諾濟粉劑（第一工業公司製品）之商品名銷售。 乙炔系界面活性劑包含炔醇，炔二醇，以及於此附加環 氧烷所得界面活性劑。 炔醇係通式HOCCRiKRi-C三CH(式中R1和R2相同或 不同，代表烷基）所示化合物，R1爲甲基而R2爲 異丙基者有商標賽非諾61，R1和R2爲甲基者有歐非B， R1爲甲基而R2爲乙基者有歐非P市售品。 -21- 1283256 五、發明説明（2G ) . 炔二醇係通式 ΗΟΟ^Ι^ΚΙΙ^ΤΞΟ-^ΐΐΐ^ΟΗβ1 和 R2 相 同或不同，代表烷基）所示化合物，R1爲甲基而R2 爲異丁基者有賽非諾82, R1爲甲基而R2爲異丁基者有賽 非諾104，R1爲乙基而R2爲丁基者有賽非諾DF110，R1 和R2均爲甲基者有賽非諾γ商標產品市售。 另外，於上述炔醇或炔二醇附加環氧烷之界面活性劑， 有例如於上述炔醇或炔二醇附加環氧乙烷和/或環氧丙烷 等所得界面活性劑。附加環氧烷者有例如於賽非諾104附 加環氧乙烷者，以商標賽非諾400系列市售。 另外，賽非諾1〇4(蠟狀）與無晶形二氧化矽按40:60重 量比率混合粉碎之粉末狀預混物，有賽非諾104S，而賽 非諾DF 110(蠟狀）與無晶形二氧化矽按40:60比率混合粉 碎之粉末狀預混物，有賽非諾DF 11 0S市售（都是野龍公司 製品，日信化學公司銷售）。 聚矽氧系界面活性劑係在甲基或二甲基聚矽氧烷末端和 /或側鏈的甲基一部份，導入環氧乙烷或聚環氧丙烷，或 二者，視情形可將末端的羥基以烷基加以醚化或酯化，以 聚醚改質之聚矽氧油爲主成份之非離子性界面活性劑，有 例如西加朵系列（陶康寧聚矽氧公司製品），西加朵系列（曰 本約尼卡公司製品），聚矽氧油KF系列（信越化學公司製 品），奇尼濟克（黑雷邦化學公司製品）等商標市售。 氟系界面活性劑係通常陰離子性、非離子性、陽離子性 、或兩離子性係界面活性劑之氫原子一部份或全部，以氟 ____-22- 1283256 五、發明説明（21 ) / 原子取代所得界面活性劑，已知表面張力降低力優良，有 例如以約尼庫伊系列（庫伊奇工業公司製品），米加拂克系 列（大日本油墨化學工業公司製品），拂塔西妥系列（禮歐斯 公司製品）、賽拂隆系列（旭玻璃公司製品）、亞拂妥普（妥 濟武產品公司製品）等商標市售。 二醇類醚和酯類有將乙二醇、丙二醇、丁二醇，及其聚 合物末端羥基之一或二者，具體例有己二醇（(HeG，乙二 醇單己醚，日本乳化劑公司），己二甘醇（HeDG，二乙二醇 單己醚，日本乳化劑公司），2-乙基己二醇（EHG，乙二醇 單2-乙基己醚，日本乳化劑公司），2-乙基己二甘醇 (EHDG，二乙二醇單2-乙基己醚，曰本乳化劑公司）等以 其商標市售。 羧酸烷酯有椰子油脂肪酸、月桂酸、油酸、乳酸等羧酸 ，或順丁烯二酸、檸檬酸、反丁烯二酸、己二酸、戊二酸 、苯二甲酸等多元羧酸之甲酯、乙酯、丙酯、丁酯、己酯 、乙基己酯、月桂酯、油酯等烷酯，具體例有以亞克西普 MC(椰子脂肪酸甲酯，花王公司），亞克西普M-OL(油酸甲 酯，花王公司），比尼賽沙30(油酸異丁酯，花王公司）， 比尼賽沙124(苯二甲酸二烷酯，花王公司），乳酸丁酯（武 藏野化學硏究所）等商標市售。 本發明所用水面擴展劑之混配量，因農藥有效成份的種 類和含量，水面擴展劑種類及其添加方法，其他成份的種 類和混配量等製劑處方或劑型而異，通常在農藥固體劑中 佔0.1〜30%，以0.3〜20%爲佳，而以0.5〜10%更好。 -23- 1283256 五、發明説明（22 ) 本發明農藥固體劑可混配非揮發性液狀物質、乳化劑、 分散劑、潤濕劑、稀釋劑、撥水劑、粒子成長防止劑、以 及安定劑其他補助劑。 常溫時爲固體，半固體或液狀農藥有效成份，爲了稀釋 以便被覆浸泡，必要時可用非揮發性液狀物質。非揮發性 液狀物質宜對農藥有效成份的粒子成長、分解等沒有不良 影響，且具有可使農藥有效成份均勻被覆、飽浸於本發明 發泡體之性質，而以高沸點、低毒性、引火點高、低黏度 ，且比重小於1者爲佳。一般農藥有效成份比重大多在1 以上。在如此情況下，乳化性宜盡可能長久留在水中，爲 了廣佈擴散於水田，大多使用比重低於1之低黏度溶劑。 例如低黏度之流動石蠟、異石蠘、機油、聚丁烯、石蠟烴 系、環烷系、芳族系等各種高沸點溶劑等礦物油；椰子油 、大豆油、菜籽油等植物油；鯨油、沙丁魚油等動物油； 聚矽氧油及其衍生物；油酸、乳酸、椰子油脂肪酸、順丁 烯二酸、反丁烯二酸、苯二甲酸、己二酸等單或多元羧酸 ，及其種種酯；磷酸三丁酯或磷酸三氯乙酯等各種磷酸酯 之可塑劑；ε-己內酯、7-丁內酯等內酯類；N-甲基四氫 畊咯酮；及各種液狀界面活性劑等，較佳者有低黏度流動 石鱲、機油、異石鱲或各種酯，具體例有超油系列，斯密 Ρ系列（日本石油化學公司製品），流動石蠘No系列（中央 化成公司製品）等流動石蠘；瑞香寧油系列（出光興公司製 品）等機油；艾索帕系列，異溶膠系列（曰本石油化學公司 製品）等異石蠟等，亦可上述二種以上混合使用。 -24- 1283256 五、發明説明（23 ) 本發明所使用非揮發性液狀物質混配量，因農藥有效成 份種類或其他助劑之種類，混配量等而異，但在對農藥固 形劑的長時安定性或物理性不影響情況下，愈少愈好。其 混配量一般爲1〜60%，以2〜50%爲佳，而以3〜40%更 好。 本發明所用乳化劑，係將液狀農藥有效成份或農藥有效 成份溶液在水中乳化所必須，可視農藥有效成份或溶劑， 按選擇通常乳劑之乳化劑同樣加以選擇使用。 本發明所用乳化劑混配量，一般爲〇.〇1〜30%，以0.03 〜15%爲佳。 本發明所用分散劑用來把農藥有效成份懸浮分散於水中 ，有例如木質素磺酸鹽，（烷基）萘磺酸鹽及其縮合物，酚 磺酸鹽及其縮合物，苯乙烯磺酸鹽之縮合物，順丁烯二酸 和苯乙烯磺酸的縮合物之鹽，丙烯酸或馬來酸等羧酸縮合 物之鹽，烷基苯磺酸鹽、月桂基硫酸鹽，聚氧乙烯烷基芳 醚硫酸鹽，聚氧乙烯烷醚磷酸酯及其鹽，聚氧乙烯烷基芳 醚磷酸酯及其鹽等陰離子性界面活性劑，或三聚磷酸鈉， 六偏磷酸鈉等磷酸鹽，另外，非離子性、陽離子性、兩性 離子界面活性劑，亦可適當選擇使用。此等分散劑，大多 可用作潤濕劑。 本發明所用分散劑和潤濕劑之混配量，一般爲0.01〜 3 0%，以〇·1〜20%爲佳，而以0.2〜15%更好。 本發明所用稀釋劑，是調製固體農藥有效成份濃的預混 物時之稀釋劑，有例如皂土、滑粉、黏土、矽藻土、無晶 -25- 1283256 五、發明説明（24) 形二氧化矽、碳酸鈣、碳酸鎂等用作一般農藥載體之礦物 質微粉，此外有氯乙烯、氯化亞乙烯、聚乙烯、聚丙烯等 各種樹脂粉末，葡萄糖、砂糖、乳糖等糖類，澱粉及其衍 生物，微晶形纖維素、木粉、鋸屑、米糠、麥糠、粗糠粉 、咖啡豆粉、椰子殼粉、活性炭、纖維素粉、甘草粉等有 機物，硫酸鈉、硫酸銨、氯化鉀等水溶性無機鹽類和尿素 等。 本發明所用增量劑混配量，一般爲0.1〜80%，以0.2〜 50%爲佳，又以0.5〜20%更好。 本發明所用撥水劑，主要農藥有效成份之水溶性高時， 可抑制農藥有效成份之溶出，在水面盡量廣泛擴散後，爲 使其溶於水中而混配，有例如硬脂酸鎂、硬脂酸鈣等脂肪 酸鹽，硬脂醇等高級醇，硬脂酸等高級脂肪酸，聚矽氧油 及其衍生物，氟系界面活性劑、陽離子性界面活性劑、疏 水性氧化矽、流動石蠟及機油等。 本發明所用撥水劑混配量，因農藥有效成份種類或物理 性而異，其混配量一般爲0.05〜10%、以0.1〜5%爲佳。 本發明所用粒子成長防止劑或安定劑，可視農藥有效成 份性質之必要而混配。此外，必要時可混配色素、苦味劑 ，其他種種補助劑。 本發明農藥粒劑爲了在水面擴展後，使農藥有效成份迅 速在水中分散、乳化、溶解，需調節潤濕劑、分散劑、乳 化劑等之混配量。 如此所得本案農藥粒劑，利用下述方法，宜顯示擴展性 -26- 1283256 五、發明説明（25 ) 指數5以分上之良好水面懸浮擴展性。 「擴展性指數」係具有水面懸浮擴展性的農藥固形劑在 水面之擴展性，以〇〜15分的範圍（15分爲滿分）加以數値 化，分數愈大，水面擴展性愈佳，以5分以上爲宜，7分 以上更好，而以9點以上尤佳。水面擴展性的試驗法如下 〇 於長4公尺、寬14公分的盆，裝自來水25公升，把水 溫調至2(TC。假設四面水上的障礙物（懸浮物），將斯米西 康（住金物產公司製品，粗糠粉）2克處理成在水面均勻。 靜置後，取農藥固形劑280毫克，從該盆的一端10公分 處投入，投入後目視調查從各農藥固形劑投入處起1_5公 尺到達時間，距投入地點的最長到達距離，以及投入5分 鐘後的擴展狀態，按下列表1所載基準評判，將各項評分 合計’分別求出擴展性指數。 -27- 1283256 五、發明説明（26) 表1 擴展性評分項目及評分基準 評分項目 評判基準 評分 1.5m到達時間 2分以上 0 1分以上、2分以下 1 3 0秒以上、1分以下 2 2 0秒以上、3 0秒以下 3 10秒以上、20秒以下 4 1 0秒以下 5 最長到達距離 ------- 0.5 m以下 0 0_5m以上、1.0m以下 1 1.0m以上、1.5m以下 2 1 _5m以上、2_0m以下 3 2.0m以上、2.5m以下 4 2.5m以上、3.0m以下 5 3.0m以上、3.5m以下 6 3.5 m以上 7 處理5分鐘後的擴展狀態擴展前端回到處理地點爲止 0 從最長到達地點回到1 m以上 1 從最長到達地點回到1 m以下 2 從最長到達地點不回 3 滿分 15 如此所得本發明顯水面懸浮性之農藥粒劑，可原狀用手 或適當散粒機分撒於水田中，亦可分裝於具有水溶性的膜 或片製成的水溶紙 ，投入水田中處理，具有良好水面擴展 -28- 1283256 五、發明説明（27) 性之粒劑時，是投入水田中均勻處理，即使不用散粒機均 勻處理，只沿塍邊以所謂畫框處理，亦可使粒劑在水面自 然擴展，可得均勻處理的同樣效果。分裝於水溶紙時，若 粒劑不具有水面擴展性，水溶紙即使溶於水，內部粒劑會 不充分擴展，故以具有良好擴展性的粒劑爲宜。 水溶紙係由水溶性膜或片製成，具有在冷水中溶解或分 散，釋出內部粒劑的性質。其材料有聚乙烯醇（PVA)系， 諸如甲基纖維素鈉鹽之纖維素系，諸如聚環氧乙烷之聚醚 系，諸如黏稠性多糖之多糖物系等，本發明可用其中任一 種。凡此不止是常用宣紙或實施壓紋加工之膜，也包含由 此材料所得水溶性不織布製成之薄片。水溶性不織布不單 是水溶性不織布，還包含在水溶性不織布積層適當水溶性 膜所得積層材製成之片材。 此等材料當中，以膜本身具有擴展性的PVA尤佳。較 佳PVA聚合度1〇〇〇〜2000左右，皂化度85〜95%左右， 聚合物中有少量羧酸、磺酸等共聚合者，亦包含在內。 PVA聚合度太高時，若皂化度也太高，不易溶於冷水，故 不佳。爲改進PVA物理性或安定性，可含有通常PVA膜 所添加之可塑劑、安定性、色素等。 此等水溶性膜或片之厚度以20〜100// m爲佳。厚度在 20//m以下時，強度不足，容易破裂，用作包裝袋時，會 發生問題。而在100/z m以上時，在水中溶解很費時，且 價昂，故非良策。以30〜60//m爲宜，更好是35〜50//m。 爲顧及投擲容易，每包重量通常爲10〜200克，以20 -29. 1283256 五、發明説明（28 ) 〜100克爲佳’而以25〜70克更好。在此程度的重量，連 帶孺老幼都可輕易投擲到1 5公尺以內目標處。超此重量 時，投擲很辛苦，處理廣闊面積不易，在此以下時，受到 .風的影響，達不到目標處。 分裝形狀一般是一邊1〜30公分之長方形，或正方形， 惟不限於此，凡多角形、圓形、球形、圓筒形等均無妨。 分裝方法可在各邊用糊封閉，亦可使用超音波、高周波和 熱封等進行，就作業性而言，以熱封爲宜。 熱封方法可例如使用熱封機，比水溶紙熔點低20〜 150°C之溫度，以3〜lOOkg/cm線壓加以熱壓等方法。 本發明農藥粒劑在水面可以廣泛擴展，農藥有效成份擴 散亦可達廣範圍，通常即不必要水田投到過份遠，只要在 田邊投到2〜3公尺的前方水面即夠。 投於水田的分裝包數多，不但不能省力，且經濟上不利 。通常是每10公畝投下1〜30個，即可充分發揮生物效 果，而以每10公畝1〜20個爲佳。 所得固形劑分裝，是將紙袋、樹脂袋或貼鋁箔，亦可將 鋁或氧化矽蒸著之樹脂袋等袋或箱等外包裝，可防潮而長 時安定。因此，不必費心注意防潮，水溶紙溶入水中即破 ，故宜使用實施適當防水步驟之外包裝。 實施發明之最佳形熊 茲就實施例和試驗例詳述本發明，惟本發明不限於此等 實施例。 -30- 1283256 五、發明説明（29) 實施例1 以下列表2所示原料配方，於擠壓機進行高壓處理。所 得組成物性狀如表3所示。而表3中的油分離性以記號表 示，按油分離性良好順序，用◎、〇或X表示。 擠壓機（隋希隆EPM公司製品雙螺桿擠壓機^ 100)操作 條件，轉數：80〜160rpm，內徑與筒部比率l/D: 12，原料 投入量：40〜80kg/hr，壓力：30〜50kg/cm2，模孔徑：2.5mm (試料號碼4和12，1.5mjn)，串聯10孔，筒部溫度：8〇〜 90°C，模溫：80〜120°C。 表2 試料號碼 含澱粉物質 交聯劑 1(比較） 玉米渣（199) 赃 y\\\ 2 玉米渣（97) 三聚磷酸鈉 (3) 3 玉米渣（98) 三聚磷酸鈉（1) +三偏磷酸鈉（1) 4 大豆（98) 三聚磷酸鈉（1) +三偏磷酸鈉（1) () 表3 內表示混配量之質量份 試料號碼 體積比容發泡體外徑吸油倍數 水懸浮時間油分離性 比較） 80 20mm 0.1 1小時 X 2 9 7mm 1.5 6小時 ◎ 3 7 5mm 2.0 20小時 ◎ 4 6 3mm 2.5 22小時 ◎ 實施例2 採用實施例1同樣操作條件，按下述表4所示原料配方 -31- 1283256 五、發明説明（30 )Cx2 activity: Decomposes the cellodextrin produced by Cxl to produce glucose. In the present invention, when a hydrophobic pesticide composition having a suspension property on a water surface contains a proteinaceous natural substance or a derivative thereof, for example, a bacterial proteinase, a filamentous protease, a papain, and a peptinase are used. The bacterial protein enzyme is an enzyme produced by Bacillus subtilis, which is classified into a neutral protein enzyme and a basic protein enzyme according to its pH. It can be used to make bread, dry cleaning agents, household cleaning agents, etc. for proteins and peptides. The filamentous fungus protein enzyme has the origin of the genus Trichophyton, the origin of the genus Wine bacterium, the origin of the genus Streptomyces, and the nature varies according to the origin. Japan has been used in ancient times, soy sauce, soy sauce-14- 1283256 V. Invention description (13) Decompose soy egg quality. Most of the exogenous protein enzymes and endoprotein enzymes 'amylase content vary from strain to strain. Further, due to the strain, there are coexistence of cellulase, phospholipase, RNA enzyme, and pectinase. Papaya enzymes are made from papaya fruit and are used to prevent beer from becoming cloudy. In particular, a combination of a basic amino acid such as a peptide, a guanamine or an ester, leucine, a glycine, and the like is hydrolyzed as a raw material of semi-ripe papaya. The pepsin can hydrolyze peptide bonds adjacent to the aromatic or dicarboxylic acid-based L-amino acid residues. No effect on ester or guanamine. Very low pH at pH 1.8~2.5 can also work. In addition, as a proteolytic enzyme for anti-inflammatory drugs, there are trypsin, chymotrypsin, cytosolic, cyprodin, shark oil peptide, and pineapple enzyme. The granular pesticide composition having a suspension property on the surface of the present invention contains pectin when the pectin is contained. It can be used as a refining agent for hemp refining, fruit juice or wine. Pectin decomposing enzyme is a general term for a group of enzymes which can hydrolyze pectin substances, and includes pectinase, pectin esterase, pectin, pectin hydrating enzyme, polygalacturonase, pectinase and the like. Everything has an internal shape and an appearance. When the granular pesticide composition having a suspension property on the surface of the water contains a derivative such as alginic acid or a salt or an ester thereof, the enzymes acting on it include alginic acid enzyme and alginic acid lyase. Alginic acid enzyme is present in the digestive juice of abalone, snail, sea rabbit, and monk, and produces oligoaldehyde anilide, mannuronic acid, di- or trisaccharide aldehyde anilide. The alginic acid lyase is present in the genus Monospora, and the alginic acid can be decomposed by reactivity to form an oligosaccharide having a non-reducing end of uronic acid having an unsaturated bond. -15- 1283256 V. INSTRUCTION OF THE INVENTION (14) The granular pesticide composition having a suspension property on the surface of the water contains amylopectin, an amylopectin, and a branch when the viscous polysaccharide is contained. Amylase hydrolyzes the α-1,6 bonds of viscous polysaccharide starch pectin and animal starch glycogen to form linear polysaccharides such as maltotriose and sol starch. Endogenous action of viscous polysaccharides β-Amylopectinase hydrolyzes α-1,4 glucoside chains on the reducing end side adjacent to the more viscous α-1,6 glucoside chain to form iso 6-α - Glucose-based maltose. In the present invention, when a granular pesticide composition having a suspension property on a water surface contains a polysaccharide/polysaccharide polysaccharide, the enzyme which acts on it has a viluconic acid enzyme. The enzyme that acts on the natural high molecular substance or its derivative has no effect on the bond portion of the polymer chain, and can decompose any low molecular weight polymer (endotype), and the end bond of the polymer chain. The part has a function, and the constituent components can be separated one by one (outer shape). In this case, endogenous enzymes are preferred. The exogenous enzyme may also be used, but since it only acts on the end of the natural substance or its derivative, the disadvantage is that the decomposition of the natural substance or its derivative as a binding agent takes a little time (the disintegration and dispersion of the preparation takes time). In the present case, among the starch-containing substances and starches and the enzymes to be reacted, the preferred examples are starch-containing substances and starches, such as maize powder, corn slag, or wheat flour, and the enzyme is an internal type α-amylase. Or a combination of isoamylases, and more preferably a natural product or a derivative thereof is wheat flour, and the enzyme is a combination of endogenous alpha-amylase or isoamylase. The starch compounding amount varies greatly depending on the starch-containing substance and the starch-based substance and the compounding amount thereof, and the type and strength of the enzyme, but in the water-surface suspension-diffusing pesticide preparation of the present invention, it is usually 0.001 to 10 parts by mass to 0.002. ~5 parts by mass is -16-2834855. The invention description (15) is better, and more preferably 0.01 to 3 parts by mass. By adjusting the amount of enzyme mixture, the dissolution or disintegration time of the pesticide preparation in water can be adjusted. The granular pesticide composition of the present invention has a cylindrical shape and may be amorphous. When the active ingredient of the pesticide is solid, in order to exert biological activity, it is pulverized to a sufficient particle size. If necessary, other crushing aids, wetting agents, dispersing agents, etc. may be added. It is suitable to dry-pulverize with a hammer mill or a jet mill to form a premix containing high concentrations of pesticide active ingredients, and may also use a sand mill or a crucible. Mills, bead mills, etc. are wet pulverized. In the case of wet pulverization, if an oily substance is used as the medium, it can be absorbed as it is in the carrier of the present invention, but when water is used, it can be dried by a suitable dryer such as a spray dryer, or the like by a hammer mill or a jet mill. When pulverized, it can be treated in the same manner as the above dry premix. When the granule is produced, the foam of the present invention prepared in advance may be coated with a suitable non-volatile liquid substance to coat the active ingredient of the pesticide, or the active ingredient of the pesticide may be dissolved in a suitable solvent to be absorbed in the previously prepared foam of the present invention. And the standard suspension pesticide granules. When the coating method is used, for example, the previously prepared foam of the present invention is filled in a stirring mixer, a non-volatile liquid material is added, and after the surface is wetted, a pulverized product of a solid pesticide active ingredient is added, or, if necessary, A powder premix containing a surface extender or other auxiliaries is added and agitated to coat the surface of the granules. Non-volatile liquid substances can also be changed to liquid or liquid form pesticides. In the case of the absorption method, for example, the previously prepared foam of the present invention is filled in a stirring mixer, and a liquid or a liquidated pesticide such as a solvent is added. -17- 1283256 5. Inventive Note (16) Active ingredient, Or a thick oily premix that is absorbed. In the powder or oily premix of the active ingredient of the pesticide, the surface expansion agent may be mixed, and if necessary, other additives may be added. When the granules are prepared by the coating method or the absorption method, in order to maximize the effect of the surface expansion agent, it may be added after the coating or absorption of the active ingredient of the pesticide or other auxiliaries. Thus, the coating or absorption step can also be carried out in two or more stages. The mixing mixer used should preferably use a cement mixer, a Smith mixer, a tray, a Nauta mixer, a strip mixer, a rotary mixer, a V-type mixer, etc., to reduce the particle breakage at a low speed. Regarding the particle size of the granules, the small particle size is easy to submergence, and when used as a granule for spreading, it is susceptible to wind resistance. On the other hand, the particle size is mostly 20 mm or more. In addition to being easily blown by the wind, the dissolution time of the liquid active ingredient absorbed in the center portion is time consuming, and when the position is reached at the blowing position, the active ingredient of the pesticide is deviated. Usually, 90% or more enters the 0.71 mm to 15 mm area, and it is preferable to enter the area of 1 mm to 10 mm with 40% or more. In order to obtain the agrochemical granules having a good surface suspension spreadability according to the present invention, the active ingredients of the pesticide and the foam of the present invention, the surface expansion agent used in the expanded surface of the water surface, and other auxiliary agents can be compounded and prepared. The water surface extender of the present invention is prepared by mixing a pesticide excipient in a wide range of water surface, and a sodium salt or a potassium salt obtained by polymerizing a vinyl group or the like with a carboxylic acid such as acrylic acid or maleic acid or styrene sulfonic acid. a carboxylic acid or sulfonic acid type poly soap such as a salt or an ammonium salt; a soap such as sodium oleate or potassium stearate; a mono- or dialkyl sulfosuccinate; and a surfactant of the additional alkylene oxide , sodium dodecyl benzene sulfonate, alkyl sulfate, α-olefin sulfonate, α-sulfonic acid fatty acid-18- 1283256 V. Description of invention (17) Salt, α-olefin fatty acid salt, oleyl methyl cattle Anionic surfactant such as sulfonate; polyoxyethylene alkyl aryl ether, polyoxyethylene alkyl ether, polyoxyethylene aryl aryl ether, polyoxyethylene alkyl aryl ester, polyoxyethylene sorbitan ester, sorbose Various nonionic surfactants such as alkyl anhydrides of alcohol anhydrides, anthrone-based surfactants, acetylene-based surfactants, and pluronic-type surfactants; polyoxyethylene alkyl aryl ether, polyoxyethylene alkyl ether, polyoxyethylene aromatic Phosphate or sulfate such as aryl ether, polyoxyethylene alkyl ester, sorbitan alkyl ester, etc., as appropriate A surfactant which can be neutralized with a suitable base; a fluorine-based surfactant; various cationic surfactants; a zwitterionic surfactant; a glycol such as ethylene glycol, propylene glycol, butanediol, and a polymer thereof Ester and ether; mobile earthworm or naphthenic or aromatic high boiling point solvent; low viscosity polybutene, glazing oil, engine oil and other mineral oils; various animal and vegetable oils; rosin and other resins; camphor white α - Butene; camphor; naphthalene; hydrophobic ruthenium oxide, etc., preferably mono- or dialkyl succinate and the surfactant of the additional alkylene oxide, α-olefin sulfonate, α-sulfonate, Α-olefin fatty acid salt, oleyl methyl taurate, alkyl sulfate, acetylene surfactant, anthrone surfactant, fluorine surfactant, glycol ether or ester, and The alkyl ester of a carboxylic acid is more preferably an α-olefin sulfonate, an α-olefin fatty acid salt, an acetylene surfactant, or an ester of a glycol. Among such surface extenders, dispersing agents, binders, granulating enhancers or emulsifiers may be used. The mono- or dialkyl sulfosuccinate and the surfactant of the additional alkylene oxide are not only the dialkyl sulfosuccinates used in the pesticides, but also the monoalkyl sulfosuccinates. A polyalkylene oxide (C2 to C4), which is a salt obtained by reacting an alkyl ether with sulfosuccinic acid per molecule or two molecules. -19- 1283256 V. INSTRUCTIONS (18) Wherever there is Nuuk 29 1 PG (product of Japan Emulsifier Co., Ltd.), Niko SWCE, Nikok SWC, Nikok YSK (Products of First Industrial Pharmaceutical Company) ), Nuuk to EP-70G (product of Zhudong Oil Company), GERODON SOS (product of Yanyeyi Pharmaceutical Co., Ltd.), Beilix 〇Τ-Ρ (product of Kao Company), Yelong CT-1 (Dongbang Chemical Industry) Company products), give Napo SV1970J (Herster Japan company products), Limba 860K, Limba 870E (Lion company products), etc. (Dioctyl sulfosuccinate), BILLES TR (Kao company products ) (di(tridecyl) sulfosuccinate), Blix CS (product of Kao Corporation) (sodium dicyclohexyl sulfosuccinate), linbate (product of Lion Company) (tallowamide) Sodium sulfosuccinate), Nuoke 292PG (product of Japan Emulsifier Co., Ltd.) (sodium diethylhexyl ethoxy sulfosuccinate), ampoules ACR/4 (Rodidia Zironas products (sulfonate) The sodium salt of lauric ethoxy half-ester of diacid can be sold under the trade name. The α-olefin sulfonate is made from crude oil (petroleum). The salt of sulfonate has excellent biodegradability, is very stable to the skin and eyes, has stability to acid and alkali, is excellent in hard water resistance, and has such characteristics as human or environment, such as C12 to c16 α-olefin sulfonate. The salt of the α-olefin sulfonate is not particularly limited, and examples thereof include sodium, potassium, calcium, ammonium, and various amine salts, and sodium, ammonium or calcium salts are preferred. Specific examples of the α-olefin sulfonate include, for example, forests. Paula LB-490, Limpopa LB-840, Limpopa PJ-400, Yulin Pola PJ-400, Limpopo-800, Dt-95 (product of Lion King), Μ-3801, M -3801 G (product of the first industrial pharmaceutical company), live Starbucks OSB (Herster Japan company products), etc. α-sulfonated fatty acid salt is a sulfonate based on natural oils and fats, for example, -20- 1283256 (19) The α-sulfonated fatty acid salt of C10 to C14. The salt of the α-sulfonic acid fatty acid salt is, for example, sodium, potassium, calcium, ammonium, and various amine salts, but sodium, ammonium, Calcium salt is preferred. Specific examples of α·sulfonate fatty acid salts include, for example, FA-6513, FA-616B, and FA-617B (products of Lion King), Yamazaki, Yamatake FM-2 (product of Sakamoto Oil Co., Ltd.), etc. ^ - Olefin fatty acid salt carboxylic acid is obtained by reacting α-olefin, and there is, for example, a lauryl thiopropionic acid obtained by reacting α-olefin of Cu with 3-hydrothiopropionic acid. The salt is produced and sold by Nobastrol SA-66T and Nobsil SA-66TE (products of Nippon Oil & Fats Co., Ltd.). The oil-based methyl taurate oil is obtained by reacting chlorine with hydrazine-methyl taurine. The salt thereof is not particularly limited, and examples thereof include sodium, calcium, potassium, ammonium salts and the like, and sodium or calcium salts are preferred. Specific examples of the oleyl methyl taurate are, for example, Daisy's powder (product of Sakamoto Oil Co., Ltd.), Stark Τ Τ powder (Hirst Japan product), Akepu Τ powder (Hurst Japanese company products) and so on. The alkyl sulfates are, for example, lauryl sulfate, and are sold under the trade names of Yamal 10 powder (product of Kao Corporation) and Monogushi powder (product of Daiichi Kogyo Co., Ltd.). The acetylene surfactant comprises an acetylenic alcohol, an acetylenic diol, and a surfactant obtained from the additional oxane. The acetylenic alcohol is a compound of the formula HOCCRiKRi-C tri-CH (wherein R1 and R2 are the same or different and represents an alkyl group), R1 is a methyl group and R2 is an isopropyl group. The trademark is Semperol 61, and R1 and R2 are The methyl group has ouaba B, R1 is a methyl group and R2 is an ethyl group. -21- 1283256 V. Description of the invention (2G). The acetylene glycol is a compound of the formula ΗΟΟ^Ι^ΚΙΙ^ΤΞΟ-^ΐΐΐ^ΟΗβ1 and R2 which are the same or different and represent an alkyl group, and R1 is a methyl group and R2 For isobutyl group, there is Safrano 82, R1 is methyl and R2 is isobutyl. There is Safran 104, R1 is ethyl and R2 is butyl. Safranol DF110, R1 and R2 are all A. The base has a commercial product of Safran gamma trademark. Further, as the surfactant for adding an alkylene oxide to the above alkynol or acetylene glycol, for example, the above-mentioned alkynol or acetylene glycol may be added with a surfactant such as ethylene oxide and/or propylene oxide. Additional alkylene oxides are commercially available, for example, from Safran 104 with ethylene oxide, and are commercially available under the trademark Safran 400 series. In addition, selenon 1 〇 4 (wax) and amorphous yttrium oxide are mixed in a weight ratio of 40:60 to pulverize the powder premix, which has Safran 104S, and Safran DF 110 (wax) and The amorphous form of cerium oxide is mixed at a ratio of 40:60 to the pulverized powdery premix, which is commercially available from Safranol DF 11 0S (all products of the company, sold by Nisshin Chemical Co., Ltd.). The polyoxo-based surfactant is a methyl group at the end of the methyl or dimethyl polyoxyalkylene and/or a side chain, and is introduced into ethylene oxide or polypropylene oxide, or both, as the case may be. A nonionic surfactant mainly composed of a polyether-modified polyfluorene-oxygen oil, which is etherified or esterified with an alkyl group as an alkyl group, and is, for example, a Xijiaduo series (Tao Kanging Poly Oxygen Co., Ltd.) , Xijiaduo series (products of Sakamoto Yonica), polyoxygenated oil KF series (products of Shin-Etsu Chemical Co., Ltd.), and trademarks of Chinizik (products of Heibang Chemical Co., Ltd.) are commercially available. The fluorine-based surfactant is usually a part or all of the hydrogen atom of an anionic, nonionic, cationic or two-ionic surfactant, in the form of fluorine ____-22-1283256. 5. Description of the invention (21) / The surfactant is known to be substituted by an atom, and it is known that the surface tension reducing power is excellent, for example, in the Yonikoy series (product of Kujic Industrial Co., Ltd.), the Mijiadike series (product of Dainippon Ink Chemical Industry Co., Ltd.), Trademarks such as the appropriate series (products of the company), the Sailong series (products of Asahi Glass Co., Ltd.), and the products of Aachento (products of Tojiu Products) are commercially available. The glycol ethers and esters may have one or both of ethylene glycol, propylene glycol, butylene glycol, and terminal hydroxyl groups thereof, and specific examples thereof include hexanediol ((HeG, ethylene glycol monohexyl ether, Japanese emulsifier). Company), hexane diethylene glycol (HeDG, diethylene glycol monohexyl ether, Japan emulsifier company), 2-ethyl hexane diol (EHG, ethylene glycol mono 2-ethylhexyl ether, Japan emulsifier company) 2-Ethylhexanediethylene glycol (EHDG, diethylene glycol mono-2-ethylhexyl ether, sputum emulsifier company), etc., is commercially available under the trade name. Carboxylic acid alkyl esters include coconut oil fatty acid, lauric acid, and oil. a carboxylic acid such as an acid or a lactic acid, or a methyl ester, an ethyl ester, a propyl ester or a butyl ester of a polycarboxylic acid such as maleic acid, citric acid, fumaric acid, adipic acid, glutaric acid or phthalic acid. , hexyl ester, ethyl hexyl ester, lauryl ester, oil ester and other alkyl esters, specific examples are Aksip MC (coconut fatty acid methyl ester, Kao company), Yaxipu M-OL (methyl oleate, Kao Corporation), Binishisa 30 (Isobutyl oleate, Kao Company), Binishisa 124 (dialkyl phthalate, Kao Corporation), butyl lactate (Musashino Chemical 硏The trademark is commercially available, etc. The blending amount of the water surface extender according to the present invention is based on the type and content of the active ingredient of the pesticide, the type of the surface extender and the method of adding the same, the type of the other ingredients, and the formulation amount or the dosage form of the compounding amount. The difference is usually 0.1 to 30% in the solid agent of the pesticide, preferably 0.3 to 20%, and more preferably 0.5 to 10%. -23- 1283256 5. Invention Description (22) The pesticide solid agent of the present invention can be compounded Non-volatile liquid substances, emulsifiers, dispersants, wetting agents, thinners, water repellents, particle growth inhibitors, and other stabilizers for stabilizers. Solid, semi-solid or liquid pesticide active ingredients at room temperature, In order to be diluted so as to be soaked in the coating, a non-volatile liquid substance may be used if necessary. The non-volatile liquid substance should have no adverse effect on the growth and decomposition of the active ingredient of the pesticide, and can uniformly coat and saturate the active ingredient of the pesticide. The properties of the foam of the present invention are preferably high boiling point, low toxicity, high ignition point, low viscosity, and specific gravity less than 1. Generally, the specific gravity of the active ingredient of the pesticide is mostly above 1. Under the circumstance, the emulsifying property should be kept in the water for as long as possible. In order to spread it widely in the paddy field, most of the low-viscosity solvents with a specific gravity lower than 1. For example, low-viscosity mobile paraffin, isolith, motor oil, polybutene, paraffin hydrocarbon Mineral oils such as various high-boiling solvents such as naphthenic and aromatic systems; vegetable oils such as coconut oil, soybean oil, and rapeseed oil; animal oils such as whale oil and sardine oil; polyoxygenated oils and their derivatives; oleic acid and lactic acid , mono- or polycarboxylic acids such as coconut oil fatty acid, maleic acid, fumaric acid, phthalic acid, adipic acid, and various esters thereof; various phosphate esters such as tributyl phosphate or trichloroethyl phosphate Plasticizer; ε-caprolactone, 7-butyrolactone and other lactones; N-methyltetrahydro-clavone; and various liquid surfactants, preferably with low viscosity mobile sarcophagus, engine oil , different kinds of esters or various esters, specific examples include super oil series, Smith series (products of Japan Petrochemical Company), mobile stone 蠘 No series (centralized company products) and other mobile sarcophagus; Ruixiang Ning oil series (Yuguangxing Company products) and other oils; Esop series Iso sol series (said present Petrochemical products), iso-paraffin and the like, the above-described two or more kinds may be mixed to use. -24- 1283256 V. INSTRUCTIONS (23) The amount of non-volatile liquid substance used in the present invention varies depending on the type of active ingredient of the pesticide or the type of other auxiliary agent, the amount of the compound, etc., but in the case of the pesticide solidifying agent The long-term stability or physicality does not affect the situation, the less the better. The compounding amount is generally from 1 to 60%, preferably from 2 to 50%, and more preferably from 3 to 40%. The emulsifier used in the present invention is required to emulsify the liquid pesticide active ingredient or the pesticide active ingredient solution in water, and the emulsifier of the usual emulsion may be selected and used as the active ingredient or solvent of the pesticide. The amount of the emulsifier used in the present invention is generally from 1 to 30%, preferably from 0.03 to 15%. The dispersant used in the present invention is used for suspending and dispersing the active ingredient of the pesticide in water, such as lignosulfonate, (alkyl) naphthalenesulfonate and its condensate, phenolsulfonate and its condensate, styrenesulfonic acid. a salt condensate, a salt of a condensate of maleic acid and styrenesulfonic acid, a salt of a carboxylic acid condensate such as acrylic acid or maleic acid, an alkylbenzenesulfonate, a lauryl sulfate, a polyoxyethylene oxide. Anionic surfactants such as aryl ether sulfates, polyoxyethylene alkyl ether phosphates and salts thereof, polyoxyethylene alkyl aryl ether phosphates and salts thereof, or phosphates such as sodium tripolyphosphate and sodium hexametaphosphate. Further, a nonionic, cationic or zwitterionic surfactant may be appropriately selected and used. Most of these dispersants can be used as wetting agents. The compounding amount of the dispersing agent and the wetting agent used in the present invention is generally 0.01 to 30%, preferably 〇1 to 20%, more preferably 0.2 to 15%. The diluent used in the present invention is a diluent for preparing a premix of a solid pesticide active ingredient, such as bentonite, slip powder, clay, diatomaceous earth, amorphous-25-1283256, and invention description (24) Mineral powder such as cerium oxide, calcium carbonate, magnesium carbonate or the like used as a general pesticide carrier, and various resin powders such as vinyl chloride, vinyl chloride, polyethylene, and polypropylene, sugars such as glucose, sugar, and lactose, starch and Its derivatives, microcrystalline cellulose, wood flour, sawdust, rice bran, wheat bran, rough meal, coffee bean powder, coconut shell powder, activated carbon, cellulose powder, licorice powder and other organic substances, sodium sulfate, ammonium sulfate, chlorine Water-soluble inorganic salts such as potassium and urea. The blending amount of the extender used in the present invention is generally 0.1 to 80%, preferably 0.2 to 50%, more preferably 0.5 to 20%. When the water-repellent agent used in the invention has high water solubility of the active ingredient of the main pesticide, the dissolution of the active ingredient of the pesticide can be inhibited, and after the water surface is widely dispersed as much as possible, it is mixed in water to be mixed, such as magnesium stearate and hard. Fatty acid salts such as calcium citrate, higher alcohols such as stearyl alcohol, higher fatty acids such as stearic acid, polyoxygenated oils and their derivatives, fluorine-based surfactants, cationic surfactants, hydrophobic cerium oxide, and mobile paraffin Motor oil, etc. The mixing amount of the water repellent used in the present invention varies depending on the type or physical property of the active ingredient of the pesticide, and the compounding amount thereof is generally 0.05 to 10%, preferably 0.1 to 5%. The particle growth preventing agent or stabilizer used in the present invention may be compounded in accordance with the necessity of the effective ingredient properties of the pesticide. In addition, if necessary, it is possible to mix pigments, bittering agents, and other various supplements. In order to disperse, emulsify, and dissolve the active ingredient of the pesticide in water quickly after spreading on the water surface, the pesticide granule of the present invention needs to adjust the compounding amount of the wetting agent, the dispersing agent, the emulsifier, and the like. The thus obtained pesticide granules of the present invention preferably exhibit expandability by using the following method -26 - 1283256 V. Invention Description (25) Index 5 to distinguish the good surface suspension expandability. The "Expansion Index" is a spread of a water-based suspension-extending pesticide solidifying agent on the surface of the water. It is counted in a range of 〇15 to 15 (15 points). The larger the score, the better the water surface expandability. More than 5 points is appropriate, 7 points or more is better, and more than 9 points is especially good. The water surface expansion test method is as follows: a tank measuring 4 meters long and 14 centimeters wide, holding 25 liters of tap water, and adjusting the water temperature to 2 (TC. Assume that the obstacles on the four sides of the water (suspension) will be Smissikang ( Stored in the product of gold products, coarse powder) 2 g treated to be even on the water surface. After standing, take 280 mg of pesticide solidifying agent, put it from the end of the pot 10 cm, and visually investigate from the input of each pesticide solid agent. The arrival time of 1_5 meters, the longest arrival distance from the input location, and the extended state after 5 minutes of input, the benchmarks listed in Table 1 are judged, and the scores are aggregated to obtain the scalability index separately. -27- 1283256 (Notes) (26) Table 1 Extensibility scoring items and scoring benchmark scoring items Judging criteria score 1.5m arrival time 2 points or more 0 1 point or more, 2 points or less 1130 seconds or more, 1 minute or less 2 2 0 seconds or more, 30 seconds or less 3 10 seconds or more, 20 seconds or less 4 1 0 seconds or less 5 longest reach ------- 0.5 m or less 0 0_5 m or more, 1.0 m or less 1 1.0 m or more, 1.5 m or less 2 1 _5 m or more , 2_0m or less 3 2 .0m or more, 2.5m or less, 42.5m or more, 3.0m or less, 53.0m or more, 3.5m or less, 63.5m or more, 7 extended state extended after 5 minutes, and the front end returns to the processing point. 0 returns from the longest arrival point to 1 m or more 1 returns from the longest arrival point to 1 m or less 2 from the longest arrival point does not return 3 out of 15 The thus obtained hydrolyzed suspension granules of the present invention can be sprinkled in paddy fields by hand or by appropriate granules. It can also be dispensed into water-soluble paper made of water-soluble film or sheet, and put into the paddy field for treatment. It has a good water surface expansion -28-1283256. 5. When the granules of the invention (27) are used, it is uniformly treated in the paddy field. Even if it is not treated evenly by the pelletizer, it can be treated with the so-called picture frame along the edge of the crucible, so that the granules can naturally spread on the water surface, and the same effect of uniform treatment can be obtained. When the water-soluble paper is dispensed, if the granules do not have a water surface Expandability, even if the water-soluble paper is soluble in water, the internal granules will not expand sufficiently, so it is preferable to use a granule with good expandability. The water-soluble paper is made of a water-soluble film or sheet and has a solubility in cold water or Dispersing, releasing the properties of internal granules. The material is polyvinyl alcohol (PVA), cellulose such as methyl cellulose sodium, polyether such as polyethylene oxide, polysaccharide such as viscous polysaccharide Any one of the inventions can be used in the present invention. Any of these is not only a commonly used rice paper or a film for embossing, but also a sheet made of a water-soluble non-woven fabric obtained from the material. The water-soluble non-woven fabric is not only a water-soluble non-woven fabric, but also includes A sheet made of a laminate obtained by laminating a water-soluble non-woven fabric of a suitable water-soluble film. Among these materials, PVA which is extensible in the film itself is particularly preferable. Preferably, the PVA has a polymerization degree of about 1 to about 2,000, a degree of saponification of about 85 to 95%, and a small amount of a copolymer of a carboxylic acid or a sulfonic acid in the polymer is also included. When the degree of polymerization of PVA is too high, if the degree of saponification is too high, it is not easily dissolved in cold water, which is not preferable. In order to improve the physical properties or stability of the PVA, it may contain a plasticizer, stability, pigment, or the like which is usually added to the PVA film. The thickness of such water-soluble films or sheets is preferably from 20 to 100 / / m. When the thickness is 20/m or less, the strength is insufficient and it is easily broken. When used as a packaging bag, problems occur. When it is above 100/z m, it is time-consuming to dissolve in water, and it is expensive, so it is not a good strategy. It is preferably 30 to 60//m, more preferably 35 to 50//m. In order to take into account the easy to throw, the weight of each package is usually 10 ~ 200 grams, to 20 -29. 1283256 five, the invention description (28) ~ 100 grams is better 'and better than 25 ~ 70 grams. At this level of weight, even young and old can easily throw targets within 15 meters. When this weight is exceeded, the throwing is very difficult, and it is not easy to handle a wide area. When it is below, it is affected by the wind and cannot reach the target. The split shape is generally a rectangle of 1 to 30 cm on one side, or a square, but is not limited thereto, and any polygon, circle, sphere, or cylindrical shape may be used. The dispensing method can be closed with paste on each side, and can also be performed by using ultrasonic waves, high frequency, heat sealing, etc., and heat sealing is preferable in terms of workability. The heat sealing method can be carried out, for example, by using a heat sealer, at a temperature lower than the melting point of the water-soluble paper by 20 to 150 ° C, by hot pressing at a linear pressure of 3 to 100 kg/cm. The pesticide granules of the invention can be widely expanded on the water surface, and the active ingredient of the pesticide can be spread to a wide range. Usually, it is not necessary to cast the rice field too far, as long as the front water surface of 2 to 3 meters is thrown at the side of the field. The number of sub-packages invested in paddy fields is not only labor-saving, but also economically unfavorable. It is usually 1 to 30 per 10 acres, and the biological effect can be fully utilized, and 1 to 20 per 10 acres is preferred. The obtained solid preparation agent is packaged in a paper bag, a resin bag or an aluminum foil, or a bag or a box such as a resin bag in which aluminum or ruthenium oxide is evaporated, and is moisture-proof and stable for a long period of time. Therefore, it is not necessary to pay attention to moisture proof, and the water-soluble paper is broken when dissolved in water, so it is preferable to use a package that is properly waterproofed. BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail with respect to examples and test examples, but the invention is not limited to the examples. -30- 1283256 V. INSTRUCTION DESCRIPTION (29) Example 1 The raw material formulation shown in the following Table 2 was subjected to high pressure treatment in an extruder. The properties of the obtained composition are shown in Table 3. On the other hand, the oil separation property in Table 3 is indicated by a symbol, and is represented by ◎, 〇 or X in the order of good oil separation. Extrusion machine (隋希隆 EPM company twin-screw extruder ^ 100) operating conditions, number of revolutions: 80~160rpm, inner diameter and barrel ratio l/D: 12, raw material input: 40~80kg/hr, pressure: 30~50kg/cm2, mold aperture: 2.5mm (sample number 4 and 12, 1.5mjn), 10 holes in series, barrel temperature: 8〇~ 90°C, mold temperature: 80~120°C. Table 2 Sample No. Starch Substrate Crosslinker 1 (Comparative) Corn Slag (199) 赃y\\\ 2 Corn Slag (97) Sodium Tripolyphosphate (3) 3 Corn Slag (98) Sodium Tripolyphosphate (1) + sodium trimetaphosphate (1) 4 soybean (98) sodium tripolyphosphate (1) + sodium trimetaphosphate (1) () Table 3 shows the mass of the compounded amount of the sample number volume specific volume foam outer diameter oil absorption Comparison of oil separation time in multiple water suspension time) 80 20mm 0.1 1 hour X 2 9 7mm 1.5 6 hours ◎ 3 7 5mm 2.0 20 hours ◎ 4 6 3mm 2.5 22 hours ◎ Example 2 Using the same operating conditions as in Example 1, the following Table 4 shows the raw material formula -31- 1283256 V. Description of the invention (30)

，於擠壓機進行高壓處理。所得組成物性狀如表5所示。 表4 試料 號碼 澱粉類 含澱粉 物質 脂質 乳化劑 熱凝固劑 交聯劑 5 玉蜀黍（100) 0 0 0 0 0 (比較） 6 氧化澱粉（1〇〇) 0 0 0 0 0 (比較） 7 氧化澱粉（82) 0 椰子油 蔗糖脂肪 大豆蛋白 三聚磷酸 (1) 酸酯（1) (10) 鈉（5) 8 氧化澱粉（50) 玉米渣 揶子油 蔗糠脂肪 大豆蛋白 三聚磷酸 (42.5) (1) 酸酯（0.5) (3) 鈉（3) 9 羥丙基 0 0 0 0 三偏磷酸 (比較）化澱粉（97) 鈉（3) 10 羥丙基 0 0 0 麩質 三偏磷酸 化澱粉（87) (1〇) 鈉（3) 11 羥丙基 0 白絞油 甘油脂肪 麩質 三偏磷酸 化澱粉（82) (4) 酸酯（1) (10) 鈉（3) 12 羥丙基 大豆 凡士林 甘油脂肪 麩質 三偏磷酸 化澱粉（50) (40.5) (1) 酸酯（0.5) (3) 鈉（3) ()表示混配量之質量份 -32- 1283256 五、發明説明（31 ) 表5 試料號碼 體積比容 發泡體外徑 吸油倍數 水懸浮時間 油分離性 5(比較） 110 20mm 0.1 30分鐘 〇 6(比較） 120 30mm 0.2 10分鐘 〇 7 8 5mm 1.3 12小時 ◎ 8 5 5mm 2.0 15小時 ◎ 9(比較） 130 3 5mm 0.1 5分鐘 X 10 10 8mm 0.3 1小時 〇 1 I 7 8mm 0.6 5小時 〇 12 5 3mm 2.0 1 5小時 ◎ 實施例3 取丁基拉草原體（a.i.90%)43.75份，EHDG(二乙二醇單 2-乙基己醚，曰本乳化劑公司製品）3.00份，NE-2609(聚 氧乙烯多環苯醚，日本乳化劑公司製品）1.50份，及DBC( 十二烷基苯磺酸鈣70%，日本乳化劑公司製品）1.50份， 加以混合，得油預混物。另外取亞朵索拂隆原體 (a.i.98.8%)0.95份，隆非普439(珠岩，三井金屬礦業公司 製品）7.90份，以及M-3 801G(a -烯烴磺酸鈉，第一工業 製藥公司製品）0.50份，加以混合，利用鎚磨機粉碎，得 粉末預混物。取實施例2試料號碼8的發泡體38.40份’ 充塡入諾塔混合機，加油預混物49.75份，經混合、吸收 後，加粉末預混物9.35份，混合被覆，再加2.50份的隆 非普439，混合被覆，得含丁基拉草37.5 0%和亞朵索拂隆 0.85%之本發明農藥粒劑。所得粒劑40克分裝於海西隆 -33- 1283256 五、發明説明（32 ) C-200(厚40/z m之PVA膜，日合膜公司製品），得本發明 水田投擲用製劑，本製劑是水田每1 0公畝按5包比例投 擲施用。 實施例4 將丁基拉草原體43.75份和EHDG3.00份混合，得油預 混物。另取亞朵索拂隆原體0.95份，隆非普43 9爲6.40 份，彼尼克斯N(木質素磺酸鈉，日本製紙公司製品）1.〇〇 份和GEROPON SDS(二辛基磺丁二酸鈉，鹽野義製藥公司 製品）1·〇〇份，加以混合，利用鎚磨機粉碎，得粉末預混 物。取實施例2的試料號碼7之發泡體41.40份，充塡於 諾塔混合機，加油預混物46.75份，經混合、吸收後，加 粉末預混物9.35份，混合被覆，再加隆非普439爲2.50 份，混合被覆，得含丁基拉草37.50%和亞朵索拂隆0.85% 之本發明農藥粒劑。所得粒劑40克分裝於海西隆C-200， 得本發明水田投擲用製劑。本製劑係按每10公畝水田5 包的比例投擲施用。 實施例5 取丁基拉草原體 29.17 份，EHDG3.00 份，NE-2609 1.50 份，DBC1.50份混合，得油預混物。另取亞朵索拂隆原體 0.64份，隆非普439爲5.26份，M-3 801 G0.33份混合， 利用鎚磨機粉碎，得粉末預混物。取實施例1的試料號碼 2之發泡體54.60份，充塡於諾塔混合機，加油預混物 35.17份，經混合、吸收後，加粉末預混物6.23份，混合 被覆，再加隆非普4.00份，混合被覆，得含丁基拉草 -34- 1283256 五、發明説明（33 ) 25.00%，亞朵索拂隆0.5 7%，得本發明農藥粒劑。本製劑 按每10公畝水田300克的比例，從塍邊等撒佈施用。 實施例6 發泡載體之製造 按下列表6所示原料配方，使用雙螺桿擠壓機製造製造 發泡載體。所得發泡載體之物理性如表7所示。 擠壓機（隋希隆EPM公司製雙螺桿擠壓機α 100)操作條 件：轉數80〜160rpm，內徑與筒部比率L/D:12，原料投入 量40〜8 0kg/hr，壓力30〜50kg/cm2，模孔徑1.5mm，串 聯10孔，筒部溫度80〜90°C，模溫80〜12〇t。 表6 _發泡載體之處方 E料號碼天然物或其衍生物 交聯劑 ' ^ 薄力粉（98) 三偏磷酸 2 "玉米渣（& 三偏磷酸 3 氧化澱粉（5〇) +玉米粉（3 8)三聚磷酸鈉（3) +麩質（3) +四隆奇Ep*(5) +椰子油（1) *羧甲基纖維鈉鹽、第一麩質工業製藥公司製品 ()內表示混配量之質量份。 表7 _發-泡載體之物理性 試料號碼 體積比容 發泡體外徑 吸油倍數水懸浮時間 水中崩解性 1 11 3mm 1.5 20小時 不崩解 2 9 5mm 1.5 6小時 不崩解 3 7 3mm 1.8 18小時 不崩解 -35- 1283256 五、發明説明（34) 實施例7 含薄力粉和α -澱粉酵素之農藥粒劑及水田投擲用製劑 取丁基拉草原體（a.i.90%)43.75份，EHDG(二乙二醇單 2-乙基己醚，日本乳化劑公司製品）3.〇〇份，NE-2609(聚 氧乙烯多環苯醚，日本乳化劑公司製品）0.50份，DBC(十 二烷基苯磺酸鈣70%，日本乳化劑公司製品）〇·50份，表 夸伊斯塔傑Μ8(α -澱粉酵素，大和化成公司製品）0.2〇份 ，加以混合，得油預混物。另取亞朵索拂隆原體 (a.i.98.8%)0.95份，隆非普439(粉狀珠岩，三井金屬礦業 公司製品）5.40份，巴列克斯（木質素磺酸鈉，日本製紙公 司製品）1.00份，GEROPON SDS(二辛基丁二酸鈉，鹽野 義製藥公司）2.00份，加以混合，利用鎚磨機粉碎，而得 粉末預混物。 取實施例6試料號碼1之發泡體40.20份，充塡於諾塔 混合機內，加油預混物47.95份，經混合、吸收後，加粉 末預混物9.35份，混合被覆，再加隆非普43 9爲2.50份 ，混合被覆，得含丁基拉草37.50%和亞朵索拂隆0.85%之 本發明農藥粒劑。所得粒劑40克分裝於海西隆C-200(厚 40 // m的PVA膜，日合膜公司製品），得本發明水田投擲 用製劑。本製劑按水田每10公畝5包的比例投擲施用。 實施例8 含玉米渣和X-澱粉酵素之農藥製劑及水田投擲用製劑 在實施例7內，除實施例6試驗號碼1之發泡載體改用 實施例6試料號碼2之發泡載體外，和實施例1同樣，製 -36- 1283256 五、發明説明（35 ) 得含丁基拉草37.50%和亞朵索拂隆0.85%之本發明農藥製 劑。所得製劑40克分裝於海西隆C-200，得本發明水田投 擲用製劑。本製劑按水田每1 0公畝5包的比例投擲施用。 實施例9 盒薄力粉、α -澱粉酵素和蛋白酵素之農藥製劑及水田投 擲用製劑 在實施例7內，除表夸伊斯塔傑Μ8 0.20份改爲表夸伊 斯塔傑Μ8 0.10份和普隆奇AS 10(蛋白酵素，大和化成公 司製品）0.10份外，和實施例7同樣，製得含丁基拉草 37.50%和亞朵索拂隆0.85%之本發明農藥製劑。所得製劑 40克分裝於海西隆C-200，得本發明水田投擲用製劑。本 製劑按水田每1 〇公畝5包的比例投擲施用。 實施例10 含氧化酵素、玉米粉、西隆靜^、α -澱粉酵泰和纖維素酵 素之農藥製劑，以及水田投擲用製劑 在實施例7內，除表夸伊斯塔傑Μ8 0.20份改爲表夸伊 斯塔傑Μ8 0.10份和西隆濟（纖維素酵素，阪急生物工業 公司製品）〇· 10份外，且實施例6試料號碼1之發泡載體 改爲實施例6試料號碼1之發泡載體外，和實施例7同樣 ，得含丁基拉草37.50%和亞朵索拂隆0.85%之本發明農藥 製劑。所得製劑40克分裝於海西隆C-200，得本發明水田 投擲用製劑。本製劑按水田每1 〇公畝5包的比例投擲施 用。 試驗例1 -37- 1283256 五、發明説明（36 ) 果如表8所示。如表8所示，本發明水面懸浮性粒劑投入 水中後約24小時懸浮水面，然後徐徐沉沒，48小時後， 粒劑幾已沉降，又，此等粒劑擴展性指數亦高，可見到在 水面擴展良好。此等實施例之粒劑剛投入水中時不會沉沒 ’且顯示良好擴展性。 表8 复施例粒劑之懸浮件和擄展件指數 試驗粒劑 水面懸浮性 擴展性指數 實施例3 24小時後無沉降粒劑 然後開始徐沉降 48小時後粒劑幾乎都沉降 24小時後無沉降粒劑 11 實施例4 48小時後粒劑幾乎都沉降 24小時後無沉降粒劑 10 實施例5 48小時後粒劑幾乎都沉降 12 試驗例2 溶出試驗 在室溫20°C條件下，把1〇公升常水裝入內部尺寸爲橫 6〇公分X縱34公分X高10公分（面積2040平方公分）的塑 膠容器（水深約5公分），水溫調至20°C。試料正確秤量約 4〇毫克（實施例3和4)和約60毫克（實施例5)，在中心部 處理。處理24小時後，如第1圖所示在容器對角線上的 三點對水取樣，同時全部回收沉降水中或懸浮水面的粒劑 。以高速液體層析，分析水中有效成份濃度和粒劑中有效 成份，求出有效成分的水中溶出率及粒劑中有效成份殘餘 率。結果如表9所示。實施例3〜5之任何樣品均顯示在 -38- 1283256 五、發明説明（37 ) 處理1日後的亞朵索拂隆和丁基拉草合計大約100%之溶 出率，粒劑中則幾未見有效成份殘留。 表9 溶出試驗結果 試驗粒劑 亞朵索拂隆 丁基拉草 水中濃度（ppm) n = 3 平均 水中溶 出（％) 粒劑中殘 留率（％) 水中濃度（ppn) n = 3 平均 水中溶 出（％) 粒劑中殘 留率（％) 實施例3 0.03 1.40 0.03 1.45 0.03 0.03 100 0 1.44 1.43 95 1 實施例4 0.03 1.32 0.03 1.44 0.03 0.03 100 0 1.42 1.39 93 2 實施例5 0.03 1.44 0.03 1.36 0.03 0.03 100 0 1.3 9 1.40 93 4 水中濃度理論値爲亞朵索拂隆：0.03ppm及丁基拉草：l.50ppm。 試驗例3 崩解件試驗 在室溫20°C條件下’於500毫升容量的燒杯裝500毫 升的3度硬水，水溫調至20°C。在燒杯內放入實施例7〜 10之農藥製劑和實施例6試料號碼丨〜3之發泡載體各三 粒，觀察粒之崩解時間。結果如表1所示。 •39- 1283256 五、發明説明（38) 表10 崩解件試驗 號碼 試驗製劑磲@體 水中崩解時間 1 貫施例7之農藥製劑 20分鑊 2 實施例8之農藥製劑 30分鏤 3 貫施例9之農藥製劑 15分鑊 4 實施例1 0之農藥製劑 10分鐘 5 實施例6試料號碼1之發泡載體 未崩解 6 實施例6轼料號碼2之發泡載體 未崩解 7 實施例6試料號碼3之發泡載體 未崩解 實施例ό的發泡載體均未崩解，含有此等發泡載體和酵 素的實施例7〜10農藥製劑，都在處理3〇分鐘內崩解。 產業上利用價値 根據本發明可得懸浮水面，極富吸油能力之發泡體。此 等發泡體可例如用作水田投擲劑或水田撒佈用農藥載體， 因含有高濃度液狀原體，水田處理藥量可以大減。此等技 術隨著農家人口高齡化，要求省力化，對最近農業需求大 有貢獻。 圖式簡單說明 第1圖表示試驗例2之試料處理位置和水取樣位置。 -40-, high pressure treatment in the extruder. The properties of the obtained composition are shown in Table 5. Table 4 Sample number Starch starch-containing substance Lipid emulsifier Thermal coagulant Crosslinker 5 Hosta (100) 0 0 0 0 0 (Comparative) 6 Oxidized starch (1〇〇) 0 0 0 0 0 (Comparative) 7 Oxidized starch (82) 0 Coconut oil sucrose fat soy protein tripolyphosphate (1) acid ester (1) (10) sodium (5) 8 oxidized starch (50) corn scorpion scorpion oil cane scorpion fat soy protein tripolyphosphate (42.5) (1) Acidate (0.5) (3) Sodium (3) 9 Hydroxypropyl 0 0 0 0 Trimetaphosphoric acid (Comparative) Starch (97) Sodium (3) 10 Hydroxypropyl 0 0 0 Gluten Trimetaphosphate Starch (87) (1〇) Sodium (3) 11 Hydroxypropyl 0 White Gynose Glycerin Fat Gluten Tri-phosphorylated Starch (82) (4) Acidate (1) (10) Sodium (3) 12 Hydroxyl Propyl Soybean Vaseline Glycerol Fat Gluten Tri-phosphorylated Starch (50) (40.5) (1) Acidate (0.5) (3) Sodium (3) () means the mass of the compounded amount - 32 - 1283256 V. Invention Description (31) Table 5 Sample number Volume specific volume Foam outer diameter Oil absorption multiple Water suspension time Oil separation 5 (Comparative) 110 20mm 0.1 30 minutes 〇 6 ( Comparative) 120 30mm 0.2 10 minutes 〇 7 8 5mm 1.3 12 hours ◎ 8 5 5mm 2.0 15 hours ◎ 9 (comparative) 130 3 5mm 0.1 5 minutes X 10 10 8mm 0.3 1 hour 〇 1 I 7 8mm 0.6 5 hours 〇 12 5 3mm 2.0 1 5 hours ◎ Example 3 Take 43.75 parts of butyl pull grassland (ai90%), 3.00 parts of EHDG (diethylene glycol mono 2-ethylhexyl ether, emulsifier company), NE-2609 (polyoxyethylene polycyclic phenyl ether, manufactured by Japan Emulsifier Co., Ltd.) 1.50 parts, and 1.50 parts of DBC (calcium dodecylbenzenesulfonate 70%, manufactured by Nippon Emulsifier Co., Ltd.), and mixed to obtain an oil premix. In addition, 0.95 parts of Azotosol protoplast (ai 98.8%), 7.90 parts of Longfeipu 439 (Zhuyan, Mitsui Metal Mining Co., Ltd.), and M-3 801G (sodium a-olefin sulfonate, first industry) 0.50 parts of the pharmaceutical company's product, mixed, and pulverized by a hammer mill to obtain a powder premix. Take 38.40 parts of the foam of sample No. 8 in Example 2, fill the Nouta mixer, and add 49.75 parts of the premix. After mixing and absorbing, add 9.35 parts of the powder premix, mix and cover, and add 2.50 parts. The amphetamine 439 was mixed and coated to obtain a pesticide granule of the present invention containing 37.5% of butyl oxalate and 0.85% of oxidoxone. 40 g of the obtained granules were placed in Haixilong-33- 1283256. 5. Description of the invention (32) C-200 (PVA film of 40/zm thick, product of Nippon Film Co., Ltd.), and the preparation for paddy field throwing of the present invention, The preparation is applied in a paddy field at a ratio of 5 packs per 10 hectares. Example 4 43.75 parts of butyl lagras and 3.00 parts of EHDG were mixed to obtain an oil premix. Another 0.95 parts of the original Solon tomogen, and Longfol 43 9 was 6.40 parts, Penny N (sodium lignosulfonate, manufactured by Nippon Paper Co., Ltd.) 1. 〇〇 和 and GEROPON SDS (dioctyl sulfonate) Sodium succinate, product of Yanyeyi Pharmaceutical Co., Ltd.) 1 〇〇, mixed, and pulverized by a hammer mill to obtain a powder premix. Take 41.40 parts of the foam of sample No. 7 of Example 2, and fill it with a Nauta mixer, and add 46.75 parts of the premix. After mixing and absorbing, add 9.35 parts of the powder premix, mix and coat, and then add Jialong. The non-Pu 439 was 2.50 parts, and the mixed coating was carried out to obtain the pesticide granule of the present invention containing 37.50% of butyl lysine and 0.85% of azodone. 40 g of the obtained granules were dispensed in Hexilong C-200, and the preparation for paddy field throwing of the present invention was obtained. The preparation is applied at a rate of 5 packs per 10 acres of paddy field. Example 5 A mixture of 29.17 parts, EHDG 3.00 parts, NE-2609 1.50 parts, and DBC 1.50 parts were mixed to obtain an oil premix. Another 0.64 parts of the original M. sylvestre was taken, and the Longfeipu 439 was 5.26 parts, and the M-3 801 G 0.33 parts were mixed and pulverized by a hammer mill to obtain a powder premix. Take 54.60 parts of the foam of sample No. 2 of Example 1, and fill it with a Nauta mixer, and add 35.17 parts of the premix. After mixing and absorbing, add 6.23 parts of the powder premix, mix and coat, and then add Jialong. 4.00 parts of non-Pu, mixed coated, obtained with butyl leaching grass -34 - 1283256 5, invention description (33) 25.00%, subdoxone 50 7%, obtained the pesticide granules of the present invention. The preparation is applied from the edge of the crucible or the like in a ratio of 300 g per 10 acre of paddy field. Example 6 Production of a foamed carrier A foamed carrier was produced by using a twin-screw extruder as shown in the raw material formulation shown in Table 6. The physical properties of the obtained foamed carrier are shown in Table 7. Extrusion machine (隋希隆 EPM company twin-screw extruder α 100) Operating conditions: number of revolutions 80~160rpm, inner diameter and barrel ratio L/D: 12, raw material input amount 40~8 0kg/hr, pressure 30~ 50kg/cm2, mold aperture 1.5mm, 10 holes in series, barrel temperature 80~90°C, mold temperature 80~12〇t. Table 6 _ foaming carrier where the material number of the natural substance or its derivative crosslinker ' ^ thin powder (98) trimetaphosphoric acid 2 " corn slag (& trimetaphosphoric acid 3 oxidized starch (5 〇) + corn flour (3 8) Sodium tripolyphosphate (3) + gluten (3) + Telongqi Ep* (5) + coconut oil (1) * Carboxymethyl fiber sodium salt, first gluten industrial pharmaceutical company products () The mass fraction of the compounding amount is shown in Table 7. Table 7 _ hair-bubble carrier physical sample number volume specific volume foam outer diameter oil absorption multiple water suspension time water disintegration 1 11 3mm 1.5 20 hours non-disintegration 2 9 5mm 1.5 6 hours does not disintegrate 3 7 3mm 1.8 18 hours does not disintegrate -35- 1283256 V. Description of the invention (34) Example 7 Pesticide granules containing thin powder and α-amylase and paddy throwing preparations (ai90%) 43.75 parts, EHDG (diethylene glycol mono 2-ethylhexyl ether, manufactured by Japan Emulsifier Co., Ltd.) 3. Oyster, NE-2609 (polyoxyethylene polycyclic phenyl ether, Japan emulsifier company) Product) 0.50 parts, DBC (calcium dodecylbenzenesulfonate 70%, manufactured by Japan Emulsifier Co., Ltd.) 〇·50 parts, Table Quaistaj Μ8 (α-amylase) , Dahe Chemical Company's products) 0.2 parts, mixed, oil premix. Another 0.92 parts of Adolphin solanum (ai98.8%), Longfeipu 439 (Powdered Pearl Rock, Mitsui Metal Mining Company) Product) 5.40 parts, 1.00 parts of Barrex (sodium lignosulfonate, Nippon Paper Co., Ltd.), 2.00 parts of GROPON SDS (sodium dioctylsuccinate, Yanyeyi Pharmaceutical Co., Ltd.), mixed and hammered The machine was pulverized to obtain a powder premix. 40.20 parts of the foam of the sample No. 1 of Example 6 was charged, and the mixture was filled in a Nota mixer, and 47.95 parts of the premix was added. After mixing and absorbing, the powder was premixed. 9.35 parts of the mixture, mixed with the coating, and then added with 25% of the amphetamine 43. The mixture was coated to obtain the pesticide granule of the present invention containing 37.50% of butyl lysine and 0.85% of oxidized toldol. The obtained granules were 40 g. The preparation of the paddy field throwing preparation of the present invention is carried out in a seaweed C-200 (a PVA film having a thickness of 40 // m, and a product of a Japanese film company). The preparation is thrown and applied in a ratio of 5 packs per 10 hectares of paddy fields. 8 Pesticide preparation containing corn residue and X-amylase and preparation for paddy field throwing in Example 7, except for implementation The foaming carrier of the test No. 1 of Example 6 was changed to the foaming carrier of the sample No. 2 of Example 6, and the same as in Example 1, the method of -36-1283256, and the description of the invention (35) obtained 37.50% of the butyl-containing grass. The pesticide preparation of the present invention is 0.85% of the product of the present invention. 40 g of the obtained preparation is dispensed in Haixilong C-200, and the preparation for paddy field throwing of the present invention is obtained. The preparation is thrown and applied in a ratio of 5 packs per 10 hectares of paddy fields. Example 9 A pesticide preparation of a thin powder, an α-amylase and a protein enzyme, and a preparation for paddy field throwing were carried out in Example 7, except that the table of Kwajstaj Μ8 0.20 was changed to the table Quaistaj Μ8 0.10 parts and A pesticide preparation of the present invention containing 37.50% of butyl lavender and 0.85% of butoloxanone was prepared in the same manner as in Example 7 except that 0.10 parts of Longch AS 10 (Protein, Daiwa Kasei Co., Ltd. product). 40 g of the obtained preparation was dispensed in Hexilon C-200, and the preparation for paddy field throwing of the present invention was obtained. The preparation is thrown and applied in a ratio of 5 packs per 1 〇 of the paddy field. Example 10 A pesticide preparation containing oxidase, corn flour, silibone, α-amylmentase and cellulase, and a paddy throwing preparation were carried out in Example 7, except that the table was added to the scale of 0.20. Table 60: 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 In the same manner as in Example 7 except for the foaming carrier, the agricultural chemical preparation of the present invention containing 37.50% of butyl lavage and 0.85% of soloxoprostol was obtained. 40 g of the obtained preparation was dispensed in Hexilon C-200 to obtain a paddy preparation for use in the present invention. The preparation is thrown at a rate of 5 packs per 1 〇 of the paddy field. Test Example 1 - 37 - 1283256 V. Description of Invention (36) The results are shown in Table 8. As shown in Table 8, the surface suspended granules of the present invention suspend the water surface about 24 hours after being put into water, and then slowly sink. After 48 hours, the granules have settled, and the granules have a high expansibility index. It expands well on the water surface. The granules of these examples did not sink when just placed in water' and showed good spreadability. Table 8 Resuspension of the granules and the expansive index of the granules of the granules. Example 3: No granules after 24 hours, and then the sedimentation of the granules was almost 24 hours after the sedimentation for 24 hours. Settling granules 11 Example 4 After 48 hours, the granules were almost settled for 24 hours without sedimentation granules 10 Example 5 After almost 48 hours, the granules almost settled 12 Test Example 2 Dissolution test At room temperature 20 ° C, 1 liter of liters of normal water is packed into a plastic container (water depth of about 5 cm) with an internal dimension of 6 cm cm X vertical 34 cm X height 10 cm (area 2040 cm 2 ), and the water temperature is adjusted to 20 ° C. The samples were weighed approximately 4 mg (Examples 3 and 4) and approximately 60 mg (Example 5) and processed at the center. After 24 hours of treatment, the water was sampled at three points on the diagonal of the container as shown in Fig. 1, and all the granules in the settling water or suspended water surface were recovered. The high-speed liquid chromatography is used to analyze the concentration of the active ingredient in the water and the effective ingredients in the granule, and to determine the dissolution rate of the active ingredient in water and the residual content of the active ingredient in the granule. The results are shown in Table 9. Any of the samples of Examples 3 to 5 are shown in -38 to 1283256. 5. Description of the invention (37) Approximately 100% of the dissolution rate of the solo solsone and the butyl lavage after 1 day of treatment, and a few in the granules. See residual active ingredients. Table 9 Dissolution test results Test granules Azodocendron butyl chlorpyrifos water concentration (ppm) n = 3 Average water dissolution (%) Residue rate in granules (%) Water concentration (ppn) n = 3 Average water dissolution (%) Residual rate in granules (%) Example 3 0.03 1.40 0.03 1.45 0.03 0.03 100 0 1.44 1.43 95 1 Example 4 0.03 1.32 0.03 1.44 0.03 0.03 100 0 1.42 1.39 93 2 Example 5 0.03 1.44 0.03 1.36 0.03 0.03 100 0 1.3 9 1.40 93 4 The theoretical concentration of water is azodoxone: 0.03ppm and butyl lavender: l.50ppm. Test Example 3 Disintegration test 500 liters of 3 degree hard water was placed in a beaker of 500 ml capacity at room temperature of 20 ° C, and the water temperature was adjusted to 20 ° C. The pesticide preparations of Examples 7 to 10 and the foaming carriers of Example 6 sample numbers 丨 to 3 were placed in a beaker, and the disintegration time of the granules was observed. The results are shown in Table 1. • 39- 1283256 V. Description of invention (38) Table 10 Disintegration test number Test preparation 磲 @ Body water disintegration time 1 Pesticide formulation of Example 7 20 minutes 镬 2 The pesticide preparation of Example 8 is 30 minutes 镂The pesticide preparation of Example 9 was 15 minutes. 4 The pesticide preparation of Example 10 was 10 minutes. 5 The foaming carrier of Example 6 sample No. 1 was not disintegrated. 6 The foamed carrier of Example 6 was number 2 was not disintegrated. Example 6 The foamed carrier of sample No. 3 was not disintegrated. The foamed carrier of Example 未 did not disintegrate, and the pesticide formulations of Examples 7 to 10 containing these foaming carriers and enzymes all disintegrated within 3 minutes of treatment. . INDUSTRIAL APPLICABILITY According to the present invention, a foam having a suspended water surface and having a large oil absorption capacity can be obtained. These foams can be used, for example, as a paddy throwing agent or a pesticide carrier for paddy field spreading, and the amount of the paddy field treatment can be greatly reduced due to the high concentration of the liquid precursor. These technologies require labor-saving as the peasant population ages and contribute significantly to recent agricultural needs. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows a sample processing position and a water sampling position of Test Example 2. -40-

Claims (1)

1283256 公告本 _補见丨 六、申請專利範圍 第901 1 0107號「具有高吸油性之生物分解性水面懸浮發 泡體’其製法及含有他之組成物」專利案 (93年12月20日修正） 六、申請專利範圍： 1. 一種發泡體，係於含澱粉物質95.0至99.0質量份，添 加混合交聯劑〇. 1至5質量份，經擠壓機處理之發泡體 直徑爲模徑之1至5倍，體積比容爲1至20ml/g，具 有本身重量0.3至5倍的吸油能力，可在水面懸浮10 分鐘以上者。 2. —種發泡體，係於含澱粉物質和澱粉類（含澱粉物質：澱 粉類=0至80:100至20)45至95質量份，添加熱凝固物 質1至30質量份和交聯劑〇. 1至5質量份，加以混合 ，在擠壓機處理前之混合物係含脂質0.1至8質量份和 乳化劑0· 1至5質量份，經擠壓機處理之發泡體直徑爲 模徑1至5倍，體積比容爲1至20ml/g，具有本身重 量0.3至5倍的吸油能力，可在水面懸浮10分鐘以上 者。 3. —種製造發泡體之方法，其特徵爲含澱粉物質95.0至 99.0質量份添加混合交聯劑0.1至5質量份，以擠壓機 在模溫100至150°C加壓擠出處理，而得發泡體直徑爲 模徑之1至5倍，體積比容爲1至20ml/g，具有本身 重量0.3至5倍的吸油能力，可在水面懸浮10分鐘以 上者。 1283256 六、申請專利範圍 4·一種製造發泡體之方法，其特徵爲含澱粉物質和澱粉類 (含澱粉物質：澱粉類=0至80:100至20)45至90質量份 ’添加熱凝固物質1至30質量份和交聯劑〇. 1至5質 量份，加以混合，在擠壓機加壓處理前之混合物係含 脂質0.1至8質量份和乳化劑0· 1至5質量份，以擠壓 機在模溫100至150°C加壓擠出處理，而得發泡體直徑 爲1至5倍，體積比容爲1至20ml/g，具有本身重量 0.3至5倍的吸油能力，可在水面懸浮10分鐘以上者 〇 5 · —種水面懸浮性粒狀農藥組成物，其係於如申請專利範 圍第1或2項之發泡體，吸收本身重量0.2至7倍量的 油狀農藥原體或農藥之高沸點有機溶劑溶液，再於必 要時含有選自α-烯烴磺酸鹽、α-磺脂肪酸鹽、烯 烴脂肪酸鹽、油基甲基牛磺酸鹽、單或二烷基磺丁二 酸鹽以及於此附加環氧烷所得界面活性劑、烷基硫酸 鹽、炔系、聚矽氧系、氟系界面活性劑、二醇類之醚 或酯類、以及羧酸烷酯類之高沸點溶劑一種或二種以 上之水面擴展劑，被覆農藥的固體原體粉碎物，由農 藥固體原體與固體載體等一同粉碎的預混物，或不含 農藥的固體載體粉末，使具有流動性、水面擴展指數 在5以上者。 6.如申請專利範圍第5項之水面懸浮性粒狀農藥組成物， 其中係含有水面擴展劑，該水面擴展劑之混配量爲 1283256 六、申請專利範圍 0.1 〜30%。 7. 如申請專利範圍第5項之水面懸浮性粒狀農藥組成物， 其中農藥有效成份含有選自丁基拉草、普拉草、阿尼 隆活速、比福列西妥、洽隆活普索、濟美他美妥林等 液狀原體，或比西拂隆美索、百速隆、亞濟莫速拂隆 、亞朵索拂隆、依速隆、西諾速拂隆之磺醯基尿素系 除草劑一種或二種以上者。 8. 如申請專利範圔第5項之水面懸浮性粒狀農藥組成物， 其中含有對含澱粉物質或澱粉類作用之酵素者。 9. 如申請專利範圍第8項之水面懸浮性粒狀農藥組成物， 其中含澱粉物質或澱粉類係爲玉米粉、玉米渣或小麥 粉，酵素爲澱粉葡萄糖酵素、α-澱粉酵素、万-澱粉酵 素或異澱粉酵素者。 10·如申請專利範圍第5項之水面懸浮性粒狀農藥組成物 ’其含有纖維素酵素、細菌蛋白酵素、絲狀菌蛋白酵 素、木瓜酵素、胃蛋白酵素、或果膠酵素者。 11 ·如申請專利範圍第8項之水面懸浮性粒狀農藥組成物， 其中酵素係內型（end〇)酵素者。1283256 Announcement _ Supplementary Sixth, Patent Application No. 901 1 0107 "Biodegradable Water Surface Suspension Foam with High Oil Absorption" and Its Patent Composition (December 20, 1993) Amendment) VI. Scope of application: 1. A foam, which is 95.0 to 99.0 parts by mass of starch-containing material, and 1 to 5 parts by mass of mixed crosslinking agent. The diameter of the foam treated by the extruder is It has a volume ratio of 1 to 5 times and a volume specific volume of 1 to 20 ml/g. It has an oil absorption capacity of 0.3 to 5 times its own weight and can be suspended on the surface for more than 10 minutes. 2. A kind of foam, which is 45 to 95 parts by mass of a starch-containing substance and a starch (starch-containing substance: starch type 0 to 80: 100 to 20), 1 to 30 parts by mass of a thermally coagulated substance, and cross-linking 〇1. 5 parts by mass, mixed, the mixture before the treatment by the extruder is 0.1 to 8 parts by mass of the lipid and 0.1 to 5 parts by mass of the emulsifier, and the diameter of the foam treated by the extruder is The mold has a diameter of 1 to 5 times, a volume specific volume of 1 to 20 ml/g, and an oil absorption capacity of 0.3 to 5 times its own weight, which can be suspended on the surface for more than 10 minutes. 3. A method for producing a foam, characterized by containing 95.0 to 99.0 parts by mass of a starch-containing substance, 0.1 to 5 parts by mass of a mixed crosslinking agent, and press-extruding at a mold temperature of 100 to 150 ° C in an extruder The foam has a diameter of 1 to 5 times the diameter of the mold, a volume specific volume of 1 to 20 ml/g, and an oil absorption capacity of 0.3 to 5 times its own weight, which can be suspended on the surface for more than 10 minutes. 1283256 VI. Patent application scope 4. A method for producing a foam characterized by containing starch and starch (containing starch: starch = 0 to 80: 100 to 20) 45 to 90 parts by mass 'addition of heat coagulation 1 to 30 parts by mass of the substance and 1 to 5 parts by mass of the crosslinking agent, and the mixture before the pressure treatment of the extruder is 0.1 to 8 parts by mass of the lipid and 0.1 to 5 parts by mass of the emulsifier. Pressing and extruding at a mold temperature of 100 to 150 ° C in an extruder to obtain a foam having a diameter of 1 to 5 times, a volume specific volume of 1 to 20 ml/g, and an oil absorption capacity of 0.3 to 5 times its own weight. , which can be suspended on the surface for more than 10 minutes. 水5 · A water-suspended granular pesticide composition, which is a foam of the first or second aspect of the patent application, and absorbs 0.2 to 7 times its own weight of oil. a high-boiling organic solvent solution of a pesticide or a pesticide, and optionally containing an α-olefin sulfonate, an α-sulfonated fatty acid salt, an olefin fatty acid salt, an oleyl methyl taurate, a mono- or di-alkane a sulfosuccinate and a surfactant obtained from the addition of an alkylene oxide, an alkyl sulfate, an acetylene, One or two or more kinds of water surface extenders of an oxygen-based or fluorine-based surfactant, a glycol-based ether or an ester, and a high-boiling solvent of a carboxylate, and a solid raw material-pulverized material coated with a pesticide, and a pesticide A premix which is pulverized together with a solid carrier or the like, or a solid carrier powder which does not contain a pesticide, and which has fluidity and a water surface expansion index of 5 or more. 6. The surface suspended particulate pesticide composition of claim 5, wherein the surface expansion agent comprises a surface expansion agent, the compounding amount of the surface expansion agent is 1283256, and the patent application range is 0.1 to 30%. 7. For the surface suspended particulate pesticide composition of claim 5, wherein the active ingredient of the pesticide contains a compound selected from the group consisting of butyl praline, praache, alonone, piracetox, and sulco Liquid precursors such as Pusuo, Jimei Tamiline, or sulfonate than Xiqiao Longmeisuo, Baisonglong, Yazi Mosuo Qianlong, Adoluo Qianlong, Yisuolong, and Sinovel One or more of the urea-based herbicides. 8. For example, the surface suspended particulate pesticide composition of Patent No. 5, which contains enzymes which act on starchy substances or starches. 9. For example, the water-suspended granular pesticide composition of claim 8 of the patent scope, wherein the starch-containing material or starch is corn flour, corn residue or wheat flour, and the enzyme is starch glucose enzyme, α-amylase, 10,000- Amylin or isoamylase. 10. The surface suspended particulate pesticide composition of claim 5, which contains cellulose enzyme, bacterial protein enzyme, filamentous protein enzyme, papaya enzyme, pepsin, or pectin. 11 · For example, the surface suspended granular pesticide composition of the scope of patent application, wherein the enzyme is end-type enzyme.
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