1241162 五、發明説明（1 ) 【技術領域】 本發明係有關一種水性懸浮性農藥製劑，其以1，Γ-亞 胺二（八亞甲基）二瓠=參（烷基苯磺酸鹽）爲有效成分，對低 溫領域的週期性溫度變化具有優越的穩定性。 【背景技術】 本發明製劑的農藥有效成分Ι,Γ-亞胺二（八亞甲基）二銀 =參（烷基苯磺酸鹽），是一種廣爲人知的優良農園藝用殺 菌劑（特公平2-7564號、美國特許第4659739號），特別是 烷基苯磺酸鹽的烷基鏈以碳數12的成分爲主成分之碳數 10〜13的1，1’-亞胺二（八亞甲基）二觚=參（烷基苯磺酸鹽） (熔點92〜96°C)被命名爲亞胺八勁烷基苄基酸鹽，爲一種 具有廣效性的農園藝用殺菌劑且已實用化。 通常，將常溫下呈固體的農藥原體製成水懸浮型農藥製 劑時，可配合使用水溶性或水懸浮性合成高分子或陰離子 界面活性劑或非離子界面活性劑等，調製成懸浮型製劑（ 懸浮液）。 惟將熔點爲30°C〜10(TC的農藥原體懸浮化所製成的懸 浮型製劑置於溫差劇烈的條件下時，因分散的固態原體或 熔解或固化，晶體成長的同時分散狀況也被破壞。又，使 農藥原體溶解在一般使用的水不溶性有機溶劑後在水中乳 化成懸浮劑（乳濁液），在分散於水中的微小液滴內亦發生 農藥原體的結晶化，因此發生乳濁液被破壞而析出結晶的 問題。 本發明使用的農藥有效成分ι，ι’-亞胺二（八亞甲基）二Μ 1241162 五、發明説明（2 ) =參（烷基苯磺酸鹽）在農藥原體的製劑加工中使用眾知的 方法亦有顯著的結晶析出，不易製成穩定的水性懸浮製劑 。亦即，經過懸浮化的懸浮型製劑因發生前述農藥有效成 分的固化或結晶化使分散狀態瓦解。又，此農藥有效成分 在一般使用的水不溶性有機溶劑中的溶解性顯著不佳，故 亦不易進行乳化。 因此，本發明者們依特開平8-225402號公報（美國特許 第5728734號說明書）之揭示內容開發出含有（a)l，lf-亞胺 二（八亞甲基）二觚=參（烷基苯磺酸鹽）、（b)分散穩定劑， 其構造如一般式（1)1241162 V. Description of the Invention (1) [Technical Field] The present invention relates to an aqueous suspension pesticide formulation, which uses 1, Γ-iminebis (octamethylene) difluorene = ginseng (alkylbenzenesulfonate) As an active ingredient, it has excellent stability against periodic temperature changes in the low temperature field. [Background Art] The active ingredient of the pesticide of the present invention, I, Γ-imine bis (octamethylene) di silver = ginseng (alkylbenzene sulfonate), is a well-known excellent agricultural and horticultural fungicide ( JP 2-7564, U.S. Patent No. 4,659,739), especially the alkyl chain of alkylbenzene sulfonates with a carbon number of 12 as the main component of 1,1'-imine di of carbon number of 10 to 13 (Octamethylene) dipyridine = ginseng (alkylbenzene sulfonate) (melting point 92 ~ 96 ° C) is named imine octadecyl benzyl acid salt, which has a wide range of agricultural and horticultural purposes Fungicides have been put into practical use. Generally, when a pesticide precursor that is solid at room temperature is made into a water-suspended pesticide formulation, a water-soluble or water-suspended synthetic polymer or an anionic surfactant or a non-ionic surfactant can be used to prepare a suspension-type formulation. ( suspension). However, when a suspension preparation made by suspending a pesticide precursor having a melting point of 30 ° C to 10 ° C is placed under a condition of severe temperature difference, the dispersed solid state or melted or solidified, the crystal grows and dispersed at the same time. It is also destroyed. In addition, the pesticide raw material is dissolved in a commonly used water-insoluble organic solvent and emulsified into a suspension (emulsion) in water. The pesticide raw material also crystallizes in minute droplets dispersed in the water. Therefore, the emulsion is destroyed and crystals are precipitated. The active ingredient of the pesticide used in the present invention is ι, ι'-imine bis (octamethylene) di M 1241162 5. Description of the invention (2) = reference (alkylbenzene Sulfonate) in the preparation of pesticide precursors using well-known methods also have significant crystal precipitation, it is not easy to make stable aqueous suspension formulations. That is, suspension-type suspension formulations due to the occurrence of the aforementioned active ingredients of pesticides Solidification or crystallization disintegrates the dispersed state. In addition, the active ingredient of the pesticide has a significantly poor solubility in a water-insoluble organic solvent generally used, and therefore it is not easy to emulsify. Therefore, the present invention According to the disclosure of Japanese Unexamined Patent Publication No. 8-225402 (U.S. Patent No. 5,728,734), it was developed to contain (a) l, lf-iminebis (octamethylene) difluorene = ginseng (alkylbenzenesulfonate ), (B) dispersion stabilizer, its structure is as shown in general formula (1)
R-0-(CH2CH20)n-H (式中，R表示爲碳原子數8〜18的烷基或烯基，n爲〇〜4 的整數。）表示的化合物，或磷脂質、（c)含有碳原子數6 〜20的烷基或烯基之界面活性劑、以及（d)水之水性懸浮 型農藥製劑。 此水性懸浮型農藥製劑在50°C的長期保存試驗、-5°C的 長期保存試驗，以及在溫差劇烈的條件下，具體而言以高 溫（50°C)3日及低溫（-10°C)3日爲週期的保存試驗進行12 週的長期間保存試驗之結果，因農藥有效成分等未發生分 離沉澱，而保持穩定的懸浮狀態，故被視爲一種具有優越 穩定性且對環境及使用者安全性高的水性懸浮型農藥製劑。 但是，此製劑對低溫下的溫度變化較弱。亦即，因寒冷 地區的冬季連日、週期性地發生晝夜氣溫變化在5°C〜-l〇°C 的範圍，此狀態下此製劑在冬季期間長期保存3〜4個月 -4- 1241162 五、發明説明（3 ) 後，此製劑將仍保持懸浮狀態變成高黏度或固化成乳液狀 ’待春季氣溫上升至20°C前後始恢復良好的流動狀態。又 ’此製劑恢復流動狀態後其懸浮狀態亦不佳，而且懸浮物 中產生農藥有效成分的微小析出物會阻塞噴灑機等，相當 不易噴灑。 因此，先前開發的1，1’-亞胺二（八亞甲基）二銀=參（烷基 苯磺酸鹽）的水性懸浮型農藥製劑，在氣溫多次重複在0°c 前後的低溫週期的寒冷地區的冬季，其保存穩定性仍不足。 【發明的揭示】 本發明欲解決的課題，係提供不僅在季節間的長週期中 溫度變化大的保存條件下具有優良的儲存穩定性，在晝夜 的短週期中溫度在5°c〜-10°c的範圍變化的冬季長期保存 ，亦具有優越保存穩定性的1，Γ-亞胺二（八亞甲基）二銀= 參（烷基苯磺酸鹽）的水性懸浮型農藥製劑。 本發明者們爲了解決課題進行各種硏究的結果，發現在 上述揭示的處方中在磷脂質方面藉由使用碘價小於20的 加氫磷脂質，可製得不僅在季節間的長週期中溫度變化大 的保存條件下，特別是晝夜間短週期中溫度在5°C〜-1(TC 的範圍變化的保存條件下仍保持穩定的懸浮狀態，並可抑 制產生農藥有效成分的微小析出物之保存穩定性的水性懸 浮型農藥製劑而完成本發明。 即本發明爲了解決上述課題，提供一種水性懸浮型農藥 製劑，其特徵係含有（a)l，l’-亞胺二（八亞甲基）二瓠=參（烷 基苯磺酸鹽）、（b)如一般式（1) 1241162 五、發明説明（4 )R-0- (CH2CH20) nH (wherein R is an alkyl or alkenyl group having 8 to 18 carbon atoms, n is an integer of 0 to 4), a compound represented by phospholipid, or (c) contains carbon An alkyl or alkenyl surfactant with 6 to 20 atoms, and (d) an aqueous suspension pesticide formulation of water. This aqueous suspension pesticide formulation has a long-term storage test at 50 ° C, a long-term storage test at -5 ° C, and under severe temperature differences, specifically at high temperature (50 ° C) for 3 days and low temperature (-10 ° C) The result of a long-term storage test conducted on a 3-day periodic storage test for 12 weeks. Because the active ingredients of pesticides did not separate and precipitate, but remained in a stable suspension state, it was regarded as a kind of material with excellent stability and environmental protection. User-friendly water-borne suspension pesticide formulation. However, this formulation is weak against temperature changes at low temperatures. That is, due to the continuous day-to-day and winter temperature changes in the cold region in the range of 5 ° C to -10 ° C, this preparation can be stored for 3 to 4 months in the winter for a long period of 4-1241162. After the description of the invention (3), the preparation will remain suspended and become highly viscous or solidify into an emulsion. 'It will return to a good flowing state before the spring temperature rises to 20 ° C. In addition, the suspension state of the preparation is not good after the flow state is restored, and the fine precipitates of the active ingredients of pesticides in the suspension will block the spraying machine, etc., and it is quite difficult to spray. Therefore, the previously developed aqueous suspension type pesticide formulation of 1,1'-imine bis (octamethylene) bissilver = ginseng (alkylbenzene sulfonate) repeatedly repeated low temperatures around 0 ° c at temperatures In the cold regions of the cycle, the preservation stability is still insufficient. [Disclosure of the invention] The problem to be solved by the present invention is to provide excellent storage stability not only under storage conditions with large temperature changes during long periods between seasons, but also at temperatures between 5 ° c and -10 in short periods during the day and night. Long-term storage in winter with a range of ° c, also an aqueous suspension pesticide formulation of 1, Γ-imine bis (octamethylene) bissilver = ginseng (alkylbenzene sulfonate) with excellent storage stability. As a result of various researches conducted by the present inventors in order to solve the problem, it has been found that the use of a hydrolyzed phospholipid with an iodine value of less than 20 in phospholipids in the above-disclosed prescription can produce a temperature not only in a long period between seasons. Under the storage conditions with great changes, especially in the short-term temperature range of 5 ° C ~ -1 (TC) during the day and night, the storage conditions remain stable and suspended, and the production of tiny precipitates of active ingredients of pesticides can be suppressed. The present invention has been accomplished by preserving a stable aqueous suspension pesticide formulation. That is, the present invention provides an aqueous suspension pesticide formulation, which is characterized by containing (a) l, l'-imine bis (octamethylene) in order to solve the above-mentioned problems. ) Difluorene = ginseng (alkylbenzene sulfonate), (b) as general formula (1) 1241162 5. Description of the invention (4)
R-0-(CH2CH2〇)n-H (式中，R表示爲碳原子數8〜18的烷基或烯基，n爲0〜4 的整數。）表示的化合物、（〇磷脂質、（d)含有碳原子數6 〜20的烷基之界面活性劑及（e)水，其中上述（c)磷脂質係 碘價小於20的加氫磷脂質。 【實施發明的最佳型態】 以下依序說明本發明的水性懸浮型農藥製劑的組成成分。 本發明使用的（a) 1，Γ-亞胺二（八亞甲基）二瓠=參（烷基苯 磺酸鹽）係本發明水性懸浮型農藥製劑的有效成分。（以下 簡稱（a)農藥有效成分）。 組成本發明中使用的（a)農藥有效成分之烷基苯磺酸鹽 ，以含有碳原子數1〜20的烷基之苯磺酸鹽較理想，從預 防藥害和藥效的觀點，含有碳原子數4〜18的烷基之苯磺 酸鹽特別理想，含有碳原子數1 0〜1 3的烷基之苯磺酸鹽 更適用。這些（a)農藥有效成分實質上皆爲水不溶性成分。 又，Ι,Γ-亞胺二（八亞甲基）二瓠=參（烷基苯磺酸鹽）中的烷 基苯磺酸鹽係含有碳原子數10〜13的烷基之苯磺酸鹽， 被稱爲「亞胺八勁烷基苄基酸鹽」的農藥成分。 其次，說明（b)—般式（1)表示的化合物。 本發明使用的（b)上述一般式（1)表示的化合物，其作用 在本發明的水性懸浮型農藥製劑中爲一分散穩定劑。 在一般式（1)中，n = 0的化合物係分子中不含氧乙烯基而 碳原子數8〜1 8的飽和脂肪族醇。 在一般式（1)中，n=l的化合物係碳原子數8〜18的飽和 -6- 1241162 五、發明説明（5 ) 脂肪族醇與乙二醇以醚鍵結的醇類，一般稱爲聚氧乙烯基 (1莫耳）單烷基醚，通常省略「單」而簡稱爲聚氧乙烯基 (1莫耳）烷基醚。又’例如n = 3所表示的醇是指飽和脂肪 族醇與三甘醇和以醚鍵結的醇類，一般稱爲聚氧乙烯基（3 莫耳）烷基醚的醇類。 碳原子數8〜18的飽和脂肪族醇可以爲直鏈狀或分支狀 ’以直鏈狀較理想。較理想的飽和脂肪族醇係含有和組成 (a)農藥有效成分的烷基苯磺酸鹽的烷基有相同碳原子數之 醇類，以碳原子數10〜13的直鏈狀醇特別理想。 上述一般式（1)表示的飽和脂肪族醇例如辛醇、癸醇、 十二醇、十六醇、十八醇等直鏈狀烷醇；2-乙基-己醇、2-乙基-己二甘醇（別名：二甘醇單-2-乙基己基醚）等分支狀 烷基醇類；聚氧乙烯基（1〜4莫耳）十二醚、聚氧乙烯基（1 〜4莫耳）十六醚等聚氧乙烯基部份的重複數n爲1〜4的 聚氧乙烯基烷基醚類等。 其次，說明本發明使用的（c)碘價小於20的加氫磷脂質。 本發明使用的（c)碘價小於20的加氫磷脂質，其作用在 本發明的水性懸浮型農藥製劑中爲一分散穩定劑。 加氫磷脂質是將由大豆、菜籽等油糧種子或蛋黃等動物 性脂質產生的卵磷脂進行加氫處理至碘價小於20爲止， 而使磷脂質的大部分不飽和脂肪酸轉變成飽和脂肪酸。本 發明又以碘價小於10的加氫磷脂質特別適用。 這些加氫磷脂質中，從價格及由天然物製得而品質變動 較少的觀點，以加氫大豆卵磷質特別理想。 -7- 1241162 五、發明説明（6 ) 本發明使用的（C)碘價小於20的加氫磷脂質，特別是加 氫卵磷脂或水溶性蛋白質廣泛應用在香料化妝品或食品領 域，經證實對環境或人體的安全性高。又，本發明使用的 一般式（1)表示的化合物若能選擇應用在香料化妝品或食品 領域者，可提高本水性懸浮製劑的安全性。此等功能皆爲 農藥有效成分的水性懸浮型製劑之分散穩定劑。 其次，說明本發明使用的（d)含有碳原子數6〜20的烷 基之界面活性劑。 本發明使用的（d)含有碳原子數6〜20的烷基之界面活 性劑可以爲離子性或非離子性。組成上述界面活性劑的烷 基可以爲直鏈狀或分支狀，以直鏈狀較適合。組成界面活 性劑的烷基，和組成（a)農藥有效成分的烷基苯磺酸鹽之烷 基具有相同碳原子數者較理想，以碳原子數10〜18的烷 基更佳，又以碳原子數10〜13的烷基特別理想。 從分散穩定劑的觀點，本發明使用的（b)—般式（1)表示 的化合物的烷基和組成（d)含有碳原子數6〜20的烷基的界 面活性劑之烷基，皆與組成（a)農藥有效成分的烷基苯磺酸 鹽之烷基具有相同碳原子數者較理想，以碳原子數1〇〜13 的烷基特別理想。 惟使用在（d)含有碳原子數6〜20的烷基的界面活性劑 之原料大多從天然物製得者，其烷基的碳原子數因有分布 範圍，若含有理想範圍的碳原子數10〜18的烷基者，可 使用含有碳原子數6〜20的烷基之界面活性劑。 本發明使用的（d)含有碳原子數6〜20的烷基之界面活 1241162 五、發明説明（7 ) 性劑，可大致分爲（d-1)聚環氧化物類非離子界面活性劑、 (d-2)脂肪酸酯類非離子界面活性劑、（d-3)陰離子類界面活 性劑、（d-4)陽離子類界面活性劑、（d-5)雙離子性界面活性 劑。 (d-Ι)聚環氧化物類非離子界面活性劑例如，聚氧乙烯基 (20莫耳）十二醚、聚氧乙烯基（15莫耳）十六醚等聚氧伸烷 基烷基醚類；聚氧乙烯基（12莫耳）十二胺基醚等聚氧伸烷 基烷基胺基醚類等。 (d-2)脂肪酸酯類非離子界面活性劑例如，十甘油十二酸 酯、十甘油十四酸酯、己甘油十八酸酯等聚甘油飽和脂肪 酸酯類；聚乙二醇（平均分子量600)十二酸酯等聚伸烷基 乙二醇飽和脂肪酸酯類；聚氧乙烯基聚丙二醇嵌段共聚物 十八酸酯等聚氧伸烷基聚丙二醇飽和脂肪酸酯類等。 (d-3)陰離子類界面活性劑例如，十二硫酸鈉等烷基硫酸 鹽類；聚氧乙烯基（20莫耳）十二醚硫酸根銨鹽等聚氧伸烷 基烷基硫酸鹽類等。 (d-4)陽離子類界面活性劑例如，十六基三甲基銨氯化物 等烷基銨鹽類；聚氧乙烯基（10莫耳）十八基甲基銨氯化物 等聚氧伸烷基烷基銨鹽類等。 (d-5)雙離子性界面活性劑例如，十二基二甲基銨三甲銨 基乙內鹽等烷基三甲銨基乙內鹽類；十二基二甲基胺化氧 等胺化氧類等。 上述的界面活性劑中，（d-2)脂肪酸酯類非離子界面活性 劑中的聚甘油飽和脂肪酸酯類，因水性懸浮型農藥製劑的 -9- 1241162 五、發明説明（8 ) 低溫穩定性佳，特別適用。 藉著在本發明的水性懸浮型農藥製劑中使用（f)水溶性蛋 白質，可具有優越的保存穩定性。（f)水溶性蛋白質例如， 乳蛋白質、植物性蛋白質、動物性蛋白質等，或由這些蛋 白質製成的蛋白製劑例如，一種以上選自脫脂奶粉、全脂 奶粉、乳白蛋白水解物、酪蛋白、酪蛋白鈉等酪蛋白的鹼 金屬鹽、乳淸蛋白、大豆粉末、魚肉粉末、明膠、蛋白粉 末、蛋黃粉末等，其中以酪蛋白鈉特別適用。 本發明的水性懸浮型農藥製劑中的（a)農藥有效成分的 比例爲1〜45重量％的範圍較佳，以5〜40重量％的範圍 特別理想。本發明的水性懸浮型農藥製劑中的（b)—般式（1) 表示的化合物之比例爲0.5〜1 0重量％的範圍較佳，以1 〜8重量％的範圍特別理想。又，本發明的水性懸浮型農 藥製劑中的（c)碘價小於20的加氫磷脂質之比例爲0.5〜 1 〇重量％的範圍較佳，以1〜8重量％的範圍特別理想。又 ’本發明的水性懸浮型農藥製劑中的（d)含有碳原子數6〜 20的烷基之界面活性劑的比例爲〇.5〜10重量〇/。的範圍較 佳，以1〜8重量％的範圍特別理想。本發明的水性懸浮型 農藥製劑中的（e)水的比例爲25〜97.5重量％的範圍較佳 ’以36〜92重量％的範圍特別理想。在本發明的水性懸浮 型農藥製劑中配合使用（f)水溶性蛋白質，本發明的水性懸 浮型農藥製劑中的（0水溶性蛋白質之比例，以加氫磷脂質 和水溶性蛋白質的總量在0.5〜1 0重量％的範圍較佳，以 1〜8重量％的範圍特別理想。 -10- ------- 1241162 五、發明説明（9 ) 本發明的水性懸浮型農藥製劑中的（a)農藥有效成分和（b) 一般式（1)表示的化合物之比例，其重量比在0.1:1〜90:1 的範圍較佳，以0.6:1〜40:1的範圍更理想。又，本發明 的水性懸浮型農藥製劑中的（a)農藥有效成分和（c)碘價小 於20的加氫磷脂質之比例，其重量比在0.1:1〜90:1的範 圍較佳，以0.6 :1〜4 0 :1的範圍更理想。本發明的水性懸 浮型農藥製劑中的（a)農藥有效成分和（d)含有碳原子數6〜 20的烷基之界面活性劑的比例，其重量比在0.1:1〜90M 的範圍較佳，以0.6:1〜40:1的範圍更理想。 在本發明的水性懸浮型農藥製劑中配合使用（f)水溶性蛋 白質時，（a)農藥有效成分和（c)碘價小於20的加氫磷脂質 與（0水溶性蛋白質二者的總量之比例，其重量比在0.1:1 〜90:1的範圍較佳，以0.6:1〜40:1的範圍更理想。又， (c)碘價小於20的加氫磷脂質和（f)水溶性蛋白質比例，其 重量比在0.1 :1〜1:1 0的範圍較理想。 又，在不破壞本發明的效果之原則下，可在本發明的水 性懸浮型農藥製劑中添加其他的任意成分。例如阻凍劑、 防腐劑、緩衝劑等。 阻凍劑例如，乙二醇、丙二醇、丙二醇單甲醚等水溶性 有機溶劑、尿素等。使用阻凍劑時，其用量以取代本發明 水性懸浮型農藥製劑中的（e)水用量之1/50〜1/4較適當。 調製本發明的水性懸浮型農藥製劑時必須將各成份充分 混合。（d)含有碳原子數6〜20的烷基之界面活性劑通常— 次添加全量，亦可以一部分添加在（a)農藥有效成分、（b) -11- 1241162 五、發明説明（1G ) 一般式（1)表示的化合物及（c)碘價小於20的加氫磷脂質的 混合物中，剩餘的部份則添加在（e)水中。水之外各成份的 混合順序並無特別限制，惟從容易形成均勻混合物的觀點 ’將（b)—般式（1)表示的化合物和（c)碘價小於20的加氫磷 脂質以及，依需求和（f)水溶性蛋白質混合後再加入（a)農 藥有效成分和（d)含有碳原子數6〜20的烷基之界面活性劑 較理想。 混合（a)農藥有效成分、（b)—般式（1)表示的化合物、（c) 碘價小於20的加氫磷脂質及（d)含有碳原子數6〜20的烷 基之界面活性劑時，同時加（e)水混合並不理想。混合（a) 農藥有效成分、（b)—般式（1)表示的化合物、（c)碘價小於 20的加氫磷脂質及（d)含有碳原子數6〜20的烷基之界面 活性劑時，適度地加熱較理想。此時，若施以高溫則容易 發生著色現象，較理想的處理溫度爲小於80°C，以50〜 70°C的範圍更理想。 添加水使成爲懸浮狀態的方法可使用舊有眾知的方法。 亦即，（1)在預先調製的含有（a)農藥有效成分、（b)—般式 (1)表示的化合物、（c)碘價小於20的加氫磷脂質、（d)含有 碳原子數6〜20的烷基之界面活性劑，及依需求所添加的 (f)水溶性蛋白質之混合物中加入水，再以高速攪拌機攪拌 的方法。 (2)在已經溶解一部分（d)界面活性劑的水中，加入預先 調製的含有（a)農藥有效成分、（b)—般式（1)表示的化合物 、（c)碘價小於20的加氫磷脂質、（d)界面活性劑的剩餘部 -12- 1241162 五、發明説明（11 ) 份、及依需求所添加的（〇水溶性蛋白質之混合物，再以高 速攪拌機攪拌的方法等。 本發明的水性懸浮型農藥製劑可藉由高速均化器和高壓 乳化機等達到更微粒子化。 如此製得的本發明水性懸浮型農藥製劑中的分散顆粒， 可能因水不溶性的（a)農藥有效成分因爲被（b)〜（d)成份包 圍，故形成穩定且具有水分散性的分散顆粒。 使用雷射繞射散射式粒度分布到測定裝置來測定本發明 水性懸浮型農藥製劑中的分散顆粒之平均粒徑，以0.1〜 2 0 // m的範圍較佳，又以0.5〜7 μηι的範圍更理想。因雷 射繞射散射式粒度分布計無法測定〇. 1 // m以下的粒徑， 以及水性懸浮型農藥製劑中分散顆粒的平均粒徑即使小於 〇. 1 μ m在使用上亦不會發生問題，因此不設定水性懸浮 型農藥製劑中平均粒徑的下限。 本發明的水性懸浮型農藥製劑的黏度以50〜5000mPa% 的範圍較理想。隨著增加（b)—般式（1)表示的化合物、（c) 碘價小於20的加氫磷脂質、（d)含有碳原子數6〜20的烷 基之界面活性劑，及依需求而添加的（f)水溶性蛋白質之添 加比例，水性懸浮型農藥製劑的黏度有增高的趨勢，除了 可增加分散顆粒的穩定性之外，亦可加強因黏性所產生抑 制分散顆粒沉澱的效果，對懸浮劑的穩定性而言是有利的 。惟從使用時的方便性和以水稀釋的簡易性之觀點，水性 懸浮型農藥製劑的黏度以100〜lOOOmPay的範圍特別適 用。 -13- 1241162 五、發明説明（12 ) 【實例】 其次，以實例及比較例說明本發明，惟本發明不受限於 此。又，除另有說明，其中的「單位」及「％」各表示「 重量單位」及「重量％」。 [實例1] 將亞胺八勁烷基苄基酸鹽30單位、十二醇3.7單位、 加氫大豆卵磷脂（日淸製油股份公司製的「貝西斯LP-20H」 、碘價=7.7)2單位、酪蛋白鈉0.5單位、己甘油十八酸酯 4單位及乙二醇5單位混合，加熱至70°C成均勻的混合物 後，再將此混合物保溫在50t，攪拌的同時緩慢地加入水 ，製得懸浮劑100單位。利用高速攪拌機3000rpm攪拌此 懸浮劑1 〇分鐘，製得水性懸浮型農藥製劑。 使用雷射繞射散射式粒度分布計測定製得的水性懸浮型 農藥製劑的平均粒徑，結果爲4.4 // m。使用B型黏度計 (30rpm/20°C)測定黏度的結果爲170mPa*s。 [實例2] 將亞胺八勁烷基苄基酸鹽30單位、十二醇3.7單位、 加氫大豆卵磷脂（日淸製油股份公司製的「貝西斯LP-20H」 、碘價=6.7)2單位、乳白蛋白水解物（和光純藥工業股份 公司製）〇.5單位、十甘油十二酸酯2單位及十甘油十八酸 酯2單位及乙二醇5單位混合，加熱至7(TC成均勻的混合 物後，再將此混合物保溫在5(TC，攪拌的同時緩慢地加入 水，製得懸浮劑100單位。利用高速攪拌機300〇rpm攪拌 此懸浮劑1 0分鐘，製得水性懸浮型農藥製劑。 -14- 1241162 五、發明説明（13 ) 進行和實例1相同的步驟，測定平均粒徑及黏度的結果 分別爲 5.2 // m 及 780mPa*s。 [實例3] 將亞胺八勁烷基苄基酸鹽30單位、十二醇4單位、加 氫大豆卵磷脂（日淸製油股份公司製的「貝西斯LP-20H」 、碘價=7.7)2單位、十甘油十二酸酯4單位及乙二醇5單 位混合，加熱至7(TC成均勻的混合物後，再將此混合物保 溫在50°C，攪拌的同時緩慢地加入水，製得懸浮劑1 〇〇單 位。利用高速攪拌機3000rpm攪拌此懸浮劑10分鐘，製 得水性懸浮型農藥製劑。 進行和實例1相同的步驟，測定平均粒徑及黏度的結果 分別爲 4.3//m 及 190mPa*s。 [實例4] 將亞胺八勁烷基苄基酸鹽30單位、二乙二醇單-2-乙基 己醚5單位、加氫大豆卵磷脂（日淸製油股份公司製的「 貝西斯LP-20H」、碘價=7.7)2單位、酪蛋白鈉0.5單位、 己甘油十八酸酯4單位及乙二醇5單位混合，加熱至70t 成均勻的混合物後，再將此混合物保溫在5(TC，攪拌的同 時緩慢地加入水，製得懸浮劑1 〇〇單位。利用高速攪拌機 3000rpm攪拌此懸浮劑10分鐘，製得水性懸浮型農藥製 劑。 進行和實例1相同的步驟，測定平均粒徑及黏度的結果 分別爲 3.5 // m 及 280mPa*s。 -15- 1241162 五、發明説明（14 ) [比較例1] 將亞胺八勁烷基苄基酸鹽30單位、十二醇2單位及油 醇2單位、大豆卵磷脂（日淸製油股份公司製的「貝西斯 1^-2(^」、碘價=8 0)2單位、十甘油十二酸酯2單位、十 甘油油酸酯1.5單位及乙二醇5單位混合，加熱至70°C成 均勻的混合物後，再將此混合物保溫在50°C，攪拌的同時 緩慢地加入水，製得懸浮劑1 〇〇單位。利用高速攪拌機 lOOOOrpm攪拌此懸浮劑10分鐘，製得水性懸浮型農藥製 劑。 進行和實例1相同的步驟，測定平均粒徑及黏度的結果 分別爲 3.2//m 及 480mPa*s。 [比較例2] 將亞胺八勁烷基苄基酸鹽30單位、十二醇4單位、大 豆卵磷脂（日淸製油股份公司製的「貝西斯LP-20H」、碘 價=80)2單位、十甘油十二酸酯4單位及乙二醇5單位混 合，加熱至70t成均勻的混合物後，再將此混合物保溫在 50°C，攪拌的同時緩慢地加入水，製得懸浮劑1 00單位。 利用高速攪拌機lOOOOrpm攪拌此懸浮劑10分鐘，製得水 性懸浮型農藥製劑。 進行和實例1相同的步驟，測定平均粒徑及黏度的結果 分別爲 4.4//m 及 250mPa，s。 [比較例3] 將亞胺八勁烷基苄基酸鹽30單位、十二醇4單位、蛋 黃卵磷脂（和光純藥工業股份公司、碘價=60)2單位、十甘 -16- 1241162 五、發明説明（15 ) 油十二酸酯4單位及乙二醇5單位混合，加熱至7〇°C成均 勻的混合物後，再將此混合物保溫在50°C，攪拌的同時緩 慢地加入水，製得懸浮劑1 00單位。利用高速攪拌機 lOOOOrpm攪拌此懸浮劑10分鐘，製得水性懸浮型農藥製 劑。 進行和實例1相同的步驟，測定平均粒徑及黏度的結果 分別爲 5.2// m 及 340mPa*s。 [比較例4] 將亞胺八勁烷基苄基酸鹽30單位、一縮二丙二醇單丁 醚5單位、大豆卵磷脂（日淸製油股份公司製的「貝西斯 LP-20H」、碘價=80)2單位、十甘油十二酸酯4單位及乙 二醇5單位混合，加熱至7(TC成均勻的混合物後，再將此 混合物保溫在50°C，攪拌的同時緩慢地加入水，製得懸浮 劑100單位。利用高速攪拌機3000rpm攪拌此懸浮劑10 分鐘，製得水性懸浮型農藥製劑。 將調製後的水性懸浮型農藥製劑隨即進行和實例1相同 的步驟，測定平均粒徑及黏度結果分別爲10.8// m及 1090mPa”。但是，在40°C靜置3日後會沉澱分離出黃色 的黏稠物，穩定的分散狀態被破壞。 (試驗例1)高溫條件下的保存試驗 將調製的水性懸浮型農藥製劑放入500ml的玻璃瓶中， 靜置保存在50°C的恆溫器1 2週。進行下列各種試驗其結 果如表1所示。 <保存穩定性試驗> -17- 1241162 五、發明説明（16) 觀察保存結束時試驗品的懸浮狀態◦並在20°C保W^TT 小時，調查懸浮狀態的復原性。 根據下述基準評估試結果。 ◎:懸浮狀態非常良好。農樂有效成分在水中的分散情形 良好。 〇：懸浮狀態良好。上層稍微有水分離現象，但若以手搖 動容器則容易地均勻分散。 △:懸浮狀態稍微不佳。部份懸浮物呈黏稠狀態附著在容 器壁上，若以棒狀物等攪拌則分散。 X:懸浮狀態不佳。大部份懸浮物呈凝膠狀，有部份更呈 凝集現象，即使以棒狀物攪拌仍不易分散。 <是否有結晶析出> 經過12週靜置保存的試驗品在20°c保存24小時後稀 釋500倍，使用光學顯微鏡觀察此稀釋中是否有結晶析出。 <篩殘留物的測定> 經過12週靜置保存的試驗品在20°C保存24小時後， 以水1 L稀釋50g的試驗品。將全量稀釋液通過網目爲 45 // m的篩。接著，將水1 L注入篩並使篩水平振動，重 覆操作此水淸洗過程5回。水淸洗後測定篩網上的析出物 ，根據下式計算結晶析出的比例。 結晶析出比例（重量％)=[析出物（g)]/[試驗品50g中的 (a) + (b) + (c) + (d) + (f)的含量（g)]xl00 (式中，（a)表示爲農藥有效成分的重量、（b)爲一般式（1)表 示的化合物的重量、（c)爲碘價小於20的加氫磷脂質的重 -18- 1241162 i、發明説明（17 ) 量、（d)爲含有碳原子數6〜20的院基之界面活性劑之重里 、（f)爲水溶性蛋白質的重量。） 表1 實例 1 實例 2 實例 3 實例 4 比較例 1 比較例 2 比較例 3 保 存 穩 定 ft 保存結 束時 ◎ ◎ ◎ 〇 ◎ ◎ 〇 2 0 〇C 復 原後 ◎ ◎ ◎ ◎ ◎ ◎ 〇 結晶析出 _有無 Μ y \ nn 無 無 Μ j\w 無 Μ 川、 Μ j\w 篩殘留物 _的比例 0 0 0 0 0 0 0 一 (試驗例2)高溫·低溫週期條件下的保存試驗 將調製好的水性懸浮型農藥製劑裝入500ml的玻璃瓶中 ，恒溫50°C保存3日後，在12小時內使從50°C冷卻至 -l〇°C，又在恒溫-10°C保存3日後，在12小時內使從 -HTC昇溫至5(TC，以此爲1個週期（1星期）進行保存12 個週期。和試驗例1相同，進行保存穩定性試驗、是否有 結晶析出、測出篩殘留物等。其結果如表2所示。 比較例3調製的水性懸浮型農藥製劑在保存試驗結束時 ，有些微環狀固化物附著在液面上方的容器壁上。經過 20°C的復原後在上層發生水分離現象。篩殘留比例爲1重 量％。 -19- 1241162 五、發明説明（18 ) 表2 實例 1 實例 2 實例 3 實例 4 比較例 1 比較例 2 比較例 3 保 存 穩 定 性 保存結 束時 ◎ ◎ ◎ 〇 〇 〇 Δ 2 0 〇C 復 原後 ◎ ◎ ◎ ◎ 〇 ◎ 〇 結晶祈出 有無 無 Μ J » ΝΝ Μ ^\ \ \ 無 無 Μ >\ νν 篩殘留物 的比例 0 0 0 S 0 0 0 1 (試驗例3)低溫條件下的保存試驄 將調製好的水性懸浮型農藥製劑裝入500ml的玻璃瓶中 ，在-5 °C保存12星期。和試驗例1相同，進行保存穩定 性試驗、是否有結晶析出、測出篩殘留物等。其結果如表 3所示。實例3調製的水性懸浮型農藥製劑在保存試驗結 束時呈現乳液狀的固化狀態，但經過20°C的復原後恢復良 好的懸浮狀態。相對於此，比較例1調製的水性懸浮型農 藥製劑在保存試驗結束時部份呈現黏稠狀態，即使經過 的復原後在上層仍發生水分離現象，而篩殘留物會阻 塞篩網。篩殘留比例爲2重量％。 比較例3調製的水性懸浮型農藥製劑在保存試驗結束時 呈現乳液狀固化狀態，即使經過20°C的復原後在上層發生 水分離現象，而篩殘留物會阻塞篩網。篩殘留比例爲3重 量％。 -20- 1241162 五、發明説明（19 ) 表3 實例 1 實例 2 實例 3 實例 4 比較例 1 比較例 2 比較例 3 保 保存結 ◎ ◎ -* 1 ◎ △ -*1 -*1 存 束時 穩 2 0°C 復 ◎ ◎ ◎ ◎ 〇 〇 Δ 定 原後 性 結晶析出 Μ j\\\ Μ y\s\ 無 Μ j\\\ 有 有 有 有無 篩殘留物 0 0 0 0 2 2 3 的比例 * 1 :呈現乳液狀的固化狀態 (試驗例4)低溫週期條件下的保存試驗 將調製好的水性懸浮型農藥製劑裝入500ml的玻璃瓶中 ，恒溫51保存6小時後，在6小時內使從51冷卻至 -l〇°C，又在恒溫-1(TC保存6小時後，在6小時內使從 -l〇°C昇溫至5°C，以此爲1個週期（24小時）進行保存84 個週期（12星期）。和試驗例1相同，進行保存穩定性試驗 、是否有結晶析出、測出篩殘留物等。其結果如表4所示。 實例3調製的水性懸浮型農藥製劑在保存試驗結束時呈 現乳液狀的固化狀態，但經過20°C的復原後恢復良好的懸 浮狀態。相對於此，比較例1、2及3調製的水性懸浮型 -21- 1241162 五、發明説明（2G) 農藥製劑在保存試驗結束時部份呈現乳液狀的固化狀態， 即使經過20°C的復原後仍不恢復良好的懸浮狀態。因此， 發生篩殘留物阻塞篩網的現象，因1次的操作不易進行全 部的篩過濾，故分3次進行過濾。篩殘留比例比較例1爲 1 2重量％、比較例2爲9重量％、比較例3爲1 8重量％。 表4 實例 1 實例 2 實例 3 實例 4 比較例 1 比較例 2 比較例 3 保 存 穩 定 性 保存結 束時 ◎ ◎ -*1 ◎ -* 1 -*1 -*1 2〇t：復 原後 ◎ ◎ ◎ ◎ X X X 結晶析出 有無 Μ j\ \\ Μ ^\\\ 並 "\、 Μ ^\\\ 有 有 有 篩殘留物 的比例 0 0 0 0 12 9 18 :1 :呈現乳液狀的固化狀態 【工業上的應用】 本發明的水性懸浮型農藥製劑，不僅在季節間的長週期 中溫度變化大的保存條件下儲存穩定性優越，即使晝夜短 週期的溫度在5°C〜- l〇°C的範圍內變化的冬季長期保存下 ，保存穩定性亦佳。 -22-R-0- (CH2CH2〇) nH (wherein R is an alkyl or alkenyl group having 8 to 18 carbon atoms, and n is an integer of 0 to 4), a compound represented by (0 phospholipid, (d) A surfactant containing an alkyl group having 6 to 20 carbon atoms, and (e) water, wherein (c) the phospholipid is a hydrogenated phospholipid having an iodine value of less than 20. [best form for carrying out the invention] The following order The components of the aqueous suspension pesticide formulation of the present invention will be described. (A) 1, Γ-iminebis (octamethylene) difluorene = ginseng (alkylbenzenesulfonate) is the aqueous suspension of the present invention. Active ingredients of pesticide formulations (hereinafter referred to as (a) active ingredients of pesticides). The alkylbenzene sulfonates of (a) active ingredients of pesticides used in the present invention are those containing alkyl groups having 1 to 20 carbon atoms. A benzene sulfonate is preferable. From the viewpoint of prevention of phytotoxicity and efficacy, a benzene sulfonate containing an alkyl group having 4 to 18 carbon atoms is particularly preferable. A benzene sulfonate containing an alkyl group having 10 to 13 carbon atoms Acid salts are more suitable. These (a) pesticide active ingredients are essentially water-insoluble ingredients. Also, I, Γ-iminebis (octamethylene) difluorene = The alkylbenzene sulfonate in ginseng (alkylbenzene sulfonate) is a benzene sulfonate containing an alkyl group having 10 to 13 carbon atoms, which is called "imine octadecyl benzyl acid salt". Pesticide components. Next, (b) —the compound represented by the general formula (1) will be described. (B) The compound represented by the general formula (1) used in the present invention has an action of 1 in the aqueous suspension pesticide formulation of the present invention. Dispersion stabilizer. In the general formula (1), a compound aliphatic compound having n = 0 and a saturated aliphatic alcohol having 8 to 18 carbon atoms is not contained in the compound-based molecule. In the general formula (1), n = 1 Compounds with 8 to 18 carbon atoms are saturated-6-1241162 5. Description of the invention (5) Alcohols in which aliphatic alcohols and ethylene glycol are bonded by ether, generally called polyoxyethylene (1 mole) monomer Alkyl ethers are usually abbreviated as "mono" and are simply referred to as polyoxyethylene (1 mole) alkyl ethers. Also, for example, the alcohol represented by n = 3 refers to a saturated aliphatic alcohol and triethylene glycol and ether-bonded Alcohols, commonly referred to as polyoxyethylene (3 mol) alkyl ethers. Saturated aliphatic alcohols with 8 to 18 carbon atoms can be linear or branched It is preferable to be a straight chain. The more preferable saturated aliphatic alcohol is an alcohol having the same carbon number as the alkyl group of the alkylbenzene sulfonate constituting (a) the active ingredient of the pesticide, and the carbon number is 10 to 13 The linear alcohols are particularly preferred. The saturated aliphatic alcohols represented by the general formula (1), for example, linear alkanols such as octanol, decanol, dodecanol, cetyl alcohol, and stearyl alcohol; 2-ethyl- Hexanol, 2-ethyl-hexanediethylene glycol (alias: diethylene glycol mono-2-ethylhexyl ether) and other branched alkyl alcohols; polyoxyethylene (1 to 4 moles) dodecyl ether, Polyoxyvinyl (1 to 4 moles) hexadecyl ether and other polyoxyethylene alkyl moieties having a repeating number n of 1 to 4 etc. Next, (c) used in the present invention will be described. Hydrolyzed phospholipids with an iodine value of less than 20. The (c) hydrogenated phospholipid having an iodine value of less than 20 used in the present invention acts as a dispersion stabilizer in the aqueous suspension pesticide formulation of the present invention. Hydrolyzed phospholipids are hydrolyzed lecithins produced from oilseeds such as soybeans and rapeseed or from animal lipids such as egg yolk until the iodine value is less than 20, thereby converting most of the unsaturated fatty acids of the phospholipids into saturated fatty acids. The present invention is particularly suitable for hydrogenated phospholipids having an iodine value of less than 10. Among these hydrogenated phospholipids, hydrogenated soybean egg phosphorous is particularly preferable from the viewpoints of low price and quality changes made from natural products. -7- 1241162 V. Description of the invention (6) The hydrogenated phospholipids (C) with an iodine value of less than 20, especially hydrogenated lecithin or water-soluble proteins used in the present invention are widely used in the field of perfumery cosmetics or food. Environmental or human safety. In addition, if the compound represented by the general formula (1) used in the present invention can be selectively applied to the field of perfumery cosmetics or food, the safety of the present aqueous suspension preparation can be improved. These functions are dispersion stabilizers for aqueous suspension formulations of active ingredients of pesticides. Next, (d) a surfactant containing an alkyl group having 6 to 20 carbon atoms used in the present invention will be described. The surfactant (d) containing an alkyl group having 6 to 20 carbon atoms used in the present invention may be ionic or nonionic. The alkyl group constituting the above-mentioned surfactant may be linear or branched, and linear is more suitable. The alkyl group constituting the surfactant and the alkylbenzene sulfonate group constituting (a) the active ingredient of the pesticide have the same number of carbon atoms, and an alkyl group having 10 to 18 carbon atoms is more preferable. An alkyl group having 10 to 13 carbon atoms is particularly preferred. From the viewpoint of a dispersion stabilizer, the alkyl group of the compound represented by (b) to the general formula (1) and the alkyl group of the surfactant (d) containing an alkyl group having 6 to 20 carbon atoms are all used in the present invention. Those having the same number of carbon atoms as the alkyl group of the alkylbenzene sulfonate constituting (a) the active ingredient of the pesticide are particularly preferred, and alkyl groups having 10 to 13 carbon atoms are particularly preferred. However, most of the raw materials used in (d) surfactants containing alkyl groups having 6 to 20 carbon atoms are prepared from natural products. The number of carbon atoms in alkyl groups has a distribution range. If it contains carbon atoms in an ideal range, As the alkyl group having 10 to 18 carbon atoms, a surfactant containing an alkyl group having 6 to 20 carbon atoms can be used. (D) Interfacial activity containing an alkyl group having 6 to 20 carbon atoms used in the present invention 1241162 5. Description of the invention (7) The agent can be roughly divided into (d-1) polyepoxide nonionic surfactant (D-2) fatty acid ester nonionic surfactant, (d-3) anionic surfactant, (d-4) cationic surfactant, (d-5) diionic surfactant. (d-1) Polyepoxide-based nonionic surfactants such as polyoxyalkylene (20 mol) dodecyl ether, polyoxyethylene (15 mol) cetyl ether, and other polyoxyalkylene alkyl groups Ethers; polyoxyethylene (12 mol) dodecyl amino ethers and other polyoxyalkylene alkylamino ethers. (d-2) Fatty acid ester nonionic surfactants, for example, polyglycerol saturated fatty acid esters such as decaglyceryl dodecanoate, decaglyceryl tetradecanoate, and hexaglyceryl stearate; polyethylene glycol (average molecular weight) 600) Polyalkylene glycol saturated fatty acid esters such as dodecyl ester; Polyoxyethylene polypropylene glycol block copolymer octadecanoate and other polyoxyalkylene polypropylene glycol saturated fatty acid esters. (d-3) Anionic surfactants such as alkyl sulfates such as sodium lauryl sulfate; polyoxyethylene (20 mol) dodecyl ether ammonium sulfates and other polyoxyalkylene alkyl sulfates Wait. (d-4) Cationic surfactants, for example, alkylammonium salts such as cetyltrimethylammonium chloride; polyoxyethylene (10 mol) octadecylmethylammonium chloride, and other polyoxyalkylenes Alkyl alkyl ammonium salts and the like. (d-5) Biionic surfactants, for example, alkyltrimethylammonium betaines such as dodecyldimethylammonium trimethylammonium betaine; amination oxygens such as dodecyldimethylammonium oxide Class, etc. Among the above surfactants, the polyglycerol-saturated fatty acid esters in the (d-2) fatty acid esters nonionic surfactants are due to the -9-12124162 of aqueous suspension pesticide formulations. 5. Description of the invention (8) Low temperature stability Good, especially applicable. By using (f) water-soluble protein in the aqueous suspension type pesticide formulation of the present invention, superior storage stability can be obtained. (F) Water-soluble proteins such as milk protein, vegetable protein, animal protein, etc., or protein preparations made of these proteins, for example, one or more selected from skim milk powder, whole milk powder, lactalbumin hydrolysate, casein, Alkali metal salts of casein such as casein sodium, lactoprotein, soybean powder, fish powder, gelatin, protein powder, egg yolk powder, etc., among which casein sodium is particularly suitable. The ratio of the (a) active ingredient of the pesticide in the aqueous suspension pesticide formulation of the present invention is preferably in the range of 1 to 45% by weight, and particularly preferably in the range of 5 to 40% by weight. The ratio of the compound represented by (b) to the general formula (1) in the aqueous suspension pesticide formulation of the present invention is preferably in a range of 0.5 to 10% by weight, and particularly preferably in a range of 1 to 8% by weight. The ratio of (c) hydrogenated phospholipids having an iodine value of less than 20 in the aqueous suspension type agricultural medicinal preparation of the present invention is preferably in the range of 0.5 to 10% by weight, and particularly preferably in the range of 1 to 8% by weight. Furthermore, the ratio of the (d) surfactant containing the alkyl group having 6 to 20 carbon atoms in the aqueous suspension type pesticide formulation of the present invention is 0.5 to 10% by weight. The range is preferably 1 to 8% by weight. The ratio of (e) water in the aqueous suspension type pesticide formulation of the present invention is preferably in the range of 25 to 97.5% by weight. 'It is particularly preferable to be in the range of 36 to 92% by weight. (F) Water-soluble protein is used in combination with the aqueous suspension pesticide preparation of the present invention. The ratio of (0 water-soluble protein in the aqueous suspension pesticide preparation of the present invention is based on the total amount of hydrogenated phospholipid and water-soluble protein. A range of 0.5 to 10% by weight is preferred, and a range of 1 to 8% by weight is particularly desirable. -10- ------- 1241162 V. Description of the Invention (9) The aqueous suspension pesticide formulation of the present invention The proportion of (a) the active ingredient of the pesticide and (b) the compound represented by the general formula (1) is preferably in the range of 0.1: 1 to 90: 1, and more preferably in the range of 0.6: 1 to 40: 1. In addition, the ratio of (a) the active ingredient of the pesticide and (c) the hydrogenated phospholipid with an iodine value of less than 20 in the aqueous suspension pesticide formulation of the present invention is preferably in a range of 0.1: 1 to 90: 1 by weight. A range of 0.6: 1 to 40: 1 is more desirable. The ratio of (a) the active ingredient of the pesticide and (d) the surfactant containing the alkyl group having 6 to 20 carbon atoms in the aqueous suspension pesticide formulation of the present invention The weight ratio is preferably in the range of 0.1: 1 to 90M, and more preferably in the range of 0.6: 1 to 40: 1. The water in the present invention When (f) water-soluble protein is used in a suspension pesticide formulation, (a) the ratio of the active ingredients of the pesticide and (c) the total amount of the hydrolyzed phospholipid with an iodine value of less than 20 to (0 the total amount of both water-soluble proteins, and its weight The ratio is preferably in the range of 0.1: 1 to 90: 1, and more preferably in the range of 0.6: 1 to 40: 1. Moreover, (c) the ratio of hydrolyzed phospholipids with an iodine value of less than 20 and (f) the proportion of water-soluble proteins, The weight ratio is preferably in the range of 0.1: 1 to 1:10. In addition, other optional ingredients can be added to the aqueous suspension pesticide formulation of the present invention without destroying the effect of the present invention. For example, freezing prevention Agents, preservatives, buffering agents, etc. Antifreeze agents such as water-soluble organic solvents such as ethylene glycol, propylene glycol, and propylene glycol monomethyl ether, urea, etc. When the antifreeze agent is used, its amount is used to replace the aqueous suspension pesticide formulation of the present invention. (E) 1/50 ~ 1/4 of the amount of water is more suitable. When preparing the aqueous suspension pesticide formulation of the present invention, the components must be thoroughly mixed. (D) Interface containing an alkyl group having 6 to 20 carbon atoms The active agent is usually added in the whole amount at one time, or part of it can be added in (a) Effective ingredients, (b) -11-1241162 V. Description of the invention (1G) A mixture of a compound represented by general formula (1) and (c) a hydrogenated phospholipid with an iodine value of less than 20, and the remainder is added to ( e) Water. There is no particular limitation on the mixing order of the components other than water, but from the viewpoint of easily forming a homogeneous mixture, 'the compound represented by (b)-general formula (1) and (c) the iodine value of less than 20 are hydrogenated. Phospholipids and (f) water-soluble proteins are mixed as required before adding (a) an active ingredient of a pesticide and (d) a surfactant containing an alkyl group having 6 to 20 carbon atoms. Mixing (a) an active ingredient of a pesticide, (b) a compound represented by the general formula (1), (c) a hydrogenated phospholipid having an iodine value of less than 20, and (d) an interfacial activity containing an alkyl group having 6 to 20 carbon atoms It is not ideal to add (e) water at the same time. Mixing (a) an active ingredient of a pesticide, (b) a compound represented by the general formula (1), (c) a hydrogenated phospholipid having an iodine value of less than 20, and (d) an interfacial activity of an alkyl group having 6 to 20 carbon atoms In the case of an agent, moderate heating is desirable. In this case, if high temperature is applied, the coloring phenomenon tends to occur, and a more preferable processing temperature is less than 80 ° C, and a range of 50 to 70 ° C is more preferable. The method of adding water to suspend can use a conventionally well-known method. That is, (1) contains (a) a pesticide active ingredient prepared in advance, (b) a compound represented by general formula (1), (c) a hydrogenated phospholipid with an iodine value of less than 20, and (d) contains a carbon atom It is a method of adding 6 to 20 alkyl surfactants and adding (f) a water-soluble protein mixture as required, and stirring with a high-speed mixer. (2) In a part of the water in which (d) the surfactant has been dissolved, add (a) an active ingredient containing pesticides, (b) a compound represented by the general formula (1), (c) Hydrophospholipid, remaining part of (d) surfactant-12-121242 5. Description of the invention (11) parts, and (0) water-soluble protein mixture added as required, and then stirred with a high-speed stirrer, etc. The aqueous suspension pesticide formulation of the present invention can be more micronized by a high-speed homogenizer, a high-pressure emulsifier, etc. The dispersed particles in the aqueous suspension pesticide formulation of the present invention thus prepared may be effective due to the water-insoluble (a) pesticide Because the components are surrounded by the components (b) to (d), stable and water-dispersible dispersed particles are formed. Laser diffraction scattering particle size distribution is used to measure the dispersed particles in the aqueous suspension pesticide formulation of the present invention. The average particle size is preferably in the range of 0.1 to 2 0 // m, and more preferably in the range of 0.5 to 7 μηι. Due to the laser diffraction scattering particle size distribution meter, it is impossible to measure the particle size of 0.1 // m or less Path to Even if the average particle diameter of the dispersed particles in the aqueous suspension pesticide formulation is less than 0.1 μm, there is no problem in use, so the lower limit of the average particle diameter in the aqueous suspension pesticide formulation is not set. The aqueous suspension type of the present invention The viscosity of the pesticide formulation is preferably in the range of 50 to 5000 mPa%. With increasing (b) —the compound represented by the general formula (1), (c) a hydrogenated phospholipid with an iodine value of less than 20, and (d) the number of carbon atoms 6-20 alkyl surfactants, and (f) the proportion of water-soluble proteins added as required, the viscosity of aqueous suspension pesticide formulations tends to increase, in addition to increasing the stability of dispersed particles, It can also enhance the effect of inhibiting the precipitation of dispersed particles due to viscosity, which is beneficial to the stability of the suspending agent. However, from the viewpoint of convenience in use and ease of dilution with water, The viscosity is particularly suitable for the range of 100 ~ 1000mPay. -13- 1241162 V. Description of the Invention (12) [Example] Second, the invention will be described with examples and comparative examples, but the invention is not limited to this. Also, In addition, the "unit" and "%" each indicate "weight unit" and "% by weight." [Example 1] 30 units of imine octadecyl benzyl acid salt, 3.7 units of dodecanol, and Hydrogen soybean lecithin ("Bexis LP-20H" manufactured by Nisshin Oil Co., Ltd., iodine value = 7.7) 2 units, 0.5 unit casein sodium, 4 units hexaglyceryl stearate, and 5 units ethylene glycol After heating to 70 ° C to form a homogeneous mixture, the mixture was kept at 50t, and water was slowly added while stirring to obtain 100 units of suspension agent. The suspension agent was stirred at 3000 rpm for 10 minutes using a high-speed mixer to obtain an aqueous solution. Suspension pesticide formulation. The average particle diameter of the prepared aqueous suspension pesticide formulation was measured using a laser diffraction scattering particle size distribution meter, and the result was 4.4 // m. The viscosity was measured using a B-type viscometer (30 rpm / 20 ° C) and it was 170 mPa * s. [Example 2] 30 units of imine octadecyl benzyl acid salt, 3.7 units of dodecanol, hydrogenated soybean lecithin ("Bexis LP-20H" manufactured by Nissin Oil Co., Ltd., iodine value = 6.7 ) 2 units, lactalbumin hydrolysate (manufactured by Wako Pure Chemical Industries, Ltd.) 0.5 units, 2 units of ten glyceryl dodecanoate, 2 units of ten glyceryl stearate, and 5 units of ethylene glycol, and heated to 7 After the TC becomes a homogeneous mixture, the mixture is kept at 5 ° C, and the water is slowly added while stirring to obtain 100 units of suspension agent. The suspension agent is stirred at 300 rpm for 10 minutes using a high-speed mixer to obtain an aqueous solution. Suspension pesticide formulation. -14- 1241162 V. Description of the invention (13) The same steps as in Example 1 were performed, and the results of measuring the average particle size and viscosity were 5.2 // m and 780 mPa * s respectively. [Example 3] Imine Octadecyl benzyl 30 units, dodecanol 4 units, hydrogenated soybean lecithin ("Bexis LP-20H" manufactured by Nissin Oil Co., Ltd., iodine price = 7.7), 2 units, 10 units Mix 4 units of diester and 5 units of ethylene glycol and heat to 7 (TC to form a homogeneous mixture. The mixture was kept at 50 ° C, and water was slowly added while stirring to obtain 100 units of suspension agent. The suspension agent was stirred at 3000 rpm for 10 minutes using a high-speed mixer to prepare an aqueous suspension pesticide formulation. The same steps as in Example 1 were performed. The results of measuring the average particle diameter and viscosity were 4.3 // m and 190 mPa * s, respectively. [Example 4] 30 units of imine octadecyl benzyl acid salt and diethylene glycol mono-2-ethylhexyl ether 5 units, hydrogenated soybean lecithin ("Bexis LP-20H" manufactured by Nisshin Oil Co., Ltd., iodine value = 7.7) 2 units, 0.5 casein sodium, 4 units hexadecyl glycerol, and 2 units Mix 5 units of alcohol, heat to 70t to form a homogeneous mixture, then keep the mixture at 5 ° C, and slowly add water while stirring to obtain 100 units of suspending agent. Use a high-speed stirrer to stir this suspending agent 10 at 3000 rpm. An aqueous suspension pesticide formulation was prepared in minutes. The same procedures as in Example 1 were performed, and the results of measuring the average particle diameter and viscosity were 3.5 // m and 280 mPa * s, respectively. -15- 1241162 V. Description of the invention (14) [Comparison Example 1] The imine octadecyl benzyl acid 30 units, 2 units of dodecanol, 2 units of oleyl alcohol, 2 units of soybean lecithin ("Bexis 1 ^ -2 (^", iodine price = 80) manufactured by Nissin Oil Co., Ltd., 12 units of ten glycerol 2 units of acid ester, 1.5 units of ten glycerol oleate, and 5 units of ethylene glycol are mixed, heated to 70 ° C to form a homogeneous mixture, and then the mixture is kept at 50 ° C. While stirring, slowly add water to prepare 100 units of suspending agent were obtained. The suspending agent was stirred at 1000 rpm for 10 minutes using a high-speed stirrer to prepare an aqueous suspension type pesticide formulation. Following the same procedure as in Example 1, the results of measuring the average particle diameter and viscosity were 3.2 // m and 480 mPa * s, respectively. [Comparative Example 2] 30 units of imine octadecyl benzyl acid salt, 4 units of dodecyl alcohol, and soybean lecithin ("Bexis LP-20H" manufactured by Nisshin Oil Co., Ltd., iodine value = 80) Mix 2 units, 4 units of ten glyceryl dodecanoate and 5 units of ethylene glycol, heat to 70t to form a homogeneous mixture, and then keep the mixture at 50 ° C. Slowly add water while stirring to prepare a suspension agent. 1 00 units. This suspension was agitated with a high-speed stirrer at 1000 rpm for 10 minutes to prepare an aqueous suspension pesticide formulation. The same procedure as in Example 1 was performed, and the results of measuring the average particle diameter and viscosity were 4.4 // m and 250 mPa, s, respectively. [Comparative Example 3] 30 units of imine octadecyl benzyl acid salt, 4 units of dodecanol, 2 units of egg yolk lecithin (Wako Pure Chemical Industries, Ltd., iodine price = 60), Shikan-16-1241162 V. Description of the invention (15) 4 units of oil dodecanoate and 5 units of ethylene glycol are mixed, heated to 70 ° C to form a homogeneous mixture, and then the mixture is kept at 50 ° C, and slowly added while stirring. Water to make 100 units of suspension. This suspension was stirred at 1000 rpm for 10 minutes using a high-speed mixer to prepare an aqueous suspension pesticide formulation. Following the same procedure as in Example 1, the results of measuring the average particle diameter and viscosity were 5.2 // m and 340 mPa * s, respectively. [Comparative Example 4] 30 units of imine octadecyl benzyl acid salt, 5 units of dipropylene glycol monobutyl ether, soybean lecithin ("Bexis LP-20H" manufactured by Nissin Oil Co., Ltd., iodine Price = 80) 2 units, 10 units of ten glyceryl dodecanoate, and 5 units of ethylene glycol, heat to 7 (TC into a homogeneous mixture, then keep the mixture at 50 ° C, slowly add while stirring 100 units of suspension agent were prepared. The suspension agent was stirred at 3000 rpm for 10 minutes using a high-speed mixer to prepare an aqueous suspension pesticide preparation. The prepared aqueous suspension pesticide preparation was then subjected to the same steps as in Example 1 to determine the average particle size. And the viscosity results were 10.8 // m and 1090 mPa, respectively. However, after standing at 40 ° C for 3 days, a yellow sticky substance was precipitated and separated, and the stable dispersion state was destroyed. (Test Example 1) Storage test under high temperature conditions The prepared aqueous suspension pesticide formulation was put into a 500 ml glass bottle, and it was left to stand in a thermostat at 50 ° C for 12 weeks. The following various tests were performed, and the results are shown in Table 1. < Storage stability test > -17- 1241162 V. Description of the invention 16) Observe the suspension state of the test product at the end of storage. Investigate the restorability of the suspension state at 20 ° C for W ^ TT hours. Evaluate the test results according to the following criteria. ◎: The suspension state is very good. The dispersion in water is good. ○: The suspension state is good. The upper layer has a slight water separation phenomenon, but if the container is shaken by hand, it is easily and uniformly dispersed. △: The suspension state is slightly poor. Part of the suspended matter is sticky to the container wall If it is stirred with a stick, etc., it will be dispersed. X: The suspension state is not good. Most of the suspended matter is gel-like, and some are more agglutinated. Even if it is stirred with a stick, it is not easy to disperse. ≪ Precipitation of crystals> The test article stored for 12 weeks was stored at 20 ° C for 24 hours and then diluted 500 times. The optical microscope was used to observe whether crystals were precipitated during the dilution. ≪ Measurement of sieve residues > After 12 weeks After the test product stored at 20 ° C was stored for 24 hours, 50 g of the test product was diluted with 1 L of water. The entire dilution was passed through a sieve with a mesh of 45 // m. Next, 1 L of water was poured into the sieve and the sieve was filtered. Horizontal vibration Repeat this process of washing with water 5 times. After washing with water, measure the precipitate on the sieve, and calculate the proportion of crystal precipitation according to the following formula. Crystal precipitation ratio (wt%) = [precipitate (g)] / [test The content of (a) + (b) + (c) + (d) + (f) in 50 g of product (g)] xl00 (where (a) is the weight of the active ingredient of the pesticide, and (b) is the general The weight of the compound represented by formula (1), (c) is the weight of a hydrogenated phospholipid with an iodine value of less than 20-181241162 i, the description of the invention (17), and (d) is a compound containing 6 to 20 carbon atoms. Among the weight of the surfactants in the base, (f) is the weight of water-soluble protein. ) Table 1 Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Storage stability ft At the end of storage ◎ ◎ ◎ ◎ ◎ 〇 2 0 〇C After restoration ◎ ◎ ◎ ◎ ◎ ◎ 〇 Crystal precipitation_presence or absence Μ y \ nn Without Μ j \ w Without Μ Chuan, Μ j \ w The proportion of sieve residue_ 0 0 0 0 0 0 0 (Test Example 2) Storage test under high temperature and low temperature cycle conditions will be prepared Aqueous suspension type pesticide preparations were put into 500ml glass bottles, and stored at a constant temperature of 50 ° C for 3 days, and then cooled from 50 ° C to -10 ° C within 12 hours, and stored at a constant temperature of -10 ° C for 3 days. The temperature was increased from -HTC to 5 (TC) within 12 hours, and the cycle was stored for one cycle (one week) for 12 cycles. As in Test Example 1, a storage stability test was performed, whether crystals were precipitated, and sieve residue was measured. The results are shown in Table 2. At the end of the storage test of the aqueous suspension pesticide formulation prepared in Comparative Example 3, some microcyclic solidified substances adhered to the container wall above the liquid surface. After 20 ° C recovery Water separation occurs in the upper layer. The sieve residual ratio is 1% by weight. -19- 1241162 V. Description of the invention (18) Table 2 Example 1 Example 2 Example 3 Example 4 Comparative example 1 Comparative example 2 Comparative example 3 Storage stability At the end of storage ◎ ◎ ◎ 〇〇〇Δ 2 0 〇C After recovery ◎ ◎ ◎ ◎ 〇 ◎ 〇 Crystallization for the presence or absence of Μ J »ΝΝ Μ ^ \ \ \ No without Μ > \ νν Ratio of sieve residue 0 0 0 S 0 0 0 1 (Test Example 3) Storage test under low temperature conditions The prepared aqueous suspension pesticide formulation was put into a 500 ml glass bottle and stored at -5 ° C for 12 weeks. As in Test Example 1, the storage stability test was performed, whether there was crystal precipitation, and the sieve residue was detected. The results are shown in Table 3. At the end of the storage test, the aqueous suspension pesticide formulation prepared in Example 3 exhibited an emulsion-like solidified state, but returned to a good suspended state after recovery at 20 ° C. In contrast, Comparative Example 1 was prepared At the end of the storage test, some of the aqueous suspension pesticide formulations were sticky. Even after recovery, water separation still occurred in the upper layer, and the sieve residue would block the sieve. The sieve residual ratio was 2% by weight. At the end of the storage test, the aqueous suspension pesticide formulation prepared in Comparative Example 3 exhibited an emulsion-like solidified state. Even after water recovery at 20 ° C, water separation occurred in the upper layer, and the sieve residue blocked the sieve. The sieve residual ratio was 3 % By weight. -20- 1241162 V. Description of the invention (19) Table 3 Example 1 Example 2 Example 3 Example 4 Comparative example 1 Comparative example 2 Comparative example 3 Storage retention ◎ ◎-* 1 ◎ △-* 1-* 1 Save Beam stability at 2 ° C. ◎ ◎ ◎ ◎ 〇〇Δ After the original crystals are precipitated, Μ j \\\ Μ y \ s \ No Μ j \\\ With or without sieve residue 0 0 0 0 2 2 Ratio of 3 * 1: Emulsion-like cured state (Test Example 4) Storage test under low-temperature cycle conditions The prepared aqueous suspension pesticide formulation was put into a 500ml glass bottle, and stored at a constant temperature of 51 for 6 hours. Cool down from 51 to -10 ° C in 1 hour, and keep it at -1 (TC for 6 hours, then raise the temperature from -10 ° C to 5 ° C in 6 hours, which is a cycle (24 Hours) for 84 cycles (12 weeks). As in Test Example 1, a storage stability test was performed, whether crystals were precipitated, and sieve residues were detected. The results are shown in Table 4. The aqueous suspension pesticide formulation prepared in Example 3 showed an emulsion-like solidified state at the end of the storage test, but returned to a good suspended state after recovery at 20 ° C. In contrast, the aqueous suspensions prepared by Comparative Examples 1, 2 and 3-21-1241162 V. Description of the invention (2G) The pesticide preparations partially showed an emulsion-like solidified state at the end of the storage test, even after 20 ° C recovery It still does not return to a good suspension afterwards. Therefore, the sieve residue clogged the sieve, and it was not easy to perform the whole sieve filtration in one operation, so the filtration was performed in three times. The sieve residual ratio was 12% by weight in Comparative Example 1, 9% by weight in Comparative Example 2, and 18% by weight in Comparative Example 3. Table 4 Example 1 Example 2 Example 3 Example 4 Comparative example 1 Comparative example 2 Comparative example 3 Storage stability At the end of storage ◎-* 1 ◎-* 1-* 1-* 1 2〇t: After restoration ◎ ◎ ◎ ◎ XXX Precipitation of crystals MH j \ \\ Μ ^ \\\ and " \, Μ ^ \\\ ratio of sieve residues 0 0 0 0 12 9 18: 1: presents an emulsion-like solidified state [industrial Application] The aqueous suspension pesticide formulation of the present invention not only has excellent storage stability under the storage condition of large temperature change in long periods between seasons, but also has a short period of time between 5 ° C and -10 ° C. The storage stability is also good under long-term storage in winter, which varies within the range. -twenty two-