201200021 六、發明說明： 【發明所屬之技術領域】 本發明涉及-種農用化學組合物。本發明特別涉及一種穩定的、環境 友好的水乳劑（EW)殺蟲製劑’其包含作為殺蟲劑的苯甲醯基臟活性化 合物以及作為溶劑的醚》本發明還涉及製備上述組合物的方法及其在作物 保護中的用途。本發明特別涉及防止殺蟲劑苯曱醯基苯基脲類衍生物的結 晶，以及減少水乳製劑的植物毒性。 【先前技術】 已知的用於控制的昆蟲生長調節劑包括苯甲醯基笨基脲類 (benzoylphenyl urea，BPU)化合物，樣品其實例可選自以下在市面上出售的 化合物·雙苯氟腺、顏腺、氟鈴腺、殺鈴脲、除蟲脲、氣咬脈、氣蟲腺、 多氟脲（noviflumuron)及氟笨脲。苯甲醯基苯基脲類化合物通常以乳劑出 售。然而’此類製劑需要大量有機溶劑，如芳香烴類'氣代烴類等，這些 有機溶劑的毒理和生態毒理雜均廣為人知。基於這些賴的製劑帶來了 毒性、環境和氣味方©關題。因此，持續需要暖抑制環境友好的基於 苯甲酿基苯基腺類化合物的製劑。水乳劑（EW)為一種環境友好的製劑。 水乳劑的實例是本領域所熟知的。 CN10137996描述了-種水乳製劑（EW)，其含有1%至5〇%的風蜗腺 作為活性成分、1%至10%的溶劑、〇5%至5%的防;東劑、〇 1%至1%的抗 泡劑、1%至臟的乳化劑、〇.1%至5%的增_及水份。儘管該製劑比起 同樣活性成分的基於溶劑的乳劑在環境友好方面更可接受，但該製劑中所 使用的溶劑為一甲苯或甲苯’兩者均嚴重損害環境。 需要通過聰環境友好性溶劑纽進現有技術。如果所聊的溶劑可 以為製劑帶來其它益處（制是改善保質期），則其是最有利的。 美國國豕％境保護局對殺蟲製劑中除活性成分以外的成分進行了檢 201200021 查。在歐洲，歐洲共用體委員會正處於立法監管使用揮發性有機化合物 (VOC)的最後階段’會要求含有這些VOC的製劑加上生態標籤。事實上， 加拿大和德國已經有了生態毒性標籤系統。 在這些情況下，希望儘快開發出具有上述問題之傳統農用化學品的替 • 代物，以為市場提供對人類和環境友好，且可實際應用於商業性農業生產 • 的農用化學品。過去曾斌驗或使用過多種替代性溶劑。這些替代性溶劑的 例子包括脂肪烴、醇、二醇、聚乙二醇、二醇醚、酮及具高溶解力的極性 溶劑如γ-丁酸内酯、N-曱基吡咯烧酮等。 脂肪烴類的問題在於其對固體殺蟲劑的溶解力通常較低。其它上述溶 劑雖然適於溶解殺蟲劑，但同時本身亦可溶于水。這種水溶解性導致殺蟲 劑的結晶現象。所述結晶化使得製劑不適於喷麗。 在本發明中’出乎意料地發現，某些雙亞烧基二醇雙/單《4 烷基醚溶劑不僅可以防止笨曱酸基苯基尿素類衍生物在儲存時在水乳劑 (EW)中的結晶，而且這些溶_迄今為止在農用化學製射使用的其它产 劑更為環保。 〃办 【發明内容】 本發明提供了-鶴定的、環境友好的水乳劑(岡殺 =崎及某些W雙道二醇雙/單_CrC4_作為水乳= =(包含-種或多種笨㈣基苯細類作為活性農用化學成分）的: 途°每些作為溶劑的_不但環境友好，而且有利地降 苯基脲類在最終製财的結晶。 ·止本甲基 因此’在第一方面，本發明提供了一種農用化學組合物， 酿基__齡及CrQ雙亞絲二物單《成細/本 (^^^職了—獅地^咖姆組合物： (a) l/o-50/o的本甲醯基苯基脲活性成分； 201200021 (b) 5%-50%的CrC4雙亞烷基二醇雙/單_C丨_c4烷基醚作為溶劑；以及 (c) 選自以下的任選的一種或多種添加劑：表面活性劑、増稠劑、消泡 劑、防凍劑和水；所有成分總共為100% » 在一個實施方案中，所述Cr(：4雙亞烷基二醇雙/單-(VC4烷基醚為選自 以下的一種或多種醚：二乙二醇二甲醚、二乙二醇曱醚、二丙二醇二甲鍵、 二丙二醇甲醚、二丁二醇二曱醚、二丁二醇曱醚、二乙二醇二乙醚、二乙 二醇乙醚、二丙二醇二乙醚，二丙二醇乙醚、二丁二醇二乙醚、二丁二醇 乙醚、一乙二醇二丙醚、二乙二醇丙醚，二丙二醇二丙_、二丙二醇丙醚、 二丁二醇二丙醚、二丁二醇丙醚、二乙二醇二丁醚、二乙二醇丁醚、二丙 二醇二丁醚、二丙二醇丁醚、二丁二醇二丁醚、二丁二醇丁醚及其混合物。 在優選的實施方案中，所述笨曱醯基笨基脲活性成分是至少一種選自 以下的化合物：雙苯氟脲、虱蟎脲、氟鈐脲、殺鈴脲、除蟲脲、氟啶脲、 氟蟲脲、多氟脲及氟苯脲及其混合物。 另一方面，本發明提供了一種配製以苯甲醯基苯基脲類作為活性成分 的農業可接㈣穩定水乳製細方法，其巾所述活性成分與選自—種或多 種CVC4雙亞烷基二醇雙/單/广^烷基醚的溶劑一起配製。特別地，本發 明提供了-種調製農用化學製細方法，所述方法包括以下步驟： 1. 將一種或多種殺蟲活性的苯甲醯基苯基脲與一種或多種c2_C4雙亞 院基二醇雙/單烷基醚混合，以獲得均勻油相； 2. 混合至少一種選自以下的添加劑：表面活性劑 、增稍劑、消泡劑、 防;東劑和水’所有成份總和為1嶋，轉得均勻水相； 3. 利用混合（例如借助設備（如高剪切混合器、高壓孔板均質機等））， 將水相和油相合併，以獲得可分散的水乳劑 (EW)。 本發明的濃縮水乳織現出高度的物理和化學穩定性，制是在·沉 至55 C的溫度_在存儲_未觀察到結晶現象。該製綱表現出改進 的玉衣境友好性β 201200021 【實施方式】 本甲酿基本基腺為水不溶性化合物。這些化合物在市場上被配製成乳 劑(Emulsion Concentrate)產品。乳劑中大量的有機溶劑如二曱苯或甲苯均會 產生問題，特別是當製劑最終使用時會對環境產生污染。因此，持續需要 ' 開發苯甲醯絲細化合物的環境友好製劑。水乳製劑是-種具有降低的 • 對環境科可能的製劑H在笨f喊苯基賴作為活性成分的水乳 製劑中個的溶劑與其它乳劑中制的相似。因此，環境污㈣題依然存 在。需要提供-種在以笨甲酿基笨基腺作為活性成分之水乳製劑中使用的 /谷劑’其具有降低的對環境的影響。已知水溶性溶劑董十殺蟲齊丨（特別是苯 甲酿基苯基麵）具有高度溶解性。然而，這餘雜導致殺細結晶問 題。結晶會令製劑不適用於喷麗。因此，如果所選擇的水乳劑組合物中的 浴劑不僅？境友好的’而且還可防止製射的笨情絲基尿素類在儲 存期間出現結晶，則將是非常有利的。 μ 在本發明中，出於意料地發現’當某些CrC4雙亞炫基二醇雙/單々C4 烧基關作水乳製射麟’其不但表現出減少崎環境的影響，而 且還可避免苯甲醯絲基·活性成分在最終_中結晶。心物^在奋 足量的雙亞絲二醇雙/單_Cl_C4燒基啊減少笨甲酿絲基腺類活 性成分的結晶。 已發現’ CVQ雙亞院基二醇雙/單院細可有效減少苯甲酿基苯 基腺類活性成分化合物在水絲财。因此，錢縮齡包含 或多種CrQ雙亞烧基二醇雙/單_CrC4燒基喊可減少活性成分出現社 1，濃縮液中使用㈣雙亞院基二醇蛛CrQ絲喊比已知的^對環 更友好。 CVQ雙亞絲二醇雙/單《歲_適於製備難溶于水、甚至是不溶 于水的有機殺蟲化合物（特別是苯甲酿基笨細類）的水 C2-C4雙亞絲二醇雙/單_CrC4絲辦有效降低製軸笨帽基苯基尿素 201200021 類在儲存時出現結晶。 在本發明的製劑中’所述CrC4雙亞烷基二醇雙/單-Ci-Q烷基醚以足以 減少苯甲醯基笨基脲類化合物結晶的量存在。組合物中C2-C4雙亞烷基二醇 雙/單-Q-Q烷基醚的存在部分取決於所述笨曱醯基苯基脲類活性成分的濃 度，並且可不經過多實驗而確定。 所述CrC4雙亞烷基二醇雙/單-C丨-C4烷基醚優選以例如以下的量存 在：使得笨曱醯基笨基脲類活性成分對CrC4雙亞烷基二醇雙l_CrC4烷基 縫的重量比為1:0.1至1:7.5，更優選1:0.3至1:6，還更優選1:0.5至1:5。 所述組合物可包含單一的C2-C4雙亞烷基二醇雙/單-CrC4烷基醚或者 兩種或更多種CrC4雙亞烷基二醇雙/單_crC4烷基醚之組合。 所述CrC4雙亞烷基二醇雙/單«4烷基醚可以是任何合適的醚·》所述 OrCj雙亞烷基二醇雙/單·C|_C4烷基醚優先為選自以下的至少一種：二乙二 醇一甲喊、二乙二醇甲鍵、二丙二醇二甲趟、二丙二醇甲喊、二丁二醇二 甲鍵、二丁二醇曱醚、二乙二醇二乙醚、二乙二醇乙醚、二丙二醇二乙醚，、 二丙二醇乙醚、二丁二醇二乙醚、二丁二醇乙醚、二乙二醇二丙醚、二乙 二醇丙醚、二丙二醇二丙醚、二丙二醇丙醚、二丁二醇二丙醚、二丁二醇 丙醚、二乙二醇二丁醚、二乙二醇丁醚、二丙二醇二丁醚、二丙二醇丁醚、 一丁二醇二丁醚、二丁二醇丁醚及其混合物。合適的C2_C4雙亞烷基二醇雙 /單-CVC4烧基輔是本領域已知的並且可商購得到。 本發明的組合物為濃縮液。所述一種或多種C2_C4雙亞烷基二醇雙/單 _Q-C4烷基醚優選以至少5%、更優選以至少1〇% (以重量計）的量存在。 所述CVC4雙亞烷基二醇雙/單_crc：4烷基醚的份量可以以按重量計的5。/0至 75%、更優選5至60、還更優選10至5〇%的量存在。 如上文所述，發現CiQ雙亞烷基二醇雙/單_Ci_C4烷基醚可有效減少作 為農用化學物活性成分（特別是作為殺蟲劑）的某些苯曱醯基苯基脲類衍 生物的結晶。可納人組合物巾的合適的苯㈣基苯基顧是本領域中已知 的’並且許多可觸得到。組合物可含有—種或多種苯甲醯基苯基腺類衍 201200021 生物作為活性成分。 在一個實施方案中，所述製劑包含一種或多種選自以下的笨甲醢基苯 基脲類作為活性成分：雙苯氟脲、虱蟎脲、氟铃脲、殺鈴脲、除蟲脲、氟 咬腺、氟蟲脲、多氟脲、氟苯脲及其混合物。 - 所述苯甲醯基苯基脲類可以適當量存在以提供所需的製劑殺蟲活性。 • 特別地，所述笨曱酿基苯基脲類的存在量可以是按重量計的至少1%，優選 至少2%，更優選至少3%。所述苯曱醯基苯基脲類可以以按重量計丨至 70%，優選2至60¼，更優選3至50%的範圍存在於製劑中。優選的範圍 是按重量計的5至40%。 本發明的製劑可包含一種或多種表面活性劑。為使本發明的製劑表現 出有利的生態可接受性，優選使用表面活性劑，其中親脂性部分來自于安 全的天然產品。這些表面活性劑通常用於食品及化妝品工業。用於本發明 製劑中的優選表面活性劑的H.L.B在7至17之間。 取決於所要配製的活性化合物的性質，合適的表面活性化合物為非離 子型、陽離子型和/或陰離子型表面活性劑，或所述表面活性劑的混合物， 所述表面活性劑或表面活性劑混合物具有良好的乳化、分散和潤濕能力。 非離子型表祕_優縣選自町的—種❹種：聚氧乙雜祕油、 聚丙稀和聚氧乙婦的加聚物、聚氧化乙稀、三叔丁基苯盼聚氧乙基醇、聚 • 乙二醇醚以及辛基苯S«氧乙基醇。聚氧乙稀失水山_ (p却^%1咖 -S〇rbltan)的脂肪酸醋（如聚氧乙稀失水山梨醇三油酸醋）也是合適的非離 子型表面活性劑。 陽離子型表面活性劑優選為作為化取代基的帶有至少—個kb院基 的季敍鹽’附有至少-種Q-C22 -院基鍵（作為N_取代基），以及作為其它 取代基的未取代或齒化低級絲、节基或經基_低級烧基。鹽優選域化物、 硫酸二甲S旨或硫酸二乙s旨的m首選是_化物、硫酸二"或硫酸二 乙醋的形式。實例為硬脂基三甲基氯化錄和:^基雙(2_氣乙基)乙基溪化録。 合適的陰離子型表面活性齡括水雜脂肪酸鹽及水溶性合成表面活 201200021 性化合物。烷基芳基磺酸鹽的典型例子有十二烷基苯磺酸、二丁基萘磺酸 或萘績酸與甲链之縮合物的鈉、約或三乙醇銨鹽。相應的鱗酸鹽（例如對 壬基苯齡與4 1 Μ摩爾環氧乙院之加成物的咖“旨的鹽）或雜也是合適 的。 所述表面活性劑可⑽任何合_量存在，以提供所需驗態濃縮製 劑的分性散和穩定性。特別地…種或多種表面活性劑可以按重量計的至 少5%，優選至少，更優選至少15%存在。優選地，表面活性劑的納濃 度可以是按重量計的5至5G%，更優奴按重量計的ω至俱。在多個實 施方案中’發現表面活性劑的濃度心5至2S% (按重量計）的細内是合 組合物中所包含的其它成分是本領域眾所周知的，其包括例如防床 劑、消鋪和增麵。這些成分均可觸得到，本領域技術人肢認並瞭 解其用途。這些附加成分可以任何有效量存在，通常输重量計的Μ至 1%，更優選為按«計的〇.2至〇.75%。在多個實施方案+，上述各成分 的濃度為按重量計的0.5%是合適的。 本發明還提供了-_於製備以笨曱醯基苯基職作為活性成分的具 有提高的農業可接受穩錢的水減_綠，其雙魏基二醇 雙/單-CrQ絲瓣為賴無性成分—起配製。特观，本發^共了 -種製備苯甲醯絲細紐體濃縮製劑的方法，包括以下步驟. 1·將-種或多種殺蟲活性的苯㈣基苯基雌與—種或多種^4雙 亞院基二醇雙/單-C1-C4院基越混合，以獲得均勻油相，· 2.混合-種或多種選自以下的添加劑：表面活性劑、增稍劑、消泡劑、 防凍劑和水，以獲得均勻水相；以及 3彻混合（例如借助設備（如高剪切混合器、高觀板均質機等）） 將所述水祕加卿述油相t，赠得可分韻水乳劑。 少笨== 树明提供τ队雙_二醇雙/單以絲_於減 乂本甲醯基絲臟貞活性成分在濃縮液製射結晶的用途。 201200021 又-方面’本發明提供了—種控制—地點上的害蟲（特別是尾蟲）的 方法，所述方法包括向該地點施用有效量的上述製劑。 此外’本發明還提供了上述濃縮製劑在控制—地點上的害射的用途。 本發明的34些漢縮水乳劑在多種情況下表現出了改賴物理和化學穩 .定性’特別是在_敗至55T溫度範_的儲存期間，很少或沒有結晶現、 • 象觀察到。該製劑也是環境友好的。 本發明製劑的優點在於，可使用商業上可行濃度的穩定的水乳劑，而 沒有任何顯著或有害的結晶形成。 與市壯嶋的細概，本發_飾表獅低贿馳物毒性。 ，發明的魏製_具有科燃、财膚毒性和财_紐等優點。 最後’可以認為本發明水乳劑在生態毒理性方面是安全的，因為它們由 安全的基本惰性的齡製成。這使得孩製财用，而且還可符合美國辦 的嚴格要求和歐洲對揮發性有機化合物的控制標準。 現將參考町實施财的某錢選實施轉，詳細贿本發明。應春 理解’本發明並非旨在局限於這些特定的實施方案；相反，本發明旨在: =所有替代、改變以及等價形式，其可涵蓋於如所㈣請專利範圍所界定 的範圍内。因此’以下實施例（其包括優選的實施方案）將舉例說明本發 明的實施；應當理解，所示的詳_容是以舉例的方式說明僅旨在閣明 本發明優軸實财案，其目的在於提供認為最有肢㈣轉的本發明 的方法以及原理和概念。 實施例 在以下各實施例中，根據以下通用方法製備組合物： 製備油相： 八揚φ量的—種綱CrQ雙姚基：醇雙/單％絲_入混 =㈣Γ溶劑；向該混合槽中加入指定量的—種或多種笨曱酼基苯基 =成分;繼續授拌三十分鐘，直至所有苯甲酿基 疋全溶解，形成均相溶液； 乂刀 201200021 2.製備水相： 將選自表面活性劑、增稠劑 水在另一混合糟中混合； 3.高剪切混合： 在高剪切混合下向所雜相中加人所述水相，叫得可分散的水乳製 劑。混合物借助設備（例如高剪切混合器、高壓孔板均質機等）製備混合 物。 測試了樣品的低溫穩定性和熱貯存穩定性。低溫穩定性是在禮 溫設備内峨30天。誠存财性是在地_糾職μ ^完成測 試後，將製劑通過342目_過據’並觀察製劑的動性和結晶形成狀況。 還測定了製劑稀釋時的性能。特別地，在3〇〇c測試在比例為· CIPACD鮮水（aPACDstand卿）中的稀釋獻心小時， 所測晶體形成和分離狀況。 τ 對根據本發明的以下樣品進行了用於檢查相對植物毒性的測試並盘市 售Lufe_n 50水細產品進行了比較。就錄的嚴重性的 樣。 分為以下幾類： Α樣口0 第0類：無植物毒性 第1類：輕度對植物毒性 第2類.強烈植物毒性 實施例1 〇〇製備了表1所描述的液態製劑，其含有所示的^雙亞燒基二醇雙/ 早-C|-C4絲敝活性成分輕腺，其巾脲與㈣雙亞 翠_C|_以基__為約1:5。獅例1 _丨含有織量計·;Γ的 CA雙魏基二醇雙/單«4燒基醚。 的 ____ 表1 實施例1:虱蟎脲水乳劑 201200021 成分 組成 風蜗脲原藥 50公斤(作為純品） 十二烧基苯續酸納 100kg 吐溫80 100kg 聚氧乙烯失水山梨醇單油酸酯 二乙二醇二甲喊 250kg 黃原膠 5kg 丙二醇 3 kg 水 492kg 總計 1000kg 實施例2 製備了表2所描述的液態製劑，其含有所示的C2-C4雙亞烷基二醇雙/ 單-CrC4烷基醚及活性成分雙苯氟脲，其中雙苯氟脲對C2-C4雙亞烷基二醇 雙/單-CrC4烷基醚的比例為約1 : 4。實施例2的製劑含有按重量計40%的 C2-C4雙亞烷基二醇雙/單-Q-Q烷基醚。 表2 實施例2:雙苯氟脲水乳劑 成分 組成 雙苯氟脲原藥 100kg(作為純品） 十二院基苯續酸納 100kg 吐溫80 100kg 聚氧乙烯失水山梨醇單油酸酯 二乙二醇甲謎 400kg 黃原膠 5kg 丙二醇 5kg 13 201200021 -------- 水 290kg 總計 1000kg 實施例3 製備了表3所描述的液體製劑，其含有所示的CrC4雙亞烷基二醇雙/ 單-CrC4烧基喊及活性成分氟鈐脲，其中氟鈴脲對crc4雙亞烷基二醇雙/ 單-C1-C4烧基醚的比例為約1 : 3 ^實施例3的製劑含有按重量計24〇/〇的 CrC»雙亞燒基二醇雙/單_(^_(^4烷基醚。 表3 實施例3:乱鈴脈永乳劑 成分 組成 氟鈐脲原藥 80kg(作為純品） 十二炫基本項酸納 100kg 吐溫80 -- 100kg 聚氧乙烯失水山梨醇單油酸酉旨 二丙二醇二甲feU ' 240kg~~' --- 黃原膠 5kg 丙二醇 ' _ --- 水 〜 470kg 總計 1000kJ~· -—- 實施例4 製備了表4所描述的㈣侧，其含有卿的CrC4雙魏基二醇雙/ 單-C「C4烧基喊及活性成分殺鈴脲，其中殺鈴呢對㈣雙亞烧基二醇雙/ 單-C「C4絲__為約丨：2 4補4的_含有按重量計 10%的 CVC4雙亞烷基二醇雙/單^^仏烷基醚。 201200021 實施例4:殺鈴脲水乳劑 成分 組成 殺鈴脲原藥 50kg(作為純品） 十二烧基苯績酸鈉 100kg EL360 乙氧基化蓖麻油 100kg 二丙二醇二甲醚 100kg 黃原膠 5kg 丙二醇 5kg 水 640kg 總計 1000kg 實施例5 製備了表5所描述的液體製劑，其含有所示的C2-C4雙亞烷基二醇雙/ 單-Q-C4烷基醚及活性成分除蟲脲，其中除蟲脲對C2_C4雙亞烷基二醇雙/ 單-Q-Q烷基醚的比例為約1 : 5。實施例5的製劑含有按重量計50%的 C2-C4雙亞烷基二醇雙/單-CrC4烷基醚。 表5 實施例5:除蟲脲水乳劑 成分 組成 除蟲脲原藥 100kg(作為純品） 十二烧基苯續酸納 100kg 吐溫80 100kg 聚氧乙烯失水山梨醇單油酸酯 二丙二醇甲醚 500kg 15 201200021 黃原膠 5kg 丙二醇 5kg 水 190kg 總計 1000kg 實施例6 製備了表6所描述的液體製劑’其含有所示的（^(^雙亞烷基二醇雙/ 單-CrC4炫基謎及活性成分氟啶脲’其中氟啶脲對c2-c4雙亞烷基二醇雙/ 單-Ci-Q烷基醚的比例為約丨：0.5。實施例6的製劑含有按重量計1〇%的 C2-C4雙亞烷基二醇雙/單·〇ν(：4烷基醚。 表6 實施例6:氟啶脲水乳劑 成分201200021 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to an agrochemical composition. The invention particularly relates to a stable, environmentally friendly aqueous emulsion (EW) insecticidal formulation comprising a benzamidine-based active compound as an insecticide and an ether as a solvent. The invention also relates to a process for the preparation of the above composition And its use in crop protection. In particular, the present invention relates to the prevention of crystallization of the insecticide phenylmercaptophenyl urea derivative and to the reduction of phytotoxicity of aqueous emulsion formulations. [Prior Art] Known insect growth regulators for control include benzoylphenyl urea (BPU) compounds, and examples of the sample may be selected from the following commercially available compounds, bisphenyl fluoride gland , pigment gland, fluorosis gland, triflumuron, diflubenzuron, gas venous vein, gas worm gland, polyflumuron (noviflumuron) and fluorobenzamide. The benzepidine phenylurea compound is usually sold as an emulsion. However, such preparations require a large amount of organic solvents such as aromatic hydrocarbons, gaseous hydrocarbons, etc., and the toxicological and ecological toxicological impurities of these organic solvents are widely known. Formulations based on these remedies bring toxicity, environment and odor. Therefore, there is a continuing need for a formulation that inhibits environmentally friendly benzoylphenyl-based gland-based compounds. Water emulsion (EW) is an environmentally friendly formulation. Examples of aqueous emulsions are well known in the art. CN10137996 describes an aqueous milk preparation (EW) containing 1% to 5% by weight of the wind snail as an active ingredient, 1% to 10% of a solvent, 5% to 5% of an anti-; East, 〇1 % to 1% antifoaming agent, 1% to dirty emulsifier, 〇1% to 5% _ and moisture. Although the formulation is more environmentally friendly than the solvent-based emulsion of the same active ingredient, the solvent used in the formulation is either toluene or toluene' both seriously damaging the environment. Existing technologies need to be added through Cong environmentally friendly solvents. It is most advantageous if the solvent in question can bring other benefits to the formulation (the system is to improve shelf life). The United States Department of Health and Environmental Protection Bureau inspected the ingredients other than the active ingredients in the insecticide preparations 201200021. In Europe, the European Community Commission is in the final stages of legislative regulation of the use of volatile organic compounds (VOCs) and will require formulations containing these VOCs plus eco-labels. In fact, eco-toxic labeling systems are already available in Canada and Germany. Under these circumstances, it is hoped that as soon as possible, alternatives to traditional agrochemicals with the above problems will be developed to provide the market with agrochemicals that are human- and environmentally friendly and can be practically applied to commercial agricultural production. In the past, Zeng Bin has used or used a variety of alternative solvents. Examples of such alternative solvents include aliphatic hydrocarbons, alcohols, glycols, polyethylene glycols, glycol ethers, ketones, and polar solvents having high solubility such as γ-butyrolactone, N-mercaptopyrrolone, and the like. A problem with aliphatic hydrocarbons is that their solvency to solid pesticides is generally low. The other solvents described above are suitable for dissolving the insecticide, but are also soluble in water at the same time. This water solubility leads to crystallization of the insecticide. The crystallization makes the formulation unsuitable for spray. In the present invention, it has been unexpectedly found that certain bis-alkylene glycol bis/mono"4 alkyl ether solvents not only prevent the use of the succinyl phenylurea derivative during storage in aqueous emulsions (EW) Crystallization in the process, and these solvents have been more environmentally friendly than other agents used in agrochemical injection.发明 【 【 发明 发明 发明 发明 发明 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤Stupid (tetra)-based benzene fines as active agrochemicals): Each of the solvents as a solvent is not only environmentally friendly, but also advantageously reduces the crystallization of the phenylureas in the final production. In one aspect, the present invention provides an agrochemical composition, a brewing base__age and a CrQ double-filament two-part single "fine/this (^^^ job--shidi^cham composition: (a) l /o-50/o of the present mercaptophenylurea active ingredient; 201200021 (b) 5%-50% of CrC4 bisalkylene glycol bis/mono_C丨_c4 alkyl ether as solvent; c) an optional one or more additives selected from the group consisting of surfactants, thickeners, antifoaming agents, antifreeze agents, and water; all ingredients are 100% in total » In one embodiment, the Cr(:4 Dialkylene glycol bis/mono-(VC4 alkyl ether is one or more ethers selected from the group consisting of diethylene glycol dimethyl ether, diethylene glycol oxime ether, dipropylene glycol dimethyl bond, dipropylene glycol methyl ether , dibutyl glycol dioxime ether, dibutyl glycol oxime ether, diethylene glycol diethyl ether, diethylene glycol diethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ether, dibutyl glycol diethyl ether, dibutyl glycol ether , ethylene glycol dipropyl ether, diethylene glycol propyl ether, dipropylene glycol dipropylene, dipropylene glycol propyl ether, dibutylene glycol dipropyl ether, dibutyl glycol propyl ether, diethylene glycol dibutyl ether, Diethylene glycol butyl ether, dipropylene glycol dibutyl ether, dipropylene glycol butyl ether, dibutylene glycol dibutyl ether, dibutyl glycol butyl ether, and mixtures thereof. In a preferred embodiment, the awkward base is stupid The base urea active ingredient is at least one compound selected from the group consisting of bis-fluorofluorourea, guanidine urea, fluoroquinone urea, triflumuron, diflubenzuron, fluridazine, flubendiamide, polyfluorourea, and fluorophenylurea The present invention provides a method for preparing an agriculturally connectable (four) stable water emulsion prepared by using benzhydrylphenyl urea as an active ingredient, wherein the active ingredient is selected from the group consisting of A solvent of CVC4 dialkylene glycol bis/mono/polyalkyl ether is prepared together. In particular, the present invention provides A method for making agricultural chemicals, the method comprising the steps of: 1. mixing one or more insecticidally active benzepidine phenylureas with one or more c2_C4 bis-sulphate diol bis/monoalkyl ethers, To obtain a uniform oil phase; 2. Mix at least one additive selected from the group consisting of surfactants, extenders, defoamers, and anti-agents; the total amount of all components of the agent and water is 1 嶋, which is converted to a uniform aqueous phase; The aqueous phase and the oil phase are combined by means of mixing (for example by means of equipment such as a high shear mixer, a high pressure orifice homogenizer, etc.) to obtain a dispersible water emulsion (EW). The concentrated water emulsion of the present invention A high degree of physical and chemical stability is exhibited, and the system is at a temperature of 55 C. In storage _ no crystallization is observed. This system exhibits improved friendliness of the jade clothing. [2012] [Embodiment] The basic base gland of the brewing is a water-insoluble compound. These compounds are marketed as Emulsion Concentrate products. A large amount of organic solvents such as diphenylbenzene or toluene in the emulsion cause problems, especially when the preparation is finally used, which causes environmental pollution. Therefore, there is a continuing need to 'develop environmentally friendly formulations of benzamidine fine compounds. The water-milk preparation is a kind of solvent which has a decrease in the preparation of the environmentally-acceptable preparation H in the water-milk preparation which is an active ingredient, and is similar to that prepared in other emulsions. Therefore, environmental pollution (4) issues still exist. There is a need to provide a / granule which is used in an aqueous emulsion preparation having a stupid base as an active ingredient, which has a reduced environmental impact. The water-soluble solvent, known as chlorpyrifos (especially phenylphenylphenyl), is known to have high solubility. However, this excess leads to the problem of fine crystallization. Crystallization will make the formulation unsuitable for use in spray. Therefore, if the bath agent in the selected aqueous emulsion composition is not only? It would be very advantageous to be environmentally friendly and to prevent the formation of crystallized urea-based ureas during storage. μ In the present invention, it has been unexpectedly discovered that 'when certain CrC4 bis-thylene glycol bis/monoterpene C4 alkyls are used as water emulsions, it not only exhibits a reduction in the effect of the sacrificial environment, but also avoids benzene. The formazan-based active ingredient crystallizes in the final _. The heart material ^ in the amount of double-filament diol double / single _Cl_C4 burning base to reduce the crystallization of the active components of the stupid silk-based gland. It has been found that 'CVQ Shuangya Institute-based diol double/single-small fine can effectively reduce the active ingredients of benzoyl phenyl-based gland in water silk. Therefore, the money shrinking age contains or a variety of CrQ bis-alkylene diol bis / single _CrC4 sizzling shout can reduce the presence of active ingredients in the community 1, the use of concentrated liquids (four) double-Asian diol spiders CrQ wire shout than known ^It is more friendly to the ring. CVQ double-filament diol double/single-year-old water C2-C4 double-filament two suitable for the preparation of organic insecticidal compounds (especially styrene-based stupid) which are poorly soluble in water and even insoluble in water. Alcohol double / single _CrC4 wire to effectively reduce the shaft of the stupid base phenyl urea 201200021 class crystallize during storage. In the formulation of the present invention, the CrC4 bisalkylene glycol bis/mono-Ci-Q alkyl ether is present in an amount sufficient to reduce the crystallization of the benzamidine-based urea compound. The presence of the C2-C4 bisalkylene glycol bis/mono-Q-Q alkyl ether in the composition depends in part on the concentration of the clandyl phenylurea active ingredient and can be determined without undue experimentation. The CrC4 bisalkylene glycol bis/mono-C丨-C4 alkyl ether is preferably present, for example, in an amount such that the agglomerated sulfhydryl active ingredient is added to the CrC4 bisalkylene glycol bis l_CrC4 alkane The basis weight ratio is from 1:0.1 to 1:7.5, more preferably from 1:0.3 to 1:6, still more preferably from 1:0.5 to 1:5. The composition may comprise a single C2-C4 bisalkylene glycol bis/mono-CrC4 alkyl ether or a combination of two or more CrC4 bisalkylene glycol bis/mono-crC4 alkyl ethers. The CrC4 bisalkylene glycol bis/mono «4 alkyl ether may be any suitable ether. The OrCj bisalkylene glycol bis/mono C|_C4 alkyl ether is preferably selected from the following At least one: diethylene glycol monomethyl sulfonate, diethylene glycol methyl bond, dipropylene glycol dimethyl hydrazine, dipropylene glycol fluorene, dibutyl diol dimethyl bond, dibutyl diol oxime ether, diethylene glycol diethyl ether , diethylene glycol diethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ether, dibutyl glycol diethyl ether, dibutyl glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol propyl ether, dipropylene glycol dipropyl ether , dipropylene glycol propyl ether, dibutylene glycol dipropyl ether, dibutyl glycol propyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl ether, dipropylene glycol dibutyl ether, dipropylene glycol butyl ether, dibutyl Dibutyl ether, dibutyl glycol butyl ether and mixtures thereof. Suitable C2_C4 bisalkylene glycol bis/mono-CVC4 burned Kiev is known in the art and is commercially available. The composition of the invention is a concentrate. The one or more C2_C4 bisalkylene glycol bis/mono__Q-C4 alkyl ethers are preferably present in an amount of at least 5%, more preferably at least 1% by weight. The portion of the CVC4 bisalkylene glycol bis/mono-crc:4 alkyl ether may be 5 by weight. It is present in an amount of from /0 to 75%, more preferably from 5 to 60, still more preferably from 10 to 5%. As described above, it has been found that CiQ bisalkylene glycol bis/mono-Ci_C4 alkyl ether can effectively reduce certain phenylmercaptophenylurea derivatives as active ingredients of agrochemicals, especially as insecticides. Crystallization of matter. Suitable phenyl(tetra)phenyl groups of the human composition wipes are known in the art and many are accessible. The composition may contain one or more benzhydrylphenyl gland derivatives 201200021 as an active ingredient. In one embodiment, the formulation comprises one or more of the following alkalyl phenylureas selected from the group consisting of: diphenylfluorourea, guanidine urea, hexaflumuron, triflumuron, diflubenzuron, Fluorbite gland, flubendiamide, polyfluorourea, fluorophenylurea and mixtures thereof. - The benzhydrylphenyl ureas may be present in an amount to provide the desired insecticidal activity of the formulation. • In particular, the abbreviated phenylureas are present in an amount of at least 1%, preferably at least 2%, more preferably at least 3% by weight. The phenylnonylphenylurea may be present in the formulation in a range of from 丨 to 70% by weight, preferably from 2 to 601⁄4, more preferably from 3 to 50% by weight. A preferred range is from 5 to 40% by weight. Formulations of the invention may comprise one or more surfactants. In order for the formulation of the invention to exhibit advantageous ecological acceptability, it is preferred to use a surfactant wherein the lipophilic moiety is derived from a safe natural product. These surfactants are commonly used in the food and cosmetic industries. Preferred surfactants for use in the formulations of the invention have an H.L.B of between 7 and 17. Suitable surface-active compounds are nonionic, cationic and/or anionic surfactants, or mixtures of said surfactants, said surfactants or surfactant mixtures, depending on the nature of the active compound to be formulated. Has good emulsification, dispersion and wetting ability. Non-ionic watch secret _ Youxian selected from the town - a variety of species: polyoxyethylene miscellaneous oil, polypropylene and polyoxymethylene add-on, polyethylene oxide, tri-tert-butyl benzene hope polyoxyethylene Alcohol, polyglycol ether and octylbenzene S« oxyethyl alcohol. Fatty acid vinegar (e.g., polyoxyethylene sorbitan trioleate) is also a suitable nonionic surfactant. The cationic surfactant preferably has at least one kb of a quaternary salt as a chemical substituent, with at least one Q-C22-household bond (as an N-substituent), and as other substituents. Unsubstituted or dentated lower filament, pitch or warp-lower alkyl. The preferred salt of the salt, the dimethyl sulfate or the sulphuric acid s is preferably in the form of _, sulphuric acid <RTIgt; An example is stearyltrimethyl chloride and: bis-bis(2-gasethyl)ethyl sulphate. Suitable anionic surface active age water-containing fatty acid salts and water-soluble synthetic surface active 201200021 compounds. Typical examples of the alkylarylsulfonate are sodium, about or triethanolammonium salts of a condensate of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or naphthoic acid with a methyl chain. Corresponding sulphates (for example, a salt for the thiophene age and an adduct of 4 1 moles of epoxy oxime) or impurities are also suitable. The surfactant may be present in any amount of (10) To provide the fractional dispersion and stability of the desired eutectic concentrate formulation. In particular, the surfactant or surfactants may be present at least 5%, preferably at least, more preferably at least 15% by weight. Preferably, surface active The nanoconcentration of the agent may be from 5 to 5 G% by weight, more preferably from ω to the weight of the slave. In various embodiments, the concentration of the surfactant is found to be 5 to 2 S% by weight. The other ingredients contained in the composition are well known in the art and include, for example, anti-bed agents, bakes, and face-lifting agents. These ingredients are readily available, and those skilled in the art recognize and understand their use. The additional ingredients may be present in any effective amount, usually from 1% to 5% by weight, more preferably from 〇.2 to 75.75%. In various embodiments, the concentration of each of the above ingredients is by weight 0.5% is suitable. The present invention also provides - The thiophenyl group as an active ingredient has an improved agricultural acceptable stable water reduction _ green, and its weiwei diol bis/mono-CrQ stalk is formulated as an asexual ingredient. ^ A total of - a method for preparing a concentrated preparation of benzamidine fines, including the following steps. 1 - one or more insecticidal activity of phenyl (tetra) phenyl female and - or a variety of 4 The more mixed the diol bis/mono-C1-C4 yard base to obtain a uniform oil phase, 2. Mixing one or more additives selected from the group consisting of surfactants, builders, defoamers, antifreezes and water To obtain a uniform aqueous phase; and 3 thorough mixing (for example, by means of equipment (such as a high shear mixer, a high-view plate homogenizer, etc.)), the water secret is added to the oil phase t, and a water-soluble emulsion can be obtained. Less stupid == Shuming provides the use of τ team double _diol double / single wire _ _ 乂 乂 乂 醯 醯 醯 醯 醯 。 。 。 。 。 。 。 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 A method of controlling a pest (especially a tailworm) at a location, the method comprising administering to the site an effective amount of the above formulation. 'The present invention also provides the use of the above-mentioned concentrated preparations for control-at-site damage. The 34 Han-shrinkage emulsions of the present invention exhibit a change in physical and chemical stability in a variety of cases, especially in the case of _ During storage of the 55T temperature range, little or no crystallization is observed, as observed. The formulation is also environmentally friendly. The advantage of the formulation of the invention is that a commercially viable concentration of a stable aqueous emulsion can be used without any significant Or the formation of harmful crystals. With the details of the city's strong, this hair _ decorated table lion low bribery toxic. Invented Wei system _ has the advantages of family burning, skin toxicity and wealth _ New Zealand. Finally 'can think The aqueous emulsions of the present invention are safe in terms of ecotoxicity because they are made from a safe, substantially inert age, which makes them child-friendly and meets the strict requirements of the United States and European volatile organic compounds. Control standards. We will refer to the implementation of a certain amount of money in the implementation of the town, and we will make a detailed bribe. The present invention is not intended to be limited to the specific embodiments; rather, the invention is intended to include: all alternatives, modifications, and equivalents, which are within the scope defined by the scope of the claims. The following examples, which are included to illustrate preferred embodiments of the present invention, are intended to be illustrative of the embodiments of the invention The aim is to provide a method, principle and concept of the invention believed to be most versatile. EXAMPLES In the following examples, the compositions were prepared according to the following general methods: Preparation of oil phase: octane φ amount - species CrQ double Yao base: alcohol double / single % silk _ mixed = (d) hydrazine solvent; to the mixture Add the specified amount of one or more alkaloid phenyl = components to the tank; continue to mix for 30 minutes until all the benzoic acid hydrazine is completely dissolved to form a homogeneous solution; 乂刀201200021 2. Preparation of aqueous phase: Mixing water selected from surfactant and thickener in another mixed mixture; 3. High shear mixing: adding the aqueous phase to the impurity phase under high shear mixing, called dispersible water Milk preparation. The mixture is prepared by means of equipment such as a high shear mixer, a high pressure orifice homogenizer, and the like. The sample was tested for low temperature stability and heat storage stability. The low temperature stability is 30 days in the temperature equipment. Since the financial property is in place, the preparation is passed through the 342 mesh and the formulation is observed and the crystallization and crystal formation conditions are observed. The performance at the time of dilution of the preparation was also determined. Specifically, the crystal formation and separation conditions were measured at 3 〇〇 c in a dilution of the CIPSCD fresh water (aPACDstand). τ The following samples according to the present invention were tested for the relative phytotoxicity and compared with the commercially available Lufe_n 50 water fine product. The severity of the recording. Divided into the following categories: Α sample port 0 class 0: no phytotoxicity class 1: mild phytotoxicity class 2. strong phytotoxicity Example 1 〇〇 prepared the liquid preparation described in Table 1, containing The bis-bis-alkylene glycol bis/early-C|-C4 silk fibroin active ingredient is shown as a light gland, and its towel urea and (iv) double sapphire _C|_ base __ is about 1:5. Lion example 1 _ 丨 contains a weaving meter · Γ CA weiwei diol bis / single « 4 alkyl ether. ____ Table 1 Example 1: Urea urea water emulsion 201200021 Composition of wind worm urea drug 50 kg (as pure product) 12-burning benzoic acid sodium 100 kg Tween 80 100kg Polyoxyethylene sorbitol single Oleate Diethylene Glycol Dimethyl 250kg Xanthan Gum 5kg Propylene Glycol 3 kg Water 492kg Total 1000kg Example 2 The liquid formulation described in Table 2 was prepared containing the C2-C4 disalkylene glycol double shown. / Mono-CrC4 alkyl ether and active ingredient diphenylfluorourea, wherein the ratio of bis-fluorofluorourea to C2-C4 disalkylene glycol bis/mono-CrC4 alkyl ether is about 1:4. The formulation of Example 2 contained 40% by weight of a C2-C4 bisalkylene glycol bis/mono-Q-Q alkyl ether. Table 2 Example 2: Diphenylfluorourea water emulsion component composition Diphenylfluorourea original drug 100kg (as pure product) 12-yard benzoic acid sodium 100kg Tween 80 100kg Polyoxyethylene sorbitan monooleate Diethylene glycol mystery 400kg xanthan gum 5kg propylene glycol 5kg 13 201200021 -------- Water 290kg Total 1000kg Example 3 The liquid formulation described in Table 3 was prepared, which contained the CrC4 disalkylene group shown. The diol bis/mono-CrC4 alkyl group cites the active ingredient fluoroquinone, wherein the ratio of hexaflumuron to crc4 bisalkylene glycol bis/mono-C1-C4 alkyl ether is about 1: 3 ^ Example 3 The formulation contained 24 〇/〇 of CrC» bis-alkylene diol bis/single _(^_(^4 alkyl ether). Table 3 Example 3: 乱铃脉永乳剂组成组成氟钤; Medicine 80kg (as pure product) 12 Hyun basic acid sodium 100kg Tween 80 -- 100kg Polyoxyethylene sorbitol sorbitol monooleic acid dipropylene glycol dimethyl feU '240kg~~' --- Xanthan gum 5kg Propylene glycol ' _ --- Water ~ 470kg Total 1000kJ~· - - Example 4 The (4) side described in Table 4 was prepared, which contains Qing's CrC4 diweiyl glycol bis/single-C" C4 burns the base and sings the active ingredient to kill the sulphonyl urea, which kills the bell to the (iv) bis-alkylene diol bis / single - C "C4 silk __ is about 丨: 2 4 supplement 4 _ contains 10% by weight CVC4 bisalkylene glycol bis/monomethane alkyl ether. 201200021 Example 4: chlorfluazuron water emulsion composition 50mg of triflumuron original drug (as pure product) sodium decyl benzoate sodium 100kg EL360 Ethoxylated castor oil 100kg Dipropylene glycol dimethyl ether 100kg Xanthan gum 5kg Propylene glycol 5kg Water 640kg Total 1000kg Example 5 The liquid formulation described in Table 5 was prepared containing the C2-C4 bisalkylene glycol shown. Bis/mono-Q-C4 alkyl ether and active ingredient diflubenzuron, wherein the ratio of diflubenzuron to C2_C4 disalkylene glycol bis/mono-QQ alkyl ether is about 1: 5. Formulation of Example 5. Containing 50% by weight of C2-C4 bisalkylene glycol bis/mono-CrC4 alkyl ether. Table 5 Example 5: Diflubenzuron water emulsion component composition Diflubenzuron original drug 100kg (as pure product) Dialkyl benzoic acid sodium 100kg Tween 80 100kg Polyoxyethylene sorbitan monooleate dipropylene glycol methyl ether 500kg 15 201200021 Xanthan gum 5kg Propylene glycol 5 Kg water 190kg total 1000kg Example 6 The liquid preparation described in Table 6 was prepared, which contained the indicated (^(^bis-alkylene glycol bis/mono-CrC4 plexus and the active ingredient chlorfluazuron) The ratio of pyridine urea to c2-c4 bisalkylene glycol bis/mono-Ci-Q alkyl ether is about 丨:0.5. The formulation of Example 6 contained 1% by weight of C2-C4 bisalkylene glycol bis/mono 〇 ν (: 4 alkyl ether. Table 6 Example 6: fluridazine aqueous emulsion ingredients
氟啶腺原藥 ΐ二烷基苯磺遍瓦 :土溫 80 聚氧乙烯失水山梨醇單油酸酶 二丁二醇二甲㉟'—'- ^Fluoridine gland drug ΐdialkyl benzene sulfonate: soil temperature 80 polyoxyethylene sorbitan monooleate dibutane diol 35'-'- ^
5kg5kg
490kg490kg
黃原膠 丙二醇 水 總計 實施例7 201200021 製備了表7所描述的__，其含有所示的c2.c4雙魏基二醇雙/ 單-c,-c4烷基醚及活性成分氟蟲脲，其中氣蟲腺對C2_Q雙亞烷基二醇雙/ 單-C,-C4院基醚的比例為約丨：丨。實施例7的㈣含有按重量計25%的 c2-c4雙亞烧基二醇雙/單-Cl_c成基鰱。 表7 成分 氟蟲腺原藥 組成 250kg(作為純品） 十，一炫基本項酸鈉 100kg 吐溫80 聚氧乙烯失土山辑單油酸醋 二乙二醇 黃原膠Xanthan Gumdiol Water Total Example 7 201200021 The __ described in Table 7 was prepared, which contained the c2.c4 diweiyl diol bis/mono-c,-c4 alkyl ether and the active ingredient flubenzuron as shown. Wherein the ratio of the gas worm gland to the C2_Q dialkylene glycol bis/mono-C,-C4 oxime ether is about 丨:丨. (4) of Example 7 contained 25% by weight of c2-c4 bis-alkylene glycol bis/mono-Cl_c-based oxime. Table 7 Ingredients Fluorite gland original drug Composition 250kg (as pure product) Ten, one Hyun basic sodium salt 100kg Tween 80 Polyoxyethylene lost soil mountain single oil vinegar Diethylene glycol Xanthan gum
100kg 250kg 5kg 5kg "290kg- 1000kg 實施例8 製備了表8所描述的液體製劑，其含有所示的C2-C4雙亞炫基二醇雙/ 早-crc4院基醚及活性成分多氟腺，其中多氟脲對Ch：4雙亞烷基二醇雙/ 單-CrQ炫細的_為約丨：$。實施例8的製齡有按重量計洲的 c2-c4雙亞烧基二醇雙/單《4燒基域。 201200021 實施例8:多氟脲水乳劑 成分 組成 多氟脲原藥 50kg(作為純品） 十二烧基苯續酸納 100kg 吐溫80 150kg 聚氧乙烯失水山梨醇單油酸酯 二丙二醇二乙醚 250kg 黃原膠 5kg 丙二醇 5 kg 水 440kg 總計 1000kg 實施例9 製備了表9所描述的液體製劑，其含有所示的C2-C4雙亞烷基二醇雙/ 單-CrC4烷基醚及活性成分氟苯脲，其中氟苯脲對C2-C4雙亞烷基二醇雙/ 單-CrC4烷基醚的比例為約1 : 5。實施例9的製劑含有按重量計20%的 C2-C4雙亞烷基二醇雙/單-Q-C4烷基醚。 表9 實施例9:氟笨脲水乳劑 成分 組成 氟苯脲原藥 40kg(作為純品） 十二烧基苯續酸鈉 100kg 吐溫80 160kg 聚氧乙稀失水山梨醇單油酸西旨 201200021 二丙二醇乙謎 200kJ^^- 黃原膠 丙二醇 ~5ki—- 水 490kJ~^-- 總計 ~T〇0〇kJ~^- -^ 實施例ίο 製備了表10所描述的液體製劑，其含有所示的CrC4雙亞院基二醇雙/ 單-Q-C4烷基醚及活性成分雙苯氟脲與虱蟎尿素之組合，其中雙苯敗脈加乱 蟎脲與CrC4雙亞烷基二醇雙/單-Q-Q烷基醚的比例為約'丨：3。實施例1〇 的製劑含有按重量計30%的CrC4雙亞烷基二醇雙/單_Ch：4^基趟。 表10 實把例10.雙苯氟脲+虱蟎脲水乳劑 - 成分 組成- 雙本氟腺原藥 虱蟎脲原藥 ~~-- -1- 一 'K* 肯甘 ϊ^ΓΙγυΓΤ''—— --- 50kg(作 ~ 厂-一酉楚納 100kg ~~~'-- 吐溫80 ^---— 聚氧乙烯失水山梨醇單油酸酯 —— 3Κ^ — '**'^----- 100kg ~~~~~~'—-- 一 J -一 〇T 一 乙轉 甚周腺 —- - 300kg - 兴/^膠 -—...... 5 kg - 丙二醇 '—-—— 屮 ^ --- 5kg s~~—~- 个 ---- 她古+ ^^〜---- 290kg - 夕似口, 1000kg --- —--- 實施例11 19 201200021 製備了表11所描述的液體製劑，其含有所示的c2_C4雙亞院基二醇雙/ 單-c「c4絲敝活性成分殺铃_ a奴組合，糾麟尿素加氣鈴 脲與CrC4雙亞烷基二醇雙/單-Q-C4烷基醚的比例為約i : 15。實施例u 的製劑含有按重量計30%的CrC4雙亞烷基二醇雙/單义广仏烷基醚。 表11 實施例11:殺鈴腺+氟鈴腺;^乳劑 成分 組成 殺鈴腺原藥 l〇〇kg(作為純品） 氟鈐脉原藥 10〇kg(作為純品） 十二炫基苯項酸鈉 15¾- 吐溫80 聚氧乙烯失水山梨醇單油酸酯 Tooki''~ 二丁二醇乙喊 "300kf~~- 黃原膠 5 kg 丙二醇 1¾~~~~'- 水 ~29〇ζ - 總計 "lOOOkJ^.......... -----—^ 實施例12 μ製備了表12所描述的液體製劑，其含有所示的％雙亞烧基二醇 細及活性成分除蟲脲減饼素之組合，其情蟲尿素加| :與c2-c4雙亞絲二醇雙/單_CrC4院基_比例為約i : 2。實施例12 製劑含有按重量計30。/。的CrC4雙亞烷基二醇雙/單·Ci_C4烷基醚。 表12 實施例 成分 12:除蟲腺+氟咬&水乳兩~~~~ ——100 kg 250 kg 5 kg 5 kg "290 kg-1000 kg Example 8 The liquid preparation described in Table 8 was prepared, which contained the C2-C4 bis-thylene glycol bis/early-crc4 oxime ether and the active ingredient polyfluoroglycans as shown. , wherein the polyfluorourea to Ch: 4 double alkylene glycol bis / mono-CrQ fine _ is about 丨: $. The age of Example 8 has a c2-c4 bis-alkylene diol bis/single "4 sinter domain" by weight. 201200021 Example 8: Polyfluorourethane water emulsion component composition Polyfluorourethane original drug 50kg (as pure product) Dodecylbenzene benzoate sodium 100kg Tween 80 150kg Polyoxyethylene sorbitan monooleate dipropylene glycol II Ether 200 kg xanthan gum 5 kg propylene glycol 5 kg water 440 kg total 1000 kg Example 9 The liquid formulation described in Table 9 was prepared containing the C2-C4 bisalkylene glycol bis/mono-CrC4 alkyl ether shown and its activity. The component fluorophenylurea wherein the ratio of fluorophenylurea to C2-C4 bisalkylene glycol bis/mono-CrC4 alkyl ether is about 1:5. The formulation of Example 9 contained 20% by weight of a C2-C4 bisalkylene glycol bis/mono-Q-C4 alkyl ether. Table 9 Example 9: Fluorobenzal water emulsion component composition fluorophenylurea original drug 40kg (as pure product) sodium dodecyl benzoate 100kg Tween 80 160kg polyoxyethylene sorbitan monooleate 201200021 Dipropylene glycol B puzzle 200kJ^^- Xanthan gum propylene glycol ~5ki-- Water 490kJ~^-- Total ~T〇0〇kJ~^- -^ Example ίο The liquid preparation described in Table 10 was prepared, which contained The combination of the CrC4 double-substrate diol bis/mono-Q-C4 alkyl ether and the active ingredient bisphenyl fluorourea and hydrazine urea, wherein the bisphenol agglomerate is mixed with guanidine urea and CrC4 bis arylene The ratio of alcohol bis/mono-QQ alkyl ether is about '丨:3. The formulation of Example 1 contained 30% by weight of CrC4 bisalkylene glycol bis/single_Ch:4^ fluorene. Table 10 Example 10. Diphenylfluorourea + guanidine urea water emulsion - composition of ingredients - double fluoroadenosine guanidine urea drug ~~-- -1- a 'K* Kengan ϊ ^ ΓΙ υΓΤ υΓΤ '' —— --- 50kg (for ~ plant - one 酉 Chu Na 100kg ~~~'-- Tween 80 ^---- polyoxyethylene sorbitan monooleate - 3Κ^ — '**' ^----- 100kg ~~~~~~'--- One J-one 〇T-B turn to very gland-- - 300kg - Xing / ^ glue --...... 5 kg - propylene glycol '—-—— 屮^ --- 5kg s~~—~- ―--- Her ancient + ^^~---- 290kg - 夕似口, 1000kg --- —--- Example 11 19 201200021 The liquid preparation described in Table 11 was prepared, which contained the c2_C4 double sub-system diol bis/single-c "c4 silk 敝 active ingredient killing _ a slave combination, and the cumber urea-aerated chlorfluazuron and CrC4 The ratio of the dialkylene glycol bis/mono-Q-C4 alkyl ether is about i: 15. The formulation of Example u contains 30% by weight of CrC4 bisalkylene glycol bis/monoaliphatic dioxin. Table 11 Example 11: Killing gland + fluorobell gland; ^The composition of the emulsion consists of the original drug of the bell-gland gland l〇〇kg (as pure product) The original drug of fluoroquinone vein 10 〇kg (as pure product) Sodium benzoate sodium 153⁄4- Tween 80 polyoxyethylene sorbitan monooleate Tokii''~ dibutyl diol B shouting "300kf~~- xanthan gum 5 kg propylene glycol 13⁄4~~~~' - water ~29〇ζ - total "lOOOOkJ^.......... -----^ Example 12 μ prepared the liquid formulation described in Table 12, which contains the % double shown The combination of the alkylidene diol fine and the active ingredient diflubenzuron, the emollient urea plus | : and the c2-c4 double-silk bisene/single_CrC4 yard base _ ratio is about i: 2. Example 12 The formulation contained 30% by weight of CrC4 bisalkylene glycol bis/mono·Ci_C4 alkyl ether. Table 12 Example Component 12: Deworming gland + fluorine bite & water emulsion two ~~~~ ——
20 201200021 除蟲脲原藥 __ lbokg(作為純品） 氟啶脲原藥 50kg(作為純品） 十二院基苯碌酸納 100kg 吐溫80 " 100kg — 聚氧乙稀失水山梨醇單油酸酯 二乙二醇二丙越 300kg 黃原膠 5kg 丙二醇 5kg 水 340kg 總計 1000kg 實施例13 製備了表13所描述的液體製劑，其含有所示的C2_C4雙亞烷基二醇雙/ 單-Q-Q絲戰·成分氟蟲職錄尿素之組合，其中氟蟲尿素加多氣 脲與CrQ雙亞院基二醇雙/單A·。烷基醚的比例為約丨：丨4。實施例u 的製劑含有按重量計35%的CrC4雙魏基二醇雙/單_CrC4^基鍵。 表13 實施例13:氟蟲脲+多氟脲水乳劑 成分 氟蟲脲原藥 多氟脲原藥 -燒基苯績酸鈉 吐溫80 聚氧乙烯失水山梨醇單油酸酯 乙二醇丙醚 黃原膠 組成 2〇〇kg(作為純品） 5〇kg(作為純品） 100kg 100kg 350kg 5kg 21 201200021 丙二醇 5kT^—-—— 水 l90ki~^^~- 總計 "T〇0〇kf^·''''-- ------ 實施例14 製備了表14所描述的液體製劑’其含有所示的Ch：4雙亞院美二醇雙/ 單-CrCt烷基醚及活性成分多氟脲與氟苯尿素之組合，其中多氣尿素加氣苯 脲與CrQ雙亞烷基二醇雙/單-CrCt烷基醚的比例為約^ * U 0貫万(歹丨J 14 的製劑含有按重量計40°/。的C2-C4雙亞烷基二醇雙/單-。 表14 實施例14:多氟脲+氟苯脲水乳劑 ~~~~~^〜- 成分 mS·~~~'—-- 多氟腺原藥 氟苯腺原藥 十二烷基苯磺酸鈉 吐溫80 聚氧乙烯失水山梨醇單油酸酯 1οδΐ^~~~^-~-- 二丙二醇二丙縫 400kg ~~ - 黃原膠 5kg ~~~— 丙二醇 5 kg 水 "90kg~' --- 總計 1000kg 實施例15 製備了表所描述的液體製劑，其含有所示的CrC4雙亞燒基二醇雙/ 單C,㈣基敝雜成分雙苯1脲錢鈴尿素之組合，其中雙苯請加氣 22 201200021 鈴脲與CrC4雙亞烷基二醇雙/單-CVC4烷基醚的比例发认 G列為約1 : 5。實施例15 的製劑含有按重量計50%的CrQ雙亞烷基二醇雙/單、c 表15 -C4院基醚 實施例15:雙苯氣腺+氣鈴腺水乳每j一 -〜-- 成分 組或S' ~~- _雙苯氟脲原藥 ~~~ 氟鈴脲原藥 ' 十二烷基苯磺酸鈉 l〇Ok^- 吐溫80 ~ lOOkf^-- 聚氧乙烯失水山梨醇單油酸酯 二丙二醇丙喊 100¾~~~- 黃原膠 5kg~~--- 丙二醇 一 1¾~~- 水 190¾~~ — 總計 Toookf' ' 實施例16 沖製備了表16所描述的液體製劑，其含有所示的仏心雙亞院基二醇雙/ 單Ci-C4烧基賴^性成分風蜗腺與殺鈴尿素之組合，其+ 尿素加殺铃 . 脲與C2-C4雙亞烷基二醇雙/單-Ci-Q烷基喊的比例為約丨：2。實施例16的 製劑含有按《計施的CrC4雙亞絲二醇雙/單_c丨_c4烧細。 表16 實施例16:虱蟎脲+殺鈴脲水乳劍 成分 組成 虱蜗腺原藥 8〇kg(作為純品） 23 201200021 100 kg(作為纯品） 100kg 100kg 360kg 5 kg 5kg 250kg 1000kg 殺鈴脲原藥 --- 十二炫基苯 i 溫 80 ^ —---- 聚氧乙敝水山梨醇單油酸醋 二丁二醇二—--- 黃原膠 ~~~~— --- 丙二醇 〜 -— ^ ~~~~~— 總計 " ~~~~— 實施例17 製備了表Π所描述的液體製劑，其含有所示的C2_C4雙亞炫基二醇雙/ 單-c「c4烷基醚及活性成分虱蟎脲與除蟲尿素之組合，其中風蜗展素加除蟲 脲與c2_c4雙亞絲二_單«4絲關比例為約丨：18。實施例17 的製劑含有按重量445%的CrC4雙魏基二輕/單《道基醚。 表17 實施例17.虱蟎脲+除蟲脲水乳劑 成分 組成 ~~'~ 風蜗脲原藥 100kg(作涵系一 除蟲脲原藥 150kg(SiS^)~ 十一烧基本續酸鈉 "Tookg~~~~~—— rjL· .；® Q〇 ~- /JBL 〇\J 聚氧乙烯失水山梨醇單油酸酉旨 "T〇Okg~~~~- 二丁二醇丙喊 "450kg~~~~~~~~~~— 黃原膠 5kg —~ - 24 201200021 丙一醇 5kg 水 ' - Ί 、1 ---·^ 90kg 總計 ------ 1000kg 實施例18 製備了表18所描述的液體製劑，其含有所示的CrC4雙亞炫基二醇雙/ 單-QA絲敝雜成分_職^^尿权組合，其巾·尿素加瓦咬 腺與c2-c4雙亞烧基二醇雙/單_C|_C4烧基謎的比例為約i: 14。實施例18 的製劑含機重量計35%的CrC4雙魏基二輕/單《4院基鍵。 表18 賫施例IS:虱蟎脲+氟啶脲水乳劑 - L、----- 成，刀、 組成 禹腺原藥 5〇kg (作為純品） 齓U定服原藥 200kg (作為純品） 十一说基苯續酸納 100kg 吐》JEL 80 聚氧乙烯失水山梨醇單油酸酯 100kg — 一乙一醇一丁鱗 甘 P；卿 *------ 350kg '~~ 5kg 〜一 丙—醇 —一一- 1 ———~~-___ 5kg 她古 + —— --—------ 190kg v、\if 〇 | 1000kg — 實施例19 〇〇製備了表19所描述的液體製劑，其含有所示的C2-C4雙亞烷基二醇雙/ 單I 4、元基醚及居性成分風蜗脲與氟蟲尿素之組合，其+風瞒尿素加氣蟲 25 201200021 表19 「〜— 」也判iy.軋蝻脲+氣蟲脲水乳劑 —- Λ 公 '---- 級成 - 乳蜗腺原藥 -·~·—--- 5〇kg(作為純品） 氟蟲脲原藥 —— 5〇kg(作為純品） 十一烧基本續酸鈉 1οϊ5~~^·- 吐溫80 l〇kJ~~- 聚氧乙稀失水山梨醇單油酸酯 一乙一醇丁鱗 ^00¾ -- 黃原膠 5kg - 内一醉 ΐ, ----- 5kg - 水 ~290ki - 總计 loo〇kJ~~- 實施例20 。。製備了表2〇所描述的液體製劑，其含有所示的^雙亞院基二醇雙/ 絲敝活性紐頭職錄尿权組合，射賊尿素加多氣 脲與CVC4雙魏基二醇雙/單.CrC4^__為約丨：〖。實施例2〇的 製劑含有按《-計35%的（〕2<4雙亞絲4雙/單《4貌基謎。 表20 實施例20:虱蟎脲+多氟脲水-- 成分 組成 ''―- 虱蟎脲原藥 100kg(:ii5^)'' 多氟腺原藥 26 201200021_ 100kg 100kg 十-一烧基^ -- 吐溫 80 ^^――- &氧乙烯失水醇單油酸酯 350kg 5kg 5kg 90kg TOQOkg 二丙二醇"二〒ζ'---— . 黃原膠 ^ -- 丙二醇 ~~~ :· ^-—— 總計 ~~ —----- 實施例21 製備了表21所描述的液體製劑，其含有所示的。—。雙亞烷基二醇雙/ 單-CrC4院基醚及活性成分虱蟎脲與氟苯尿素之組合，其中虱蟎尿素加氟苯 脲與CVQ雙亞烷基二醇雙/單_CrC4烷基醚的比例為約〖：實施例21的 製劑含有按重量計20%的CrQ雙亞烷基二醇雙/單-CrC4烷基醚。 表21 實施例21:虱蟎脲+氟苯脲水乳劑 成分 組成 虱瞒脈原藥 50kg(作為純品） IL苯脲原藥 50kg(作為純品） 十二烷基苯磺酸鈉 100kg 吐溫80 100kg -- 聚氧乙烯失水山梨醇單油酸酯 二丙二醇丁醚 100kg 二丙二醇二丁醚 100kg —- 黃原膠 5kg 丙二醇 5kg —--- —--- 27 201200021 水 490kg 總計 1000kg~~~~- 實施例22 製備了表22所描述的液體製劑，其含有所示的C2-C4雙亞燒基二酵雙/ 單-Q-Q烷基醚及活性成分殺鈐脲與氟苯尿素之組合，其中殺鈴尿素加氟苯 脲與CrC4雙亞烷基二醇雙/單-Q-Ct烷基醚的比例為約1 : 2。實施例22的 製劑含有按重量計40%的CrQ雙亞烷基二醇雙/單-CVQ院基醚。 表22 實施例22:殺鈴脲+氟苯脲水乳劑 一'-- 成分 殺鈴脲原藥 100kg(作為純品） 氟苯脲原藥 100kg(作為純品） 十二烷基苯磺酸鈉 ~T〇Oki~~ 吐溫80 聚氧乙烯失水山梨醇單油酸酯 T〇Okg ' 二丁二醇二丁醚 200kg 一丙二_丁縫 200kg 黃原膠 丙二醇 ~5ki 水 了90kg 總計 -- 100¾~~ 實施例23 。。製備了表23所描述的液體製劑’其含有所示的c2_C4雙亞烧基二醉雙/ 單c, ca基㈣及力性成分殺鈐脲與多氟尿素之組合，其中殺鈴展素加多氟 28 201200021 脲與CrQ雙亞烷基二醇雙/單_Q-C4烷基醚的比例為約丨：3·3。實施例23 的製劑含有按重量計50%的CrC4雙亞烷基二醇雙/單-Crc4烷基醚。 表23 實施例23:殺鈴脲+多氟脲水乳劑 成分 組成 殺铃脈原樂 100kg(作為純品） 多氟脲原藥' — 50kg(作為純品） Γ -一炊i基本A黃酸納 100kg 吐溫80 聚氧乙烯失水山梨醇單油酸酯 100kg —J —»¥ J 500kg — ~ 畀原膠 - 而一赌 _ 5kg -------- 5kg 仝囱含·]· ~~~'--- 140kg _ 1000kg 實施例24 對實％例1至23的樣品進行了 ]代的低溫穩紐測試如天以及5代 的熱貯存穩定性測試丨4天。還+ 還在3〇0C以5%v/v的比例在CIPAC D標準水 中進行了稀釋穩定性測試24小時。 隹 ί根據本發明的以下樣品進行了用於檢查相對植物毒性的測試並與市 5G 7_產品私了比較。就植物雜症狀的嚴重性而言， 僳品分為以下幾類： 第〇類：無植物毒性 第1類：輕度植物毒性 第2類：強烈植物毒性 29 201200021 本發明乳劑具有以下特性： 實施例 在-14°C下30天 的低溫穩定性 在54°C下14 天的熱貯存 穩定性 24小時的稀釋 穩定性 （5% v/v) 實施例1 流動性良好，無 結晶形成 流動性良 好，無結晶形 成 無分離’無結晶 形成 實施例2 流動性良好，無 結晶形成 流動性良 好，無結晶形 成 無分離，無結晶 形成 實施例3 流動性良好，無 結晶形成 流動性良 好，無結晶形 成 無分離，無結晶 形成 實施例4 流動性良好，無 結晶形成 流動性良 好，無結晶形 成 無分離’無結晶 形成 實施例5 流動性良好，無 結晶形成 流動性良 好，無結晶形 成 無分離，無結晶 形成 實施例6 流動性良好，無 結晶形成 流動性良 好，無結晶形 成 無分離，無結晶 形成 實施例7 流動性良好，無 結晶形成 流動性良 好，無結晶形 成 無分離*無結晶 形成 實施例8 流動性良好，無 流動性良 無分離，無結晶 30 201200021 結晶形成 好，無結晶形 成 形成 實施例10 流動性良好，無 結晶形成 流動性良 好，無結晶形 成 無分離，無結晶 形成 實施例11 流動性良好，無 結晶形成 流動性良 好，無結晶形 成 無分離，無結晶 形成 實施例12 流動性良好，無 結晶形成 流動性良 好，無結晶形 成 無分離，無結晶 形成 實施例13 流動性良好，無 結晶形成 流動性良 好，無結晶形 成 無分離，無結晶 形成 實施例15 流動性良好，無 結晶形成 流動性良 好，無結晶形 成 無分離，無結晶 形成 實施例16 流動性良好，無 結晶形成 流動性良 好，無結晶形 成 無分離5無結晶 形成 實施例17 流動性良好，無 結晶形成 流動性良 好，無結晶形 成 無分離^無結晶 形成 實施例18 流動性良好，無 結晶形成 流動性良 好，無結晶形 成 無分離，無結晶 形成 31 201200021 實施例19 流動性良好，無 結晶形成 流動性良 好，無結晶形 成 無分離’無結晶 形成 實施例20 流動性良好，無 結晶形成 流動性良 好，無結晶形 成 無分離，無結 形成 實施例匕 流動性良好，無 結晶形成 流動性良 好，無結晶形 成 無分離’無結晶 形成 實施例22 流動性良好，無 結晶形成 流動性良 好，無結晶形 成 無分離，無結晶 形成 實施例23 流動性良好，無 結晶形成 流動性良 好，無結晶形 成 無分離，無結晶 形成 測試製劑植物毒性的試驗表明，實施例1至23均表現出第一類水準的 植物毒性。與市售Lufenuron 50產品的比較測試表明產品顯示出第二類水 準的植物毒性。總之，本發明水乳劑的植物毒性比同類市售水乳劑產品明 顯更低。 從上述實驗資料可見，本發明的水乳劑在低溫和高溫下均具有良好的 流動性及貯雜定性。料，本發明製綱表現丨物毒㈣顯低於同 類市售水乳劑產品的。製劑中存在的C2_Q雙亞炫基二醇雙/單«4烷基醚 表現出顯著輪止殺蟲活性的笨甲醯絲基尿素類衍生物結晶的性能，同 時還有助於顯著減少製劑使用時對環境的負面影響。 【圖式簡單說明】 32 201200021 無 【主要元件符號說明】20 201200021 Diflubenzuron original drug __ lbokg (as pure product) Fluoridine urea original drug 50kg (as pure product) 12-base benzoic acid sodium 100kg Tween 80 " 100kg — Polyoxyethylene sorbitol Monooleate diethylene glycol dipropylene 300 kg xanthan gum 5 kg propylene glycol 5 kg water 340 kg total 1000 kg Example 13 The liquid formulation described in Table 13 was prepared containing the C2_C4 bisalkylene glycol bis/single shown -QQ silk warfare·Combination of the composition of the fluorhexidine job urea, in which flubendiamide plus multi-gas urea and CrQ double-Asian diol bis / single A ·. The ratio of alkyl ether is about 丨: 丨4. The formulation of Example u contained 35% by weight of CrC4 diweildyl glycol bis/mono-CrC4^ linkage. Table 13 Example 13: Flufenidil + Polyfluorourea Water Emulsion Ingredients Fluroxycarbazone Original Drug Polyfluorourea Original Drug - Sodium Benzoate Sodium Tween 80 Polyoxyethylene Loss Sorbitol Monooleate Diethyl ether xanthan gum composition 2〇〇kg (as pure product) 5〇kg (as pure product) 100kg 100kg 350kg 5kg 21 201200021 Propylene glycol 5kT^————— Water l90ki~^^~- Total "T〇0〇 Kf^·''''-------- Example 14 The liquid formulation described in Table 14 was prepared which contained the Ch:4 Shuangyayuan diol bis/mono-CrCt alkyl ether shown. And a combination of the active ingredient polyfluorourea and fluorophenylurea, wherein the ratio of the multi-gas urea-added phenylurea to the CrQ bis-alkylene glycol bis/mono-CrCt alkyl ether is about ^ * U 0 million (歹丨The formulation of J 14 contained 40% by weight of C2-C4 bisalkylene glycol bis/mono-. Table 14 Example 14: Polyfluorourea + fluorophenylurea aqueous emulsion ~~~~~^~ Ingredients mS·~~~'—-- Polyfluoroadenosine fluorobenzamine drug sodium dodecyl benzene sulfonate Tween 80 polyoxyethylene sorbitan monooleate 1οδΐ^~~~^-~ -- Dipropylene glycol dipropylene joint 400kg ~~ - Xanthan gum 5kg ~~~- Propylene glycol 5 kg Water & q Uot; 90kg~' --- Total 1000kg Example 15 The liquid preparation described in the table was prepared, which contained the CrC4 bis-alkylene diol bis/single C, (tetra)-based doping component bisbenzene 1 urea bell Combination of urea, wherein bisbenzene is added to gas 22 201200021 The ratio of chlorinated urea to CrC4 disalkylene glycol bis/mono-CVC4 alkyl ether is identified as G: about 1: 5. The formulation of Example 15 contains by weight 50% CrQ bisalkylene glycol bis/single, c Table 15-C4 yard ether Example 15: bisbenzene gas gland + air bell gland water emulsion per j-~-- into group or S' ~ ~- _Diphenylfluorourea original drug ~~~ hexaflumuron original drug 'sodium dodecyl benzene sulfonate l〇Ok^- Tween 80 ~ lOOkf^-- polyoxyethylene sorbitan monooleate Dipropylene glycol propylene shouted 1003⁄4~~~- xanthan gum 5kg~~--- propylene glycol- 13⁄4~~- water 1903⁄4~~ - Total Toookf' ' Example 16 The liquid preparation described in Table 16 was prepared and contained The combination of 仏 双 双 双 双 双 双 / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / /Single-Ci-Q alkyl shunting ratio is about 丨: 2. Implementation Formulations comprise from 16 "Count Shi CrC4 glycol bis Yasi double / single _c Shu _c4 fine burned. Table 16 Example 16: 虱螨urea + chlorfluazuron water emulsion sword composition 虱 虱 原 original drug 8 〇 kg (as pure) 23 201200021 100 kg (as pure) 100kg 100kg 360kg 5 kg 5kg 250kg 1000kg to kill the bell Urea original drug --- 12 Xuanji benzene i temperature 80 ^ —---- polyoxyethylene sorbitol monooleic acid vinegar dibutyl glycol di---- xanthan gum ~~~~— -- - Propylene glycol ~ - - ^ ~~~~~ - Total " ~~~~ - Example 17 The liquid formulation described in Table E, which contains the indicated C2_C4 bis-thylene glycol bis/single-c "C4 alkyl ether and the combination of the active ingredient guanidinium and sterilized urea, wherein the ratio of spirulina plus diflubenzuron to c2_c4 double-filament bis-single is about 18: 18. Formulation of Example 17. Contains 445% by weight of CrC4 diweidi di light/single channel ether. Table 17 Example 17. Ingredients composition of guanidinium + diflubenzuron water emulsion ~~'~ 100 kg of wind sulphonic urea drug A dechimide urea drug 150kg (SiS^) ~ eleven burning basic sodium sulphate "Tookg~~~~~——rjL· .;® Q〇~- /JBL 〇\J polyoxyethylene sorbitol Monooleic acid 酉 &"T〇Okg~~~~- Butylene glycol propylene shouted "450kg~~~~~~~~~~~ Xanthan gum 5kg —~ - 24 201200021 Propyl alcohol 5kg water ' - Ί , 1 ---·^ 90kg Total ----- - 1000 kg Example 18 The liquid formulation described in Table 18 was prepared, which contained the indicated CrC4 bis-thylene glycol bis/mono-QA silk doping component _ occupation ^^ urinary right combination, and its towel·urea watt The ratio of the occlusal gland to the c2-c4 bis-alkylene diol bis/single_C|_C4 is about i: 14. The formulation of Example 18 contains 35% of the weight of the CrC4 bis-weidi di light/single "4 hospital base keys. Table 18 賫Example IS: guanidinium + fluridazine aqueous emulsion - L,----- into, knife, composition of the original drug 5 〇kg (as pure) 齓U Take the original drug 200kg (as pure product) 11 said benzene benzoic acid sodium 100kg spit" JEL 80 polyoxyethylene sorbitan monooleate 100kg — one ethyl alcohol monobutyl sulphate P; Qing *---- -- 350kg '~~ 5kg ~ one propyl-alcohol - one-one - 1 ---~~-___ 5kg Her ancient + —— --------- 190kg v, \if 〇 | 1000kg - Example 19 〇〇Prepared the liquid formulation described in Table 19 containing the C2-C4 bisalkylene glycol bis/single I 4 as indicated , combination of ketone ether and halophilic urea and flubendialdehyde urea, its + wind 瞒 urea plus worm 25 201200021 Table 19 "~ -" also judge iy. rolling urea + worm urea emulsion - Λ公'----级成- 乳乳腺腺药-·~·---- 5〇kg (as pure product) flufenicol original drug - 5〇kg (as pure product) Sodium 1οϊ5~~^·- Tween 80 l〇kJ~~- Polyoxyethylene sorbitan monooleate monoethyl ketone Ding scale ^003⁄4 -- Xanthan gum 5kg - Inside a drunk, -- --- 5kg - water ~ 290ki - total loo〇kJ~~- Example 20. . The liquid preparations described in Table 2A were prepared, which contained the combination of the indicated double-semi-diol diol double/filaria oxime activity, and the thief urea plus polyurea urea and CVC4 diweiyl diol. Double/single.CrC4^__ is about 丨: 〖. The formulation of Example 2 contained 3% of [] 2 < 4 double-filaments 4 pairs / single "4 appearances. Table 20 Example 20: guanidinium + polyfluorourea water - composition ''―- 虱螨Urea original drug 100kg (: ii5^)'' Polyfluoroadenosine 26 201200021_ 100kg 100kg Ten-one base ^ -- Tween 80 ^^ --- & oxyethylene dehydration alcohol Oleate 350kg 5kg 5kg 90kg TOQOkg Dipropylene glycol "二〒ζ'---- . Xanthan gum ^ -- Propylene glycol ~~~ :· ^-—— Total ~~ —----- Example 21 Preparation The liquid formulation described in Table 21, which contains the combination of bis-alkylene glycol bis/mono-CrC4 oxime ether and the active ingredient guanidinium and fluorophenylurea, wherein bismuth urea plus fluorine The ratio of phenylurea to CVQ bisalkylene glycol bis/mono-CrC4 alkyl ether is about 〖: The formulation of Example 21 contains 20% by weight of CrQ bisalkylene glycol bis/mono-CrC4 alkyl Table 21 Example 21: guanidinium + fluorophenylurea water emulsion component composition 虱瞒 原 original drug 50kg (as pure) IL phenylurea original drug 50kg (as pure) sodium dodecyl benzene sulfonate 100kg Tween 80 100kg -- Polyoxyethylene dehydrated Yamanashi Alcohol monooleate dipropylene glycol butyl ether 100kg Dipropylene glycol dibutyl ether 100kg —- Xanthan gum 5kg Propylene glycol 5kg —--- —--- 27 201200021 Water 490kg Total 1000kg~~~~- Example 22 Prepared Table 22 The liquid preparation described, which comprises the combination of the C2-C4 bis-alkylene diacetate/single-QQ alkyl ether and the active ingredient chlorfenapyr and fluorophenylurea, wherein the chlorfenapyr and the fluorophenylurea are The ratio of CrC4 disalkylene glycol bis/mono-Q-Ct alkyl ether is about 1: 2. The formulation of Example 22 contains 40% by weight of CrQ bisalkylene glycol bis/single-CVQ Table 22 Example 22: Triflumuron + fluorophenylurea aqueous emulsion - '-- component of the drug to kill the chloramphenicol 100kg (as pure) fluorophenylurea original drug 100kg (as pure) dodecyl benzene Sodium sulfonate~T〇Oki~~ Tween 80 Polyoxyethylene sorbitan monooleate T〇Okg ' Dibutyl diol dibutyl ether 200kg One propylene _ Ding seam 200kg Xanthan propylene glycol ~5ki Water 90 kg total - 1003⁄4~~ Example 23. The liquid formulation described in Table 23 was prepared which contained the c2_C4 bis-alkylene di-dip double/single c, ca-based (four) and force Partial seal killing compositions polyfluoro urea, and urea, wherein triflumuron abductin Cadogan fluoro 28201200021 CrQ bis urea with alkylene glycol bis / mono ratio _Q-C4 alkyl ether is from about Shu: 3.3. The formulation of Example 23 contained 50% by weight of CrC4 bisalkylene glycol bis/mono-Crc4 alkyl ether. Table 23 Example 23: Trichlorsulfuron + polyfluorourea water emulsion composition of the composition of the killing pulse of the original music 100kg (as pure) polyfluoro urea original drug '- 50kg (as pure) Γ - one 炊 i basic A yellow acid Nano 100kg Tween 80 Polyoxyethylene sorbitan monooleate 100kg —J —»¥ J 500kg — ~ 畀原胶 - and a bet _ 5kg -------- 5kg with the bake ···· ~~~'---140kg_1000kg Example 24 The samples of the samples of Examples 1 to 23 were tested for low temperature stability tests such as days and 5 days of heat storage stability test for 4 days. Also + dilution stability test was carried out in CIPAC D standard water at a rate of 5% v/v for 3 hours at 3 〇 0C. ί ί The test for examining relative phytotoxicity was carried out according to the following samples of the present invention and compared with the commercial 5G 7 product. In terms of the severity of plant symptoms, the products are classified into the following categories: Diptera: No phytotoxicity Category 1: Mild phytotoxicity Category 2: Strong phytotoxicity 29 201200021 The emulsion of the invention has the following characteristics: Example 30-day low temperature stability at -14 ° C 14 days heat storage stability at 54 ° C for 24 hours dilution stability (5% v / v) Example 1 good fluidity, no crystal formation fluidity Good, no crystal formation, no separation, no crystal formation Example 2 Good fluidity, no crystal formation, good fluidity, no crystal formation, no separation, no crystal formation Example 3 Good fluidity, no crystal formation, good fluidity, no crystal Formation without separation, no crystal formation Example 4 Good fluidity, no crystal formation, good fluidity, no crystal formation, no separation, no crystal formation, Example 5, good fluidity, no crystal formation, good fluidity, no crystal formation, no separation, No crystal formation Example 6 Good fluidity, no crystal formation, good fluidity, no crystal formation, no separation, no crystal form Example 7 Good fluidity, no crystal formation, good fluidity, no crystal formation, no separation, no crystal formation. Example 8 Good fluidity, no fluidity, no separation, no crystals 30 201200021 Crystal formation is good, no crystal formation Example 10 Good fluidity, no crystal formation, good fluidity, no crystal formation, no separation, no crystal formation Example 11 Good fluidity, no crystal formation, good fluidity, no crystal formation, no separation, no crystal formation, Example 12 Flow Good property, no crystal formation, good fluidity, no crystal formation, no separation, no crystal formation Example 13 Good fluidity, no crystal formation, good fluidity, no crystal formation, no separation, no crystal formation Example 15 Good fluidity, no Crystal formation fluidity is good, no crystal formation, no separation, no crystal formation Example 16 Good fluidity, no crystal formation, good fluidity, no crystal formation, no separation, no crystal formation, Example 17, good fluidity, no crystal formation, fluidity Good, no crystal formation Separation ^No crystal formation Example 18 Good fluidity, no crystal formation, good fluidity, no crystal formation, no separation, no crystal formation 31 201200021 Example 19 Good fluidity, no crystal formation, good fluidity, no crystal formation, no separation No crystal formation Example 20 Good fluidity, no crystal formation, good fluidity, no crystal formation, no separation, no knot formation Example, good fluidity, no crystal formation, good fluidity, no crystal formation, no separation, no crystal formation Example 22 Good fluidity, no crystal formation, good fluidity, no crystal formation, no separation, no crystal formation. Example 23 Good fluidity, no crystal formation, good fluidity, no crystal formation, no separation, no crystal formation, test preparation, phytotoxicity Tests have shown that Examples 1 to 23 all exhibit a first class of phytotoxicity. A comparative test with the commercially available Lufenuron 50 product indicates that the product exhibits a second level of phytotoxicity. In summary, the auxotoxicity of the aqueous emulsions of the present invention is significantly lower than that of similar commercial water emulsion products. It can be seen from the above experimental data that the aqueous emulsion of the present invention has good fluidity and storage properties at both low temperature and high temperature. According to the material, the product of the present invention shows that the poison (4) is lower than that of the same type of commercially available water emulsion product. The presence of C2_Q bis-decylene glycol bis/single «4 alkyl ether in the formulation exhibits a remarkable crystallization of the insecticidal activity of the carbamide-based urea derivative, while also contributing to a significant reduction in formulation use. The negative impact on the environment. [Simplified illustration] 32 201200021 None [Key component symbol description]