TW201012393A

TW201012393A - Water dispersible granule

Info

Publication number: TW201012393A
Application number: TW098128002A
Authority: TW
Inventors: Yoshio Nakamura; Eriko Okada
Original assignee: Nippon Soda Co
Priority date: 2008-08-26
Filing date: 2009-08-20
Publication date: 2010-04-01
Also published as: WO2010023863A1; JP5285074B2; TWI407905B; CN102131388B; TW201340870A; JPWO2010023863A1; TWI542282B; CN102131388A; KR101303548B1; KR20110044254A

Abstract

The present invention provides a water dispersible granule comprising an active ingredient for agrichemical having a melting or softening point of 70 DEG C or lower, an acidic white carbon, a basic white carbon, a polycarboxylic acid-type surfactant, and a sugar having a molecular weight of 400 or less, and a method of producing the same. The water dispersible granule of the present invention exhibits an excellent disintegrability and dispersibility in water even after storage under a high temperature and suppresses chemical damages.

Description

201012393 六、發明說明：【發明所屬之技術領域】本發明係關於一種水分散性粒劑，其即使於高溫保存之後’亦具有優異之水中崩解性以及分散性。本申請案係根據2008年8月26曰於曰本申請之專利特願2008-216745號而主張優先權，並於本說明書中援用其内容。【先前技術】農藥製劑中’水分散性粒劑因具有使用時的便利性、安全性以及運送時的省空間性，故需求日益增高，目前正在研發配合有各種農藥有效成分之水分散性粒劑。水分散性粒劑通常係於農藥有效成分（農藥原體）中添加混合濕潤劑、分散劑、結合劑、增量劑等助劑，再將其造粒成顆粒狀來製得。水分散性粒劑通常係以水稀釋、懸浮1〇〜1〇〇〇()倍左右來使用。水分散性粒劑被要求在投入水中後能快速崩分散，而對於提升崩解性以及分散性已有許多的提案。右朋解性或分散性不佳’則有於水中農藥有效成分分離、產生散佈不均、起因於此而有對作物產生藥害之虞。直接將常溫時為液體之農冑有效成分及低熔點之農藥有效成为進行造粒有其困難。因&，已提案出將該農藥有效成:與大量的不活性物質進行混合來製劑之方法，與將 -¾農藥有效成分之溶液吸附於載趙來製劑之方法（非專利文 201012393 獻1)。此外’目前已提出下述二者：將常溫時為液體之農藥有效成分、醣類、濕式法矽的燒成品、息土、以及阶離子性界面活性劑進行混合造粒所獲得之顆粒含水物（專二文獻 1) ;或於熔點| 70。(：以下之農藥有效成分中添加濕式法矽的燒成品以及陰離子性界面活性劑’進—步再添加溶劑以及水溶性載體進行造粒所獲得之水分散性粒劑（專利文獻 2) 。 .於該等中提案之水分散性粒劑，於造粒剛完成時或低溫保存後投人水中會顯示出良好的崩解性以及分散性。然而，於無溫度調整設備的倉庫中保存等情形而導致長時間暴露於高溫環境之後，有時會有崩解性以及分散性降低置於水中農藥有效成分會分離、產生散佈不均的問題。—、作為改良崩解性以及分散性之例子而 υ设itj將溶點或軟化點為7(rc以下之農藥有效成分、作為分散劑之n ❺ 醯化胺酸鹽、與吸附載體構成之混合物進行造粒所獲彳曰之水分散性粒劑(專利文獻3)。然而，有些國家有限制N:化胺酸鹽的使用，因此該限制使用的國家無法使用上述散性粒劑。刀先行技術文獻專利文獻1 ··曰本專利特開2007_3944〇號公報專利文獻2 :日本專利平特開3_163〇〇6號公報專利文獻3 :日本專利特開2〇〇5_1〇4959號公報非專利文獻日本農藥學會農藥製劑._法研究會 201012393 編集、農藥製劑導覽、社團法人日本植物防疫協會發行、 1997 年 1〇月 3〇日、p 22·24 。【發明内容】發明所欲解決之課題本發明之目的在於提供一種即使於高溫下保存之後仍八有優異之水中崩解性以及分散性，且藥物副作用得以抑制之水分散性粒齊j，其含有熔點或軟化點為 70°C以下之農藥有效成分。用以解決課題之手段本發月者為了解決上述課題而進行各種研究結果發現將熔點或軟化點為7〇〇c以下之農藥有效成分與酸性白碳進行混合製得冑混製劑，接著再將該，⑧t齊！、驗性白碳、聚羧酸系界面活性劑、與分子量為4〇〇以下之醣類進行混合、造粒，藉此可製得即使於高温下保存之後仍具有優異之水中崩解性以及分散性，且藥物副作用得以抑制之水分散性粒劑。本發明係根據該發現而進行進一步的研究而完成者。亦即，本發明係一種水分散性粒劑，其含有熔點或軟化點為70°C以下之農藥有效成分、酸性白碳、鹼性白碳、聚羧酸系界面活性劑、以及分子量為4〇〇以下之醣類。本發明之水分散性粒劑中，上述醣類較佳為選自葡萄糖、山梨糖醇、乳糖、蔗糖、以及麥芽糖所構成之群中至少一種。此外，上述農藥有效成分較佳為克熱淨烷笨磺酸 201012393 鹽（Iminoctadine albesilate)。卜本發明係-種水分散性粒劑之製造方法，係含有以下步驟··將熔點或軟化點為⑽以下之農藥有效成分與酸性白碳進行混合製得預混製劑；將該預混製劑、驗性白碳、聚緩酸系界面活性劑、與分子量為4〇〇以下之醣類進行混合；並將所製得之混合物進行造粒。發明效果本發明之水分散性粒劑，即使於高溫下保存之後仍具有優異之水中崩解性以及分散性。亦即，即使於無溫度調整設備:倉庫中保存等情形而導致長時間暴露於高溫環境 1崩解f生以及分散性亦不會降低。此外，因且有優異 =水中崩解性以及分散性，故置於水中農藥有效成分亦不刀離’可抑制散佈不均。其結果使得藥物副作用得以抑制。本發明之水分散性粒劑可適用於農園藝用之農藥。【實施方式】、本發明之水分散性粒劑，其含有熔點或軟化點為7(rc 以下之農藥有效成分、酸性白碳、鹼性白石炭、聚羧酸系界面活性劑、以及分子量為4〇〇以下之醣類。本發明之水分散性粒劑所使用之農藥有效成分係溶點或軟化點A 70。。以下者。該農藥有效成分可使用殺菌劑、殺蟲劑、殺瞒劑、植物生長調節劑、除草劑、殺鼠劑、抗菌劑、抗黴劑、抗藻劑等之用於—般農藥之化合物。該等化合物可單獨使用或混合使用2種以上。 7 201012393 作為炼點為70°C以下之農藥有效成分，例如可列舉 2-(1，2-二甲基丙胺）_4_乙胺基_6甲硫基-三嗪 (Dimethametryn，俗名愛落殺，熔點：65〇c )、s，s_二甲基 _2 (二氟甲基）-4-異丁基_6_(三氟甲基）·3,5·0比啶二羧硫磺酸鹽 (Dithiopyr ’ 俗名硫草定，熔點：65〇c )、2,3_二羥基 _3 3_二甲基本并咬喃-5-基乙烧笨續酸鹽（Benfuresate，俗名草黃，熔點：32〜35°〇、丁基（R)_2-[4-(4-氰基-2-氟苯氧基）苯氧基]丙酸鹽（Cyhal〇fop-butyl，俗名丁基赛伏草，熔點：5〇°c )、 s-i-甲基-1-苯乙基哌啶_丨·硫碳酸鹽（Dimepiperate，俗名草 ❿ 丹，熔點：38.8〜39.3。〇等。此外，作為常溫時為液體之農藥有效成分，例如可列舉2_氣_2’，6，-二乙基_N_(2_丙氧乙基）-乙醯胺苯（Pretilacholr，俗名普拉草）、S-苯甲基_N-(1 2- 一曱丙基）-N-乙硫基胺甲酸鹽（Esprocarb，俗名禾草畏）等。作為軟化點為70。(：以下之農藥有效成分，例如可列舉 U .亞胺基二（伸辛基）二鈒.三（烷苯磺酸鹽）（1111111〇^以丨加 albesilate，俗名克熱淨烷苯磺酸鹽，軟化點55〜6〇。〇等。該等之中，以克熱淨烷苯磺酸鹽較適用於本發明之水〇分散性粒劑。本發明之水分散性粒劑亦可含有熔點及軟化點超過7〇艺之農藥有效成分。該農藥有效成分可使用殺菌劑、殺蟲劑、殺螨劑、植物生長調節劑、除草劑、殺鼠劑、抗菌劑、抗黴劑、抗藻劑等之用於一般農藥之化合物。該等化人物可单獨使用或混合使用2種以上。作為炫點及軟化點超過70°C之農藥有效成分，例如 TJ~ 8 201012393 列舉2-異丙苯基-N-甲基胺甲酸鹽（MIPC，俗名滅必兹，溶點.88〜93C)、3,5· 一甲笨基-N-曱基胺曱酸鹽（XMC，俗名滅克蝨’熔點：99〜10(TC )、3-(4-第三丁基_2_乙氧苯基）-2-(2,6-二氟苯基）-4,5-二經基》惡嗤（Etoxazole，俗名依殺螨，熔點：101〜102°C )、0-3-第三丁苯基-6-甲氧基_2-吼啶 (甲基）硫基胺曱酸鹽（Pyributicarb，俗名稗草畏，熔點：85 7 〜86.2 C )、5-(2,4- 一氣笨氧基）-2-石肖基苯曱基甲酸鹽 (Bifenox ’俗名必芬諾，熔點：84〜86。(：）、1-(α，α -二曱基本甲基）-3-(對甲本基）尿素（Dymron，俗名汰草龍，溶點：2〇3 C)、N，N - —乙基二甲苯基續醯基_1只-1，2,4 -三〇坐-1-甲醯胺（Cafenstrole，俗名唑草胺，熔點：j 14〜116〇c )、曱基_ α-(4,6-一甲氧基响咬-2-基）胺甲醯基胺續醢基〕_鄰甲苯曱酸酯（Bensulfuron-methyl，俗名免速隆，熔點：185〜188 °C )、2·溴-Ν-(α，α_二曱基苯曱基）_3,3_二曱基丁醯胺 (Bromobutide，俗名溴芬諾，熔點：18〇、1(2_氣咪唑 ❹〔丨，2-^吡啶基磺酼基）-3_(4，6-二甲氧基吡啶_2_基）尿素 (Imazosulfuron，俗名依速隆，熔點：183〜184β(： )、1{[〇 (環丙基羰基）苯基]胺磺醯基}-3(4,6-二甲氧基_2_嘧啶基）-尿素 (Cycl〇Sulfamuron，俗名環磺隆，熔點：l49 6〜 1 53 2〇c)、甲基（E)-2-曱氧基亞胺基[α _(鄰甲苯氧基）〇_甲苯基]乙酸酯 (Kresoxim，俗名克收欣，熔點：1〇1 6〜i〇25〇c)、甲基 (E)-2-{2_[6-(2-氰苯氧基）嘧啶_4•基氧基]苯基卜3-甲氧基丙烯酸酯（Azoxystrobin，俗名亞托敏，熔點：η6β〇、5 {[2_ 胺基-5-0-(胺基羰基）-2-去氧_L_木糖基]胺基卜丨，5二去氧 9 201012393 -1-[3,4-二羥基-5-(羥甲基）-2,4-二噁-1(211)-嘧啶基]-；3-0-別呋喃糖酸（P〇ly〇xin ’俗名保粒黴素’熔點：1 60°C以上）、雙（二甲基硫胺曱醯基）二硫醚（Thiram，俗名得恩地，溶點： 155〜156°C )、N-(2,3-二氣-4-羥苯基）-1-曱基環己烷曱醯胺 (Fenhexamid，俗名環酰菌胺，熔點：153°C )、鋅離子配位錳乙烯雙二硫基胺曱酸鹽（Mancozeb，俗名鋅錳乃浦，熔點：192°C以上）、3-(3，5-二氣苯基）-N-異丙基-2,4-二噁味唑啶-1-甲醯胺（Iprodione ’俗名依普同，熔點：134°C )、3， -異丙氧基-2-曱基苯曱酿胺苯（Mepronil，俗名滅普寧，炫點：92〜93°C )、（IRS ’ 2SR ’ 5SR ; IRS，2SR，5SR)-2-(4·* 氯笨甲基）-5-異丙基-1-(1 Η-1，2,4-三唑-1_基甲基）環戊醇 (Ipconazole ’俗名種菌唑’熔點：91〜U9〇c )等。本發明之水分散性粒劑中，熔點或軟化點為7〇t以下之農藥有效成分，相對於水分散性粒劑整體較佳為Μ。質量％。炫點或軟化點超過賊之農藥有效成分的量，相對於 =有效成分整體通常為10質量%以下，較佳為5質量% [酸性白碳] 水分散性粒劑所用之酸性㈣，其非化石夕粉末之中，溶解為1%懸浮液之pH 氧為6〜7.5。酸性白碳以雷射繞射法所求 ~ Μ圭常為1〜50〇β m、較佳為10〜1〇〇、’均粒裎d50通碎等加以調整。〇〇“。其中粒徑可藉由粉 201012393 作為酸性白碳之市售品之例，可列舉CARPLEX # 80 (產品名/ DSL曰本公司製）、CARPLEX XR(產品名/ DSL 曰本公司製）、CARPLEX FPS-3(產品名/ DSL日本公司製）、CARPLEX CS-8(產品名/DSL曰本公司製）、NIPSIL NS-K(產品名/日本矽工業公司製）、NIPSIL NS-KR(產品名 /曰本矽工業公司製）、TOKUSIL NSK(產品名/ TOKUYAMA 公司製）、TOKUSIL P(產品名 / TOKUYAMA 公司製）等。 ❹ 酸性白碳的量，相對於水分散性粒劑整體較佳為1〜50 質量％、更佳為10〜30質量％。 [鹼性白碳] 本發明之水分散性粒劑所用之鹼性白碳，其非晶二氧化矽粉末之中，溶解為1°/❶懸浮液之pH通常為8〜14、較佳為9〜1 3、更佳為1 0〜1 2。該鹼性白碳以雷射繞射法所求得之平均粒徑d5〇通常為2〜100//m、較佳為5〜20#111。 _ 其中粒徑可藉由粉碎等加以調整。作為鹼性白碳之市售品之例，可列舉CARPLEX # 1 00 (產品名/ DSL曰本公司製）、CARPLEX # 1 120(產品名/ DSL 日本公司製）、TOKUSIL AL-1(產品名 / TOKUYAMA 公司製）、NIPSIL ΝΑ (產品名/日本矽工業公司製）、NIPSIL G300(產品名/日本矽工業公司製）、DUROSIL(產品名/ DSL曰本公司製）、EXTRUSIL(產品名/DSL曰本公司製）等》鹼性白碳的量，相對於水分散性粒劑整體較佳為〇. 1〜 11 201012393 5〇質量％、更佳為1〜20質量％。 [聚敌酸系界面活性劑] 本發明之水分散性粒劑所用之聚叛酸系界面活性劑，係主要具有羧酸作為構造單古早位之间刀子界面活性劑。該高刀子界面活性劑之分子|Α Λ 里較佳為1000〜50000。作為聚羧酸界面活性劑’例如可列舉⑴乙烯性不飽和單_之聚合物；（2)乙稀衫飽和單_與乙烯性㈣和n戈其酸軒所構成之聚合物；（3)乙缔性不飽和單叛酸或乙稀性不飽和二叛酸或其酸酐、與碳數為2〜6之烯所構成之聚合物；φ (4)乙㈣不飽和單叛酸或乙稀性不飽和二㈣或其酸針與芳香族乙稀化合物所構成之聚合物及該等之鹽等。作為乙烯性不飽和單缓酸，可列舉丙稀酸、甲基丙稀酸、巴豆酸等。作為乙烯性不飽和二_，可列舉馬來酸、延胡索酸、伊康酸等。作為碳數為2〜6之烯，可列舉乙婦、丙烯、丁稀、異丁烯、二異丁烯等。 · 作為芳香族乙烯化合物，可列舉苯乙烯、甲笨乙稀、乙烯基甲笨、對甲苯乙烯等。作為聚羧酸系界面活性劑之具體例，可列舉聚丙埽酸、丙烯酸與馬來酸所構成之共聚物、異丁烯與馬來酸酐所構成之共聚物、丙烯酸與伊康酸所構成之共聚物、曱基丙烯酸與伊康酸所構成之共聚物、馬來酸與笨乙烯所構成之共聚物、馬來酸與二異丁烯所構成之共聚物及該等之鹽 12 201012393 等。其中，作為鹽，例如可列舉鋰、鈉、鉀等之鹼金屬鹽；鈣、鎂等之鹼土金屬鹽；單甲胺、單乙胺、二甲胺等之胺鹽及銨鹽等。201012393 VI. Description of the Invention: [Technical Field] The present invention relates to a water-dispersible granule which has excellent water disintegratability and dispersibility even after storage at a high temperature. The present application claims priority on the basis of the Japanese Patent Application No. 2008-216745, the entire disclosure of which is incorporated herein by reference. [Prior Art] In the pesticide preparation, the water-dispersible granules are increasingly demanding because of their convenience in use, safety, and space saving during transportation. Currently, water-dispersible granules containing various active ingredients of pesticides are being developed. Agent. The water-dispersible granules are usually obtained by adding a humectant, a dispersing agent, a binder, a bulking agent and the like to the active ingredient (pesticide) of the pesticide, and granulating the granules into granules. The water-dispersible granules are usually diluted with water and suspended for 1 〇 to 1 〇〇〇 () times. Water-dispersible granules are required to rapidly disintegrate after being placed in water, and many proposals have been made for improving disintegration and dispersibility. The right-handedness or poor dispersion is the result of the separation of the active ingredients in the water, the uneven distribution, and the phytotoxicity of the crops. It is difficult to directly perform the granulation of the active ingredient of the agricultural carp and the low melting point of the liquid at normal temperature. As a result of &, the method of preparing the pesticide into a mixture with a large amount of inactive substances, and a method of adsorbing a solution of the active ingredient of the pesticide to the preparation of Zhao Zhao has been proposed (Non-patent 201012393) ). In addition, the following two have been proposed: the granules obtained by mixing and granulating the active ingredients of the liquid at room temperature, the saccharides, the burned products of the wet method, the soil, and the ionic surfactant. (Special 2 literature 1); or at the melting point | 70. (: A water-dispersible granule obtained by adding a solvent of a wet method and an anionic surfactant to the active ingredient of the following pesticides and further adding a solvent and a water-soluble carrier to granulate (Patent Document 2). The water-dispersible granules proposed in the above-mentioned products exhibit good disintegratability and dispersibility in the water after the granulation is completed or after storage at a low temperature. However, storage in a warehouse without temperature adjustment equipment, etc. In the case of prolonged exposure to a high-temperature environment, there may be a problem that disintegration and dispersibility may occur, and the active ingredients of the pesticide may be separated and unevenly distributed in the water. - As an example of improved disintegration and dispersibility And itj is used to set the water-dispersible granules obtained by granulation with a melting point or a softening point of 7 (the active ingredient of the pesticide below rc, the n ❺ sulphated aminate as a dispersing agent, and a mixture of adsorbing carriers). Agent (Patent Document 3). However, some countries have restrictions on the use of N: amide, so the country in which this restriction is used cannot use the above-mentioned granules. Knife First Technical Literature Patent Document 1 Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. ._ Law Research Association 201012393 compilation, pesticide preparation guide, Japanese Society for Plant Epidemic Prevention, issued by the Japan Society for Plant Epidemic Prevention, 1997, 1st, 3rd, and 31st, 2011. [Disclosure] The object of the present invention is to solve the problem of the present invention. Provided is a water-dispersible granule j which has excellent water disintegratability and dispersibility even after storage at a high temperature, and which has a side effect of suppressing the drug, and contains an agricultural chemical active ingredient having a melting point or a softening point of 70 ° C or less. In order to solve the above problems, the present inventors have found that the active ingredient of a pesticide having a melting point or a softening point of 7 〇〇c or less is mixed with acidic white carbon to obtain a sputum mixed preparation, and then This can be obtained by mixing and granulating the white carbon, the polycarboxylic acid-based surfactant, and the saccharide having a molecular weight of 4 Å or less. A water-dispersible granule which has excellent disintegration and dispersibility in water after storage at a high temperature and which has suppressed side effects of the drug. The present invention has been completed based on the findings. Further, the present invention A water-dispersible granule comprising a pesticidal active ingredient having a melting point or a softening point of 70 ° C or less, acidic white carbon, basic white carbon, a polycarboxylic acid-based surfactant, and a sugar having a molecular weight of 4 Å or less In the water-dispersible granule of the present invention, the saccharide is preferably at least one selected from the group consisting of glucose, sorbitol, lactose, sucrose, and maltose. Further, the agricultural chemical active ingredient is preferably gram. Hot net alkane sulfonic acid 201012393 salt (Iminoctadine albesilate). The present invention relates to a method for producing a water-dispersible granule, which comprises the steps of: mixing a pesticidal active ingredient having a melting point or a softening point of (10) or less with acidic white carbon to prepare a premixed preparation; An organic white carbon, a poly-acidic surfactant, and a sugar having a molecular weight of 4 Å or less are mixed; and the obtained mixture is granulated. EFFECTS OF THE INVENTION The water-dispersible granule of the present invention has excellent water disintegratability and dispersibility even after storage at a high temperature. That is, even in the case of no temperature adjustment equipment: storage in a warehouse, etc., it is prolonged exposure to a high temperature environment, and disintegration and dispersibility are not lowered. In addition, because of its excellent = disintegration in water and dispersibility, the active ingredients in the water are not detached from the water, and the uneven distribution can be suppressed. As a result, side effects of the drug are suppressed. The water-dispersible granule of the present invention can be applied to agricultural and horticultural pesticides. [Embodiment] The water-dispersible granule of the present invention contains a melting point or a softening point of 7 (an agricultural chemical active ingredient of less than rc, acid white carbon, basic white carbon carbon, a polycarboxylic acid type surfactant, and a molecular weight of The above-mentioned pesticide active ingredient used in the water-dispersible granule of the present invention is a melting point or a softening point A 70. The following active ingredients can be used as a bactericide, an insecticide or a miticide. A compound for use as a general pesticide, a plant growth regulator, a herbicide, a rodenticide, an antibacterial agent, an antifungal agent, an anti-algae agent, etc. These compounds may be used alone or in combination of two or more. 7 201012393 The refining point is an active ingredient of a pesticide of 70 ° C or less, and for example, 2-(1,2-dimethylpropylamine)_4-ethylamino-6-methylthio-triazine (Dimethametryn, common name: love falling, melting point: 65〇c ), s, s_dimethyl-2-(difluoromethyl)-4-isobutyl-6-(trifluoromethyl)·3,5·0-pyridyldicarboxysulfonate (Dithiopyr ' The common name is thiophanate, melting point: 65〇c), 2,3_dihydroxy_3 3_ dimethyl basic and biting -5-yl-ethyl acetonide (Benfures Ate, common name turf, melting point: 32~35°〇, butyl (R)_2-[4-(4-cyano-2-fluorophenoxy)phenoxy]propionate (Cyhal〇fop-butyl , common name butyl cypress, melting point: 5 〇 ° c), si-methyl-1-phenethyl piperidine 丨硫 thiocarbonate (Dimepiperate, commonly known as grass 丹 Dan, melting point: 38.8 ~ 39.3. 〇, etc. Further, as an active ingredient of a pesticide which is liquid at normal temperature, for example, 2_gas_2',6,-diethyl_N_(2-propoxyethyl)-acetamidobenzene (Pretilacholr, commonly known as Pula Grass), S-benzyl-3-N-(1 2-monopropyl)-N-ethylthiocarbamate (Esprocarb, commonly known as chlorpyrifos), etc. The softening point is 70. (: The active ingredient of the pesticide may, for example, be U. Iminodi(exenyl) diterpene. Tris(alkylbenzenesulfonate) (1111111〇^ with albesilate, common name caloric acid alkylbenzene sulfonate, softening point 55~6〇.〇, etc. Among them, the gram-free benzene sulfonate is more suitable for the hydrazine dispersible granule of the present invention. The water-dispersible granule of the present invention may also contain a melting point and a softening point. More than 7 〇之 pesticide active ingredients. The active ingredient of the medicine may be a compound for general pesticides such as a bactericide, an insecticide, an acaricide, a plant growth regulator, a herbicide, a rodenticide, an antibacterial agent, an antifungal agent, an anti-algae agent, etc. The person can be used alone or in combination of two or more. As a pesticide active ingredient with a brightening point and a softening point exceeding 70 ° C, for example, TJ~ 8 201012393 exemplifies 2-isopropylphenyl-N-methylamine formate (MIPC) , common name, extinction, melting point. 88~93C), 3,5· A phenyl group-N-mercaptoamine decanoate (XMC, common name 灭克虱' melting point: 99~10(TC), 3- (4-tert-butyl-2-ethoxyphenyl)-2-(2,6-difluorophenyl)-4,5-di-based oxime (Etoxazole, common name, killing, melting point: 101 ～102°C), 0-3-t-butylphenyl-6-methoxy-2-acridine (methyl)thiol phthalate (Pyributicarb, commonly known as dicamba, melting point: 85 7 ~ 86.2 C), 5-(2,4-one gas oxy)-2-stone succinyl benzoate (Bifenox' common name Bifino, melting point: 84~86. (:), 1-(α,α-dioxin basic methyl)-3-(p-carbyl) urea (Dymron, common name T. chinensis, melting point: 2〇3 C), N, N - B Dimethylphenyl hydrazino-1 only-1,2,4-tris-l-carbamamine (Cafenstrole, common name oxacillin, melting point: j 14~116〇c), sulfhydryl _ α-( 4,6-monomethoxybend-2-yl)amine-methylglycolylamine hydrazino-benzate-methyl phthalate (Bensulfuron-methyl, common name: speed-free, melting point: 185~188 °C), 2 ·Bromo-indole-(α,α-dimercaptobenzoyl)_3,3-dimercaptobutylamine (Bromobutide, commonly known as bromfenol, melting point: 18 〇, 1 (2_qi imidazolium [丨, 2-(pyridylsulfonyl)-3_(4,6-dimethoxypyridin-2-yl)urea (Imazosulfuron, common name Essence, melting point: 183~184β(:), 1{[〇(ring Propylcarbonyl)phenyl]aminosulfonyl}-3(4,6-dimethoxy-2-pyrimidinyl)-urea (Cycl〇Sulfamuron, commonly known as sulfonate, melting point: l49 6~ 1 53 2〇 c), methyl (E)-2-decyloxyimido [α _(o-tolyloxy) fluorenyl-tolyl] acetate (Kresoxim, commonly known as Kexinxin, melting point: 1〇1 6~i 〇25〇c), methyl (E)-2-{2_[6-(2-Cyanophenoxy)pyrimidin-4-yloxy]phenyl 3-methoxyacrylate (Azoxystrobin, commonly known as Atomic, melting point: η6β〇, 5 {[2_Amino-5-0-(aminocarbonyl)-2-deoxy-L-xylosyl]aminopurine,5-dideoxy 9 201012393 -1-[3,4-dihydroxy- 5-(Hydroxymethyl)-2,4-dioxin-1(211)-pyrimidinyl]-; 3-0-furfuranosyl acid (P〇ly〇xin 'common name scleromycin' melting point: 1 60 Above °C), bis(dimethylthiazinyl)disulfide (Thiram, common name: melting point: 155~156 °C), N-(2,3-diox-4-hydroxybenzene ))-1-nonylcyclohexane decylamine (Fenhexamid, common name Cycloheximide, melting point: 153 ° C), zinc ion coordination manganese ethylene bisdithiol phthalate (Mancozeb, commonly known as zinc manganese Pu, melting point: above 192 ° C), 3-(3,5-diphenyl)-N-isopropyl-2,4-dioxazolidine-1-carboxamide (Iprodione 'common name Same, melting point: 134 ° C), 3, -isopropoxy-2-mercaptobenzoquinone benzene (Mepronil, commonly known as cumin, dazzling point: 92~93 ° C), (IRS ' 2SR ' 5SR ; IRS, 2SR, 5SR) -2-(4·* chloromethyl)-5- Isopropyl-1-(1 Η-1,2,4-triazol-1-ylmethyl)cyclopentanol (Ipconazole 'common name inoculum' melting point: 91~U9〇c) and the like. In the water-dispersible granule of the present invention, the active ingredient of the agricultural chemical having a melting point or a softening point of 7 〇t or less is preferably Μ with respect to the whole of the water-dispersible granule. quality%. The amount of the active ingredient of the thief or the softening point exceeding the thief is usually 10% by mass or less, preferably 5% by mass, based on the total amount of the active ingredient (acid white carbon), the acidity used in the water-dispersible granule (4), Among the fossil eve powders, the pH oxygen dissolved in the 1% suspension was 6 to 7.5. The acid white carbon is obtained by the laser diffraction method. Μ 常 is usually adjusted by 1 to 50 〇 β m, preferably 10 to 1 〇〇 , and the average 裎 d50 is broken. 〇〇". The particle size can be obtained by using powder 201012393 as an example of commercially available acid white carbon. For example, CARPLEX # 80 (product name / DSL 曰曰), CARPLEX XR (product name / DSL 曰公司公司), CARPLEX FPS-3 (product name / DSL Japan company), CARPLEX CS-8 (product name / DSL 曰 company), NIPSIL NS-K (product name / manufactured by Nippon Paint Co., Ltd.), NIPSIL NS-KR (product name / manufactured by Sakamoto Industrial Co., Ltd.), TOKUSIL NSK (product name / manufactured by TOKUYAMA Co., Ltd.), TOKUSIL P (product name / manufactured by TOKUYAMA Co., Ltd.), etc. 量 The amount of acid white carbon relative to the water-dispersible granules as a whole It is preferably 1 to 50% by mass, more preferably 10 to 30% by mass. [Basic white carbon] The alkaline white carbon used in the water-dispersible granule of the present invention is dissolved in the amorphous cerium oxide powder. The pH of the suspension of 1 ° / ❶ is usually 8 to 14, preferably 9 to 13, more preferably 10 to 12. The average particle diameter of the alkaline white carbon obtained by laser diffraction D5〇 is usually 2 to 100/m, preferably 5 to 20#111. The particle size can be adjusted by pulverization, etc. As an example of a commercial product of alkaline white carbon, CARPLEX # 1 00 (product name / DSL 曰曰), CARPLEX # 1 120 (product name / DSL Japan), TOKUSIL AL-1 (product name / TOKUYAMA company), NIPSIL ΝΑ (product name / Japan)矽Industrial Co., Ltd.), NIPSIL G300 (product name / manufactured by Nippon Paint Co., Ltd.), DUROSIL (product name / DSL manufactured by the company), EXTRUSIL (product name / DSL manufactured by the company), etc. The total amount of the water-dispersible granules is preferably 〇. 1 to 11 201012393 5% by mass, more preferably 1 to 20% by mass. [Polyuric acid-based surfactant] used in the water-dispersible granule of the present invention The poly-reactive acid surfactant is mainly composed of a carboxylic acid as a knives interfacial surfactant between the single and the early positions. The molecule of the high-knife surfactant is preferably 1000~50000. As a polycarboxylic acid The surfactant 'for example, may be exemplified by (1) a polymer of ethylenically unsaturated mono-; (2) a polymer of a saturated shirt of ethylene and a mixture of ethylene (tetra) and n geqi acid; (3) Saturated mono- ortho-acid or ethyl ortho-saturated acid or its anhydride, with a carbon number of 2 to 6 a polymer composed of φ (4) ethyl (tetra) unsaturated monoterpicic acid or ethylenically unsaturated di(tetra) or a polymer composed of an acid needle and an aromatic vinyl compound, and the like. Examples of the unsaturated monobasic acid include acrylic acid, methyl acrylate acid, and crotonic acid. Examples of the ethylenically unsaturated di-based group include maleic acid, fumaric acid, and itaconic acid. Examples of the alkene having 2 to 6 carbon atoms include ethene, propylene, butylene, isobutylene, and diisobutylene. Examples of the aromatic vinyl compound include styrene, acetophenone, vinyl phenyl bromide, and p-methyl styrene. Specific examples of the polycarboxylic acid-based surfactant include polyacrylic acid, a copolymer of acrylic acid and maleic acid, a copolymer of isobutylene and maleic anhydride, and a copolymer of acrylic acid and itaconic acid. a copolymer of mercaptoacrylic acid and itaconic acid, a copolymer of maleic acid and stupid ethylene, a copolymer of maleic acid and diisobutylene, and the likes of these salts 12 201012393 and the like. In addition, examples of the salt include an alkali metal salt such as lithium, sodium or potassium; an alkaline earth metal salt such as calcium or magnesium; an amine salt or an ammonium salt such as monomethylamine, monoethylamine or dimethylamine.

作為異丁烯與馬來酸酐之共聚物之鹽可舉出ISOB AN 600SF35(產品名/ KURARAY公司製）；作為異丁烯與馬來酸針之共聚物之鹽可舉出Toxanon GR3 1 A(產品名/三洋化成公司製）；作為聚丙烯酸鹽可舉出BOYSS 530(產品名/花王公司製）；作為聚丙烯酸銨可舉出BOYSS 532A(產品名/ 花王公司製）；作為丙烯酸與馬來酸之共聚物之鹽可舉出 BOYSS 520(產品名/花王公司製）或BOYSS 521 (產品名/ 花王公司製）；作為馬來酸與烯之共聚物可舉出 NEWKALGEN WG-5 (產品名/竹本油脂公司製）、 S-SMA3000(產品名 / ARCO CHEMICAL 公司製）、 S-SMA1000(產品名 / ARCO CHEMICAL 公司製）、 S-SMA1440H(產品名 / ARCO CHEMICAL 公司製）、 POLYSTAR OMP(產品名/日本油脂公司製）、POLYSTAR OMA(產品名/日本油脂公司製）、POLYSTAR SMX(產品名 /曰本油脂公司製）、POLYSTAR SM-1015(產品名/日本油脂公司製）、POLYSTAR A-1060(產品名/日本油脂公司製）、Sokakan CP-5(產品名 / BASF 公司製）、Sokakan CP-7(產品名/ BASF 公司製）、Sokakan CP-9(產品名 / BASFThe salt of the copolymer of isobutylene and maleic anhydride is exemplified by ISOB AN 600SF35 (product name / KURARAY Co., Ltd.); the salt of the copolymer of isobutylene and maleic acid needle is Toxanon GR3 1 A (product name / Sanyo) As a polyacrylic acid salt, BOYSS 530 (product name / Kao company) can be cited; as polyacrylic acid ammonium, BOYSS 532A (product name / Kao company) can be cited; as a copolymer of acrylic acid and maleic acid The salt can be exemplified by BOYSS 520 (product name / Kao company) or BOYSS 521 (product name / Kao company); as a copolymer of maleic acid and alkene, NEWKALGEN WG-5 (product name / bamboo oil company) , S-SMA3000 (product name / manufactured by ARCO CHEMICAL), S-SMA1000 (product name / manufactured by ARCO CHEMICAL), S-SMA1440H (product name / manufactured by ARCO CHEMICAL), POLYSTAR OMP (product name / Japanese fat) Company system), POLYSTAR OMA (product name / manufactured by Nippon Oil & Fats Co., Ltd.), POLYSTAR SMX (product name / manufactured by Sakamoto Oil Co., Ltd.), POLYSTAR SM-1015 (product name / Nippon Oil Co., Ltd.), POLYSTAR A-1060 (product name) /Japanese fat Company system), Sokakan CP-5 (product name / BASF company), Sokakan CP-7 (product name / BASF company), Sokakan CP-9 (product name / BASF)

公司製）、SokakanCP-10(產品名/BASF公司製）、GEROPON T/36(產品名/ Rhone Poulenc 公司製）、GEROPON SC/ 213(產品名 /Rhone Poulenc 公司製）或 8οι·ρο1-7248(產品名 13 201012393 /東邦化學公司製）等。 ’相詞'於水分 1〜7質量。。聚綾酸系界面活性劑的量並無特別限定散性粒劑整體通常為0.5〜10質量％、較佳為 [醣類] 作為本發明之水分散性粒劑所用之酿類， β 別 J歹丨j舉分子量為400以下之單醣類以及雙醣類及其衍生物。較佳者。列舉葡萄糖、半乳糖、甘露糖、果糖、麥芽糖、山梨糖醇、乳糖 '蔗糖、甘露糖醇，更佳者可列舉葡萄糖、山梨糖醇、 ❹ 乳糖、蔗糖、麥芽糖。該等醣類可單獨使用，或組合使用二種以上。分子量為400以下之醣類的量並無特別限定相對於Company system), SokakanCP-10 (product name / BASF company), GEROPON T/36 (product name / Rhone Poulenc company), GEROPON SC / 213 (product name / Rhone Poulenc company) or 8οι·ρο1-7248 ( Product name 13 201012393 / manufactured by Toho Chemical Co., Ltd.). 'The word' is in the water 1~7 mass. . The amount of the polyphthalic acid-based surfactant is not particularly limited to 0.5 to 10% by mass, and preferably [saccharide] is used as the water-dispersible granule of the present invention, and β is J.单 j is a monosaccharide having a molecular weight of 400 or less and a disaccharide and a derivative thereof. Better. Examples of glucose, galactose, mannose, fructose, maltose, sorbitol, lactose, sucrose, and mannitol include glucose, sorbitol, sucrose, sucrose, and maltose. These saccharides may be used singly or in combination of two or more. The amount of the saccharide having a molecular weight of 400 or less is not particularly limited with respect to

水分散性粒劑整體通常為i〜15質量％、較佳為2〜ι〇 I %。步含有上述以外上述之構成成分本發明之水分散性粒劑可視情況進一之濕潤劑、增量劑' 結合劑。於該情形，的配合比例較佳為維持於上述範圍内。作為濕潤劑烧基苯確酸納、香醚等。例如可列舉燒基萘磺酸鈉、燒基硫酸鈉、烷基磺酸化琥珀酸鈉、聚環氧乙烯烷基芳The whole of the water-dispersible granules is usually from 1 to 15% by mass, preferably from 2 to 〇1%. The step further comprises the above-mentioned constituent components other than the above. The water-dispersible granule of the present invention may be further a humectant or a bulking agent as a binder. In this case, the blending ratio is preferably maintained within the above range. As a wetting agent, sodium benzoate, oleyl ether, etc. For example, sodium sulphate naphthalene sulfonate, sodium sulfonate, sodium sulfosuccinate succinate, poly(ethylene oxide alkyl aryl) can be cited.

作為增量劑，例如可列舉 J夕j举雲母、碳酸鈣、高嶺土、黏土、皂土、石夕藻土、彿石 '厄帖浦土、酸性白土、滑石、碳酸鎮氧化鈦、硫酸錄' 硫酸鈉、尿素等。作為結合劑，你| ^ 7 °列舉羧甲基纖維素、聚乙烯醇、聚乙烯石比嗔烧酮、糊祛糊精、可溶性澱粉等。 14 201012393 本發明之水分散性粒劑的形狀根據製備方法、條件等而有所不同，通常為不定形、立方體狀、|方體狀、三稜椎狀、圓錐狀、圓柱狀、球狀、讀狀、㈣狀、印狀、凸透鏡狀、凹透鏡狀、板狀等。以較佳為不定形、圓柱狀、球狀及橢球狀。此外’水分散性粒劑的大小，其最大長度部分較佳為0.1〜5mm。本發明之水分散性粒劑的粒徑較佳為位力50私m〜 2〇〇0"m的範圍、更佳為位於1〇〇#m〜8〇〇“m的範圍。其 /中’該等粒徑並無需使所有顆粒均成為該等範圍内的粒徑’只要全粒度分布之中佔有最多顆粒的粒徑(亦即眾數粒徑Μ立於該等範圍内即可。此外，可藉由分級而僅獲得所需粒徑之顆粒。 [水分散性粒劑之製造方法] 本發明之水分散性粒劑可使用熔點或軟化點#抓以下之農藥有效成分、酸性白碳、鹼性白碳、聚羧酸系界面As the extender, for example, J. J. Mica, calcium carbonate, kaolin, clay, bentonite, Shishizao soil, Buddha stone, eritepu soil, acid white clay, talc, carbonated titanium oxide, sulfuric acid recorded Sodium sulfate, urea, etc. As a binder, you | ^ 7 ° lists carboxymethyl cellulose, polyvinyl alcohol, polyethylene stone than ketone ketone, paste dextrin, soluble starch and so on. 14 201012393 The shape of the water-dispersible granule of the present invention varies depending on the preparation method, conditions, etc., and is usually amorphous, cubic, square, triangular, conical, cylindrical, spherical, Read shape, (four) shape, print shape, convex lens shape, concave lens shape, plate shape, and the like. Preferably, it is in an amorphous shape, a cylindrical shape, a spherical shape, and an ellipsoid shape. Further, the size of the water-dispersible granules is preferably 0.1 to 5 mm in the maximum length portion. The particle size of the water-dispersible granule of the present invention is preferably in the range of 50 m 2 to 2 〇〇 0 Å, more preferably in the range of 1 〇〇 #m 〜 8 〇〇 "m. 'These particle sizes do not need to make all the particles into the particle size within the range' as long as the particle size of the most particle size distribution occupies the largest particle size (that is, the mode particle diameter stands within the range). By grading, only particles of a desired particle size can be obtained. [Method for Producing Water-Dispersible Granules] The water-dispersible granules of the present invention can use the melting point or softening point to capture the following pesticide active ingredients, acid white carbon , alkaline white carbon, polycarboxylic acid interface

活性劑、以及分子量為400以下之酿類，並藉由公知的方法製造。、例如，可將溶，點或軟化點& 7(rc以τ之農藥有效成分、酸性白碳、鹼性白碳、聚羧酸系界面活性劑、以及分子量為400以下之酷类員’以及視情況添加之濕潤劑(二烷基續酸化琥謂鹽等）、增㈣、以及結合劑、與視情況添加之溶劑（水、醇類等），㈣進行混合、擠製造粒、乾燥，藉此方式製造。此外乾燥後亦可進行磨碎等之整粒。此外，農藥有效成分常溫時為液狀之情況，可將農藥 15 201012393 有效成分除外之成分以傲L、+. m + & 與上述相同方式進行擠製造粒獲得粒劑，並使該粒劑吸收 a及收液狀之農樂有效成分，藉此方式製造0 作為獲得本發明之水分散性粒劑的方法，以下述製法為佳.該製法含有以下步驟：將熔點或軟化點& 7〇。。以下之農藥有效成分與酸性白碳進行混合製得預混製劑；將該預混製劑、鹼性白冑、聚羧酸系界面活性劑、與分子量為彻以下之酿類進行混合；並將所製得之混合物進行造粒、、、。 ie粒後，可進一步視情況進行乾燥、粉碎、分級。 ❿ (預混合步驟）將熔點或軟化點為7〇t：以下之農藥有效成分與酸性白碳進行混合。藉此製得預混製劑。農藥有效成分與酸性白碳的混合，例如可使用旋帶式混合機（ribbon mixer)、納塔式混合機（Naut〇r mixer)、混合造粒機等之混合機。農藥有效成分可直接將原料本身與酸性白碳混合來使用，亦可將原料本身溶解於溶劑製成溶液，並將該溶液與 ❿ 酸性白碳混合來使用。作為用以將農藥有效成分溶解之溶劑，可列舉甲醇、乙酵等之醇類；丙酮、甲乙基酮等之酮類；芳香族系烴、脂肪酸酯類、苯二曱酸酯類、植物油等。農藥有效成分以液狀來使用之情形（農藥有效成分的原料本身為液體時或如上述製成溶液時），農藥有效成分會容易吸附於酸性白碳。此外，農藥有效成分與酸性白碳混人 16 201012393 時’可使之凝集成塊狀。此外’關於溶劑，亦可於農藥有辰樂有效成分與酸性白妒0¾ σ後，藉由加溫或減壓等手段來加以除去。 κη 農藥有效成分與酸性白碳混合所獲得況加以粉碎。粉碎手段並無特 °可視情 π吁于仅亚無特別限定，例如可機、鎚磨機、球磨機、喷射磨機等之乾式粉碎機泰碎 (正式混合步驟）The active agent and the brewer having a molecular weight of 400 or less are produced by a known method. For example, a melting point, a point or a softening point & 7 (rc is an active ingredient of τ, an acidic white carbon, an alkaline white carbon, a polycarboxylic acid type surfactant, and a cool class member having a molecular weight of 400 or less' And a humectant (dialkyl succinate salt, etc.), augmentation (4), a binder, and optionally added solvent (water, alcohol, etc.), and (iv) mixing, squeezing, and drying, as the case may be. In this way, it can be manufactured by grinding, etc. In addition, the whole ingredient of the pesticide can be pulverized, etc. In addition, the active ingredient of the pesticide is liquid at normal temperature, and the ingredients other than the active ingredient of the pesticide 15 201012393 can be used to be proud of L, +. m + & In the same manner as above, the granules are obtained by pulverizing, and the granules are absorbed, and the granules are absorbed into a liquid-receiving agricultural active ingredient, thereby producing 0 as a method for obtaining the water-dispersible granule of the present invention, as follows. The preparation method comprises the following steps: the melting point or the softening point & 7 〇. The following pesticide active ingredient is mixed with acidic white carbon to prepare a premixed preparation; the premixed preparation, alkaline chalk, poly Carboxylic acid surfactant, Mixing with a brewer having a molecular weight of less than or equal to the following; and granulating the obtained mixture, and then further drying, pulverizing, and classifying as appropriate. ❿ (Premixing step) Melting or softening The point is 7〇t: the following pesticide active ingredient is mixed with acidic white carbon to prepare a premixed preparation. The mixture of the active ingredient of the pesticide and the acidic white carbon, for example, a ribbon mixer or a nanobelt can be used. Mixer of tower mixer (Naut〇r mixer), mixing granulator, etc. The active ingredient of the pesticide can be directly mixed with the acid white carbon, or the raw material itself can be dissolved in a solvent to prepare a solution. The solvent is used in combination with hydrazine acid white carbon. Examples of the solvent for dissolving the active ingredient of the pesticide include alcohols such as methanol and ethyl yeast; ketones such as acetone and methyl ethyl ketone; and aromatic hydrocarbons and fatty acid esters. Class, phthalate, vegetable oil, etc. When the active ingredient of the pesticide is used in liquid form (when the raw material of the active ingredient of the pesticide is liquid or when the solution is prepared as described above), the pesticide has The ingredients are easily adsorbed to acidic white carbon. In addition, when the active ingredients of pesticides are mixed with acidic white carbon, it can be aggregated into blocks. In addition, 'the solvent can also be used as an active ingredient and acid white peony in pesticides. After 03⁄4 σ, it is removed by means of heating or decompression. κη The active ingredient of the pesticide is mixed with the acid white carbon, and the pulverization means is not particularly limited. Dry crusher for machine, hammer mill, ball mill, jet mill, etc. (formal mixing step)

接著，於預混製劑中’添加鹼性 ^ H4. \ 取竣酸系界面 /性劑與分子量為4〇〇以下之醣類、劑、其#夕夭“為丨θ人及視情況添加濕潤其他之添加劑。混合手段並無特別pp ~ 田# 付别限定，可適當選自 :預混合步驟中之手段中所列舉者。、旮 u 此式混合之降，可步添加農樂有效成分。正式混人麻；八合所添加之農藥有效成刀可為於預混合時所添加者相同，亦可不同。正式混合後可視情況將混合物粉別I® ^ 初份碎。粉碎手段並ϋΐ特 W限疋，可適當選自用於預混合步 … , 哪甲之手段中所列舉者。 (加水混練步驟）本混合步驟後，可一邊加水的大i N，閲濕—邊進行混練。加水 J万法可使用公知的條件以及手段。噴霧笙士 + ^ 于奴例如滴加、噴射、或 I · 卞為混練機，例如可列 .納塔式混合機、旋帶式混合機、拖榮了舍爾〉見合機、捏合機4。該等中較佳為捏合機。辦&口。例如可列舉自來理水、逆滲透膜（RO) 精製水；地下水、井現練中所添加之水並無特別限定火工業用水、蒸德水、離子交換樹脂處處理水、以及超過濾膜（UF)處理水等之 17 201012393 水、河川湖泊水等之天然水。混練時添加之水量，相對於混合物通常為3〜70重量％、較佳為5〜6〇重量％。混練時間隨著製k之規模以及混練機的種類而異，較佳冑3分鐘〜60分鐘、較佳為5分鐘〜20分鐘。 (造粒步驟）接著，將所製得之混練物進行造粒。作為造粒機，例如可列，籃式造粒機；队式擠出機、雙頂式—η如㈣造粒機、單頂式（Singledoom)造粒機、製粒機等擠製造粒機，輪壓機等壓縮造粒機等。該等中較佳為擠製造粒機。擠製粒控隨著所用之原料及/或添加水量而異，較佳為〇·2〜 2.0mm、更佳為〇·5〜 12mm。 (乾燥整粒步驟）明之上述方法所製得之造粒物，可直接使用作為本發使用二心生粒劑’亦可視情況進行乾燥、整粒或分級來使用作為本發明之水分散性粒劑。、乾燥步驟只要可將於混練步驟等添加之引起組成物之化學變化，則無特別 I去而不燥時間隨著添加之水量以及使用之裝置而乾設為室溫〜_、較佳為，C〜，c，且時間可 2分鐘〜3小時、較佳為丨〇八常可叹為較佳為1〇刀鐘〜j小時。作如可列舉：通風帶式乾燥機、揽拌乾燥機：：機’例振動乾燥機'床式乾燥機等。乾燥機、整粒機只要為可獲得適當粒徑者則可列舉絞肉機（平賀工作所 “、，j限疋。例如作所股份有限公司製)或掷出造粒機 18 201012393 (FUJIP AUDAL股伤有限公司）等螺旋型擠出機，或羅得普雷克斯（ROATPLEX，Hosokawa Micr〇n股份有限公司製）等堅固型粉碎機、輥式粒化機（日本GRanulat〇r公司製造）等絞碎方式之磨碎機、球形整粒機、微粉碎機等。分級機並無特別限定。例如可列舉迴轉筛或電磁振動式篩選機等。 [水分散性粒劑之施用方法] 〇本發明之水分散性粒劑可於投入水中分散稀釋後，藉由喷霧機等施用於作物或土壤等。對水的稀釋倍率，隨著水刀散11粒劑中之農藥有效成分的種類、含有量、施的而異，通常為10〜10000倍、較佳為50〜_倍更佳為500〜4000倍。用於稀釋、懸浮所用的水並無特別限制，使用軟水或硬水皆可。例如可列舉自來水、工業用水、蒸館水、離子交換樹脂處理水、逆滲透膜⑽)處理水、以及超㈣膜⑽） ❹處理水等之精製水；地下水、井水、河川湖泊水等之天然水至於硬水可舉出例如以CIPAC(C〇llab〇rative nternational Pestlcide Analytical c〇uncil，·國際農藥分析法協礒會）法之所謂CIPAC標準水D(342ppm(Ca2+ : Mg2+=4 : 1))，但不限於此。 .Next, in the premixed preparation, 'addition of alkaline ^ H4. \ to take the tannic acid interface / sex agent and the molecular weight of 4 〇〇 or less of the sugar, the agent, the #夕夭" is 丨 θ person and optionally add moist Other additives. The mixing method is not limited to pp ~ Tian #, and can be appropriately selected from those listed in the premixing step. 旮u This type of mixing can be added to the active ingredients of the farm. Formal mixed hemp; The effective pesticide added to the bacon can be the same as that added during premixing, or it can be different. After the formal mixing, the mixture powder can be crushed by I® ^. W is limited to 疋, and can be appropriately selected from those used in the pre-mixing step..., which is the method listed in the method. (Adding water mixing step) After the mixing step, the water can be mixed while the water is being mixed. Wanfa can use well-known conditions and means. Spray gentleman + ^ slaves such as dropping, spraying, or I · 卞 is a mixing machine, such as can be listed. Nata mixer, rotary belt mixer, dragging Sher> see the machine, kneading machine 4. Which is better It is a kneading machine. For example, it can be exemplified by tap water and reverse osmosis membrane (RO) refined water; water added in groundwater and well training is not limited to fire industrial water, steamed water, and ion exchange. Resin treatment water, and ultrafiltration membrane (UF) treatment water, etc. 17 201012393 Water, river water, etc. Natural water, the amount of water added during mixing is usually 3 to 70% by weight, preferably 5~ with respect to the mixture. 6〇% by weight. The kneading time varies depending on the scale of the k-forming machine and the type of the kneading machine, and is preferably from 3 minutes to 60 minutes, preferably from 5 minutes to 20 minutes. (Pelletizing step) Next, it is prepared. The kneaded material is granulated. As a granulator, for example, a basket granulator; a team extruder, a double top type - η (4) granulator, a single top type (Singledoom) granulator, A granulator, such as a granulator, a compression granulator such as a wheel press, etc. Preferably, the granulator is extruded. The granulation control varies depending on the raw materials used and/or the amount of water added, preferably 〇. · 2~2.0mm, more preferably 〇·5~ 12mm. (Drying and granulating step) The obtained granules can be directly used as the hair granules used in the present invention, and can also be used as the water-dispersible granules of the present invention by drying, granulating or classifying as appropriate. When the step or the like causes a chemical change of the composition, there is no special I to go without drying time. With the amount of water added and the device used, it is set to room temperature 〜_, preferably, C~, c, and the time is 2 minutes to 3 hours, preferably 丨〇8 often sighs preferably 1 knives clock ~ j hours. For example: ventilation belt dryer, mixing dryer:: machine 'example vibration dryer 'Bed dryer, etc.. The dryer and the granulator can be exemplified by a meat grinder as long as the appropriate particle size is available (Pinghe Work Center). For example, manufactured by Co., Ltd.) or throwing a granulator 18 201012393 (FUJIP AUDAL Co., Ltd.) and other spiral extruders, or Roy Plex (ROATPLEX, manufactured by Hosokawa Micr〇n Co., Ltd.) Such as a solid pulverizer, a roll granulator (manufactured by Japan's GRanulat〇r Co., Ltd.), etc., such as a grinding machine, a spherical granulator, a micro pulverizer, and the like. The classifier is not particularly limited. For example, a rotary screen or an electromagnetic vibration type screening machine can be cited. [Method of Application of Water-Dispersible Granules] The water-dispersible granules of the present invention can be applied to crops or soil by a spray machine or the like after being dispersed and diluted in water. The dilution ratio of water is usually 10 to 10,000 times, preferably 50 to _ times, more preferably 500 to 4,000, depending on the type, content, and application of the active ingredient of the pesticide in the water granules. Times. The water used for dilution and suspension is not particularly limited, and either soft water or hard water can be used. Examples thereof include tap water, industrial water, steamed water, ion exchange resin treated water, reverse osmosis membrane (10) treated water, and super (tetra) membrane (10)) purified water such as treated water; groundwater, well water, river water, etc. The natural water as the hard water may be, for example, CIPAC standard water D (342 ppm (Ca2+: Mg2+=4: 1) by CIPAC (C〇llab〇rative nternational Pestlcide Analytical c〇uncil, International Pesticide Analysis Association) method. ), but not limited to this. .

[水分散性粒劑之包裝形態] 本發明之水分散性粒劑可使用鋁袋、紙袋、紙盒、寶特瓶等，通常可用於粒劑或可濕性粉劑的容器或包褒。保存時為了避免受潮，較佳為鋁袋或内部鍍鋁之紙袋、聚合 201012393 物袋、寶特瓶等。此外，可將包裝於水溶性盒之水分散性粒劑填充於防止該等受潮之袋中，藉此可使保存時防止受潮、提升安全性、提升稀釋時的使用性。實施例以下表示實施例以及比較例，藉此對本發明進行具體說明，但本發明並不侷限於該等實施例。 (實施例1) 將烷苯磺酸鹽（軟化點：60。〇50質量份溶解於甲醇5〇質量份。將該溶液混合酸性白碳（鹽野義製藥股份有限公司製，產品名「CARPLEX XR」50質量份，並以50°C加溫以除去甲醇。所得之粉末狀混合物利用喷射磨機（Nipp〇n[Packaging Form of Water-Dispersible Granules] The water-dispersible granules of the present invention may be used in aluminum bags, paper bags, cartons, bottles, etc., and are generally used for containers or bags of granules or wettable powders. In order to avoid moisture, it is preferably an aluminum bag or an aluminum-plated paper bag, a polymerized 201012393 bag, a PET bottle, and the like. Further, the water-dispersible granules packaged in the water-soluble cartridge can be filled in a bag for preventing such moisture, thereby preventing moisture from being stored during storage, improving safety, and improving usability during dilution. EXAMPLES Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to the examples. (Example 1) An alkanebenzenesulfonate (softening point: 60. 50 parts by mass of hydrazine was dissolved in 5 parts by mass of methanol. The solution was mixed with acid white carbon (manufactured by Shimano Pharmaceutical Co., Ltd., product name "CARPLEX XR" 50 parts by mass and heated at 50 ° C to remove methanol. The resulting powdery mixture was processed by a jet mill (Nipp〇n

Pneumatic Mfg. Co·，Ltd.製，產品名「Supersonic Jet Mill PJM」）粉碎，製得含有烷苯磺酸鹽5〇%之顆粒（預混製劑）。將cylfufenamid(俗名環氟菌胺，日本曹達公司製，溶點：約62°C )3.4質量份、上述預混製劑40質量份、鹼性白碳（DSL曰本公司製，產品名「CARPLEX# 1120」）1〇質量份、聚羧酸鈉（竹本油脂製，產品名「NEWKALGEN WG-5」>25 質量份、山梨糖醇5質量份、磺琥珀酸鈉二辛酯（竹本油脂製’產品名「NEWKALGEN EX-70」（含有30%笨甲酸））3質量份、以及乳化钟13·6質量份’利用空氣粉碎機（Nis so Engineering Co.，Ltd.公司製，產品名「ULMΑΧ」）進行粉碎。於其中添加水46.5質量份並混練，利用〇_7mm的篩進行擠壓造粒，再以50°C的流動層乾燥機（FREUND/大川原製作所製，FLOW COATER(FLO-l))乾燥30分鐘，接著再 201012393 篩選’篩選殘留於0.1 5〜〇.5〇mm的篩上的部分，獲得水分散性粒劑。 (比較例1)Pneumatic Mfg. Co., Ltd., product name "Supersonic Jet Mill PJM" was pulverized to obtain granules (premixed preparation) containing 5 % by weight of alkane sulfonate. Cylvufenamid (common name cycloheximide, manufactured by Japan Soda Co., Ltd., melting point: about 62 ° C) 3.4 parts by mass, 40 parts by mass of the above premixed preparation, and basic white carbon (DSL company, product name "CARPLEX# 1120") 1 part by mass, sodium polycarboxylate (made by Takeshi Oil Co., Ltd., product name "NEWKALGEN WG-5"> 25 parts by mass, sorbitol 5 parts by mass, sodium sulfosuccinate dioctyl ester (made of bamboo oil) Product name "NEWKALGEN EX-70" (containing 30% benzoic acid)), 3 parts by mass, and emulsification clock, 3.6 parts by mass, using an air pulverizer (manufactured by Nis so Engineering Co., Ltd., product name "ULM ΑΧ" The pulverization was carried out, and 46.5 parts by mass of water was added thereto and kneaded, and extrusion granulation was carried out using a sieve of 〇7 mm, and a fluidized bed dryer (FREUND/Okawara Seisakusho Co., Ltd., FLOW COATER (FLO-l) was produced at 50 °C. Drying for 30 minutes, followed by 201012393 screening 'screening the fraction remaining on the sieve of 0.1 5~〇.5〇mm to obtain a water-dispersible granule. (Comparative Example 1)

除了以酸性白碳（DSL日本公司製，產品名「CARPLEXIn addition to acid white carbon (made by DSL Japan, the product name is "CARPLEX"

# 80」）取代鹼性白碳（DSL曰本公司製，產品名「carplEX # 1120」）以外’其餘進行以與實施例1相同的操作，獲得水分散性粒劑。#80") The water-dispersible granules were obtained in the same manner as in Example 1 except that the basic white carbon (manufactured by NET Co., Ltd., product name "carplEX #1120") was used.

(比較例2) 除了將山梨糖醇的量變更為〇質量份、氣化鉀的量變更為1 8.6質量份以外，其餘進行以與實施例1相同的操作，獲得水分散性粒劑。 (比較例3)(Comparative Example 2) A water-dispersible granule was obtained in the same manner as in Example 1 except that the amount of sorbitol was changed to 〇 by mass and the amount of potassium hydride was changed to 1 8.6 parts by mass. (Comparative Example 3)

# 8〇」）取代驗性白碳（DSL日本公司製，產品名「CARPLEX # 1120」）以外’其餘進行以與比較例2相同的操作，獲得水分散性粒劑。藉由下述方法進行實施例以及比較例所得之水分散性粒劑的評價。該等結果示於表1。 (自分散性的評價）於裝有lOOmL的水使得自水面至底部的距離約為 18〇mm之空間容積成為3〇社的試管中，根據農藥步驟檢 =法裝入3度硬水1(K)mL，再於其中緩慢投人水分散性粒 ^觀，水分散性粒劑沉人底部為止的狀態，並以下述基罕采列定。 21 201012393 〇：水分散性粒劑於接觸試管底部之間已開始崩解。 X:水分散性粒劑於接觸試管底部之間完全未崩解。 ◦表示有自分散性；X表示無自分散性；〇〜χ表示大致上有自分散性，但部分顆粒無自分散性。X〜◦表示大致上無自分散性，但部分顆粒有自分散性。 (崩解性的評價）於裝有UHhnL的水使得自水面至底部的距離約為刚麵之空間容積成為3〇机的試管中，根據農藥步驟檢查法裝入3度硬水⑽mL，再於其令緩慢投入水分散性粒β 劑。投入後經過30秒’將試管以2秒】次的頻率反覆進行倒轉、復原的操作’測定水分散性粒劑完全崩解為止的到轉次數（稱為崩解次數）。崩解倒轉次數越少者其崩解性越好。 (沉降量（分散性））測定崩解倒轉次數後，進—步將試管以2秒i次的頻 ❿ 率反覆進行倒轉、復原的操作3Q次。自倒轉的反覆操作結束起經過30分鐘後，測；t沉降量（mL)。沉降量越少者性越優異。 (高溫保存試驗）將實施例以及比較例所得之水分散性粒劑放入54力的恆溫室中保存14日。對於14日之古、、田位七从 H之网/JD保存後之水分散性粒劑以與上述相同之方法，對自分勒曰刀散性、朋解性以及沉降量進行評價。 22 201012393 表1 ~~™ ----------- ______________ 剛完成製造時 54°Cxl4日保存德自分散性崩解性 [次] 沉降量 ΓτηΠ 自分散性 ---—- Ο〜乂" 崩解性 [次] Λ Λ 沉降量實施例1 _____〇 11 0.01 比較例1 〇 11 <0.01 X LH 17 o.os 〇 ^ 比較例2 _____g 12 0.04 X 1 Q ----- Λ A 比較例3 〇 11 001 〜X l Ο 15 0.2 — 如表1所示，於剛完成製造時的情形，以往配方的水分散性粒劑具有自分散性，水中崩解性以及分散性亦優異然而，於尚溫保存後之情形，其自分散性消失，崩解性以及分散性降低。另一方面，本發明之水分散性粒劑即使於高溫保存後仍維持自分散性，崩解性以及分散性的降低程度亦小。本發明之水分散性粒劑即使於高溫下保存之後亦不會 © 降低崩解性以及分散性，故可適用於農園藝用之農藥。【圖式簡單說明】無【主要元件符號說明】無 23#8〇") The water-dispersible granules were obtained in the same manner as in Comparative Example 2 except that the white carbon (manufactured by DSL Japan Co., Ltd., product name "CARPLEX #1120") was used. The evaluation of the water-dispersible granules obtained in the examples and the comparative examples was carried out by the following method. These results are shown in Table 1. (Evaluation of self-dispersibility) In a test tube containing 100 mL of water so that the distance from the water surface to the bottom is about 18 〇 mm, the test tube is filled with 3 degrees hard water according to the pesticide step test method. ) mL, in which the water-dispersible granules were slowly poured, and the state in which the water-dispersible granules settled to the bottom of the granules was listed in the following Kihamese. 21 201012393 〇: Water-dispersible granules have begun to disintegrate between the bottom of the test tube. X: The water-dispersible granules did not completely disintegrate between the bottoms of the contact tubes. ◦ indicates self-dispersibility; X indicates no self-dispersibility; 〇~χ indicates substantially self-dispersibility, but some particles are not self-dispersible. X~◦ indicates that there is substantially no self-dispersibility, but some of the particles are self-dispersible. (Evaluation of disintegration) The water containing UHhnL is such that the distance from the water surface to the bottom is about 3 inches of the space volume of the rigid surface, and 3 degrees of hard water (10) mL is charged according to the pesticide step inspection method, and then Slowly put into the water-dispersible granule beta agent. The operation of inverting and restoring was repeated at a frequency of 2 seconds after the introduction of the test for 30 seconds. The number of revolutions (referred to as the number of disintegrations) until the water-dispersible granules completely disintegrated was measured. The less the number of disintegration reversals, the better the disintegration. (Settling amount (dispersibility)) After the number of times of disintegration inversion was measured, the test tube was further inverted and restored three times in a frequency of 2 seconds i. After 30 minutes from the end of the reverse operation of the inversion, the amount of sedimentation (mL) was measured. The smaller the amount of sedimentation, the more excellent the properties. (High-temperature storage test) The water-dispersible granules obtained in the examples and the comparative examples were placed in a thermostatic chamber of 54 liters for 14 days. For the water-dispersible granules after the preservation of the 14-day-old, the field seven from the H mesh/JD, the dispersibility, the solvability, and the sedimentation amount of the self-dispersing boring tool were evaluated in the same manner as described above. 22 201012393 Table 1 ~~TM ----------- ______________ 54°C×14 days of self-dispersive disintegration at the time of completion of manufacturing [times] Settlement ΓτηΠ Self-dispersibility ------- Ο ~乂" Disintegration [次] Λ 沉降 Settlement Example 1 _____〇11 0.01 Comparative Example 1 〇11 <0.01 X LH 17 o.os 〇^ Comparative Example 2 _____g 12 0.04 X 1 Q --- -- Λ A Comparative Example 3 〇11 001 ~X l Ο 15 0.2 — As shown in Table 1, the water-dispersible granules of the prior formula have self-dispersibility, disintegration in water and dispersion as soon as the manufacturing is completed. It is also excellent in the properties. However, in the case of storage after the temperature is maintained, the self-dispersibility disappears, and the disintegratability and dispersibility are lowered. On the other hand, the water-dispersible granule of the present invention maintains self-dispersibility even after storage at a high temperature, and the degree of reduction in disintegratability and dispersibility is small. The water-dispersible granule of the present invention can be applied to agricultural and horticultural pesticides even if it does not reduce disintegration and dispersibility after storage at a high temperature. [Simple description of the diagram] None [Key component symbol description] None 23

Claims

3. The water-dispersible granule according to the invention of claim 2 or 2, wherein the active ingredient of the pesticide is cetylbenzene sulfonate. 201012393 VII. Patent application scope: 1. A water-dispersible granule containing a melting point or softening point of 7 (accumulating pesticide active ingredient, acid white carbon, basic white carbon, polycarboxylic acid interface/tongue) And a water-dispersible granule according to the scope of the invention, wherein the saccharide is selected from the group consisting of glucose, sorbitol, lactose, sucrose, and maltose. At least one of the group. 4·-Water dispersible granules are manufactured by the following steps: Premixing the active ingredient of the pesticide having a melting point or softening point of 7 G ° C or less and acid carbon a preparation; mixing the premixed preparation, alkaline white carbon, octagonal antimony acid surfactant, and a saccharide having a molecular weight of 400 or less; and granulating the prepared mixture.

White

twenty four