200922467 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種農藥包裝用水溶性膜，封入除草劑等農藥 且於散布在水田等水面時，膜迅速溶解而能使封入的農藥擴散厂 【先前技術】 自以往，使用在水田等之農藥，係使用了粒狀、粉狀、液狀 4具備各種形狀、狀態的藥劑。其中，從對於農藥散 全性、及能在水田内中均勻散布之觀點，以粒狀形 狀之農樂為有效而常使用。 y 之方5述=藥t使用態樣，例如除了以原本狀11散布在水田 ί藥搬運、對於水田容易散布之觀點，目前採 =由水祕膜構成之錄物巾封人粒狀錢並散布在水田 =水面使袋狀物溶解將封入的農藥擴散到昭 專利文獻1)。 ㈣〈万去（例如參照 [專利文獻1]日本特開平4 —226901號公報 【發明内容】 (發明欲解決之問題) 然而，以往 因此，’例域之驗細水溶性不夠， ^ , i；； ； Iff 解，圓頂狀部分内殘存的農举成為 、 M邛伤未完全溶 本發明有鑑於以上情的問題。 包裝用水溶性膜。 目的為美供水溶性優異之農藥 (解決問題之方式） 改良用於封义農藥之1形水溶性進-步提升，以 究，並且非著眼於水溶性水溶性膜為目的進行-連串研 獏之主原料聚乙烯醇系樹脂本身，而； 200922467 眼於由於添加劑之配合而提升水溶性，對於各插#人^ 討，結果發現藉由配合快二_界面活性i t 時間縮短，並且使用此化合物形成1水= 亦即，本發明要旨係關於一種農華 =Γ(Α)及块二醇系界面活性删作=分= (發明之效果） 樹脂二’:二之界農二=^ =者使用因二上述水落性膜，能二二 速溶解。因此，封入的^单 ^在水面形成之圓頂部分亦迅 農藥散布效果提升。 不會餐成塊狀’能達成擴散於水田且 (A)二且重量⑻’她 空氣隆起部（空，在水面之含 又，若上述聚乙烯醇系樹 〜、 為10〜70咖.3且聚乙婦醇=AH)=重置％水溶液黏度，於20t 耳％，則能得到作為農 A)之平均皂化度為70〜98莫 本身水溶性更加良好、衣良f強度及製難，且水溶性膜 率 作一成 機械強度優異之厚度為10〜100_，則膜之 。 、7水之洛解性提升，且可得良好的製獏效 200922467 形性’且對水之溶解性非常優異。 【實施方式】 (實施發明之最佳形態) 係用以形成將各種農藥製劑 本發明之農藥包裝用水溶性膜， 封入並包裝之袋狀物用的水溶性膜。 成為亡述私包裝對象之諸農藥㈣，不制蚊，例如 投入水田等，並藉由本身崩壞而能擴散到水中之含除草劑、殺菌 劑、殺蟲劑、植物成長調整劑等農藥活性成分的製劑。 上述除草劑，例如：2, 4, 6-三氯苯基—4，—硝基苯醚(CNp)、2 曱基一4一氣本氧基硫乙酸—s—乙醋（phenothiol)、α —(2 — 萘氧基）丙醯胺苯(naproanilide)、5 —（2,4一二氣苯氧基）—2一 硝基安息香酸甲酯（bi fenox)、S — (4 —氣苄基)N，N~二乙基硫胺 曱酸S旨（benthiocarb)、S—苄基=1，2-二曱基丙基（乙基)硫胺曱酸 酯（esprocarb)、S—乙基六氫一1H —吖庚因—i—硫代甲酸酯 (molinate)、S —1 —曱基一1 —笨基乙基=派0定—1 —硫代曱酸酯 (dimepiperate)、鄰一3—第三丁基苯基=6—甲氧基一2 —吡啶基 (甲基）硫胺曱酸酯（pyributicarb)、2 —氣一2，，6，-二乙基—N — (丁氧基甲基）乙酿苯胺(butachlor)、2 —氣一2，，6，一二乙基一N —(2—丙氧基乙基）乙醯苯胺(pretilachlor)、（RS) —2—溴一N — (α, α—二曱基苄基）一3, 3 —二曱基丁基醯胺（bromobutide)、2 — 苯并嗟σ坐一2 —基氧-N—曱基乙醯苯胺(mefenacet)、1 —(α, α—二 曱基苄基）一3 —(對曱苯基)尿素(dymron)、曱基=α—(4,6 —二曱 氧基嘧啶一 2 —基胺曱醯基胺磺醯基）一鄰一甲基苯曱酸酯 (bensulfuron-methyl)、1 —(2 —氣咪唑[1，2 —a]吡啶一3-基磺醯 基）一3 —(4, 6 —二甲氧基，咬一2—基)尿素（imazosulfuron)、乙 基=5 —（4, 6-二甲氧基嘧啶一2 —基胺曱醯基胺磺醯基）一 1 —曱基 π比唾一4_羧酸δ旨（pyrazosulfuron ethyl)、2 —曱硫基一4, 6 —雙 (乙基胺基）一S—三啡(simetryn)、2 —曱硫基一4, 6 —雙（異丙基 200922467 胺基）一S —二口井(prometryn)、2 —曱基硫基一4—乙基胺基一6 — (1，2 —二曱基丙基胺基）一S —三卩并(dimethametryn)、2,4 —二氯 苯基一3’一甲氧基一4’一石肖基苯基SiKchlormetoxinyl)、5 —第三 丁基一3 — (2, 4 —二氮一5 —異丙氧基苯基）一 1, 3, 4-,二峻淋一2 —酮（oxadiazon)、4一（2, 4 — 二氣苯曱醯基）一1，3 —二曱基一5 — 0比0坐基=對曱苯續酸酯（pyrazolate)、2— [4一（2, 4 —二氣苯甲醯 基）一 1，3— 二曱基°比唾一5 —基氧]苯乙酮(pyrazoxyfen)、（RS) — 2 —(2, 4 —二氯一間曱苯基氧）丙醯胺苯(clomeprop)、2-[4 — [2, 4 一二氯一間曱苯曱醯]—1，3 —二曱基吡唑一5 —基氧]—4’一曱基 苯乙酮（benzofenap)、S, S’一二甲基=2 —二氟曱基一4 —異丁基一6 一三氟曱基°比0定一3, 5 —二硫代曱酸酯（dithiopyr)、2—氣一N — (3 —曱氧基一2— °塞吩基）一2, 6’一二曱基乙醯苯胺 (thenylchlor)、正丁基一（R) — 2— [4 —(2—氟一4一氰基苯氧基） 苯氧基]丙酸酯（cyhalofop-butyl)、3— [1 — (3, 5 —二氣苯基）~1 一甲基乙基]—2,3 —二氫一 6 —甲基一5—苯基一4H —1，3 —,口井 —4 —酮（oxaziclomefone)、3 —(4—氯一5 —環戊氧基一2—敗笨 基）一5 —異丙叉_1，3 —口号〇坐0定一2, 4 —二酮（pentoxazone)、1 — (二乙基胺甲酿基）_3 —（2, 4, 6—三曱基苯基石黃醯基）一 1，2, 4 — 三唑（cafenstrole)、N— {[(4, 6 —二曱氧基嘧啶一2 —基）胺基幾 基]} —1 一曱基一4 —(2 —甲基一2H—四0坐一5 —基）一1H—〇比〇坐― 5 —石黃醯胺（azimsulfron)、甲基=2 — [(4,6 — 二甲氧基t»密0定 — 2~~ 基）氧]一6—[(E)-l—(曱氧基亞胺基）乙基]苯甲酸酉旨 (pyriminobac-methyl)、2, 3 —二氫一3, 3 —二曱基苯并π夫喃 基=乙續酸酯（benfuresate)、（RS) —2’一[(斗一-二甲氧基喊咬^^ —基）（經基）甲基]一 1,1 —二氟一6’一（甲氧基甲基）曱續醯笨胺 (pyrimisulfan)、3 —(2-氣一4-甲磺醯基苯曱醯基）一2—苯基硫 雙環[3. 2. 1]辛一2 —稀一4 —酮（benzobicyclon)等。此等可以單 獨使用或併用2種以上。 上述殺菌劑，例如：0,0 —二異丙基一S—苄基硫磷酸酉旨 200922467 (IBP)、0—乙基一S，S’一二苯基二硫磷酸酯（EDDP)、3’一異丙氧基 —2—曱基苯龜替笨胺(mepronil)、a，a, α—三氟一3’一異丙氧 基一鄰一曱苯醯胺（flutolanil)、3, 4, 5, 6 —四氯一Ν —(2, 3 —二 氣苯基）鄰苯二甲醯胺酸(tecloftalam)、1 —(4—氣苄基）一1 一環 戊基一3 —苯基尿素(pencycurOn)、6 —（3, 5 —二氣一4—曱基笨基) —3(2H) —。荅〇并酮(diclomezine)、甲基(2—甲氧基乙醯基）一 1^—(2,6 — 二曱苯基）一01^—丙胺酸酯（1116七&18父71)、（£) — 4—氣一 α,α,α —三敗一N—(1 —口米〇坐一1—基一2 —丙氧基乙又）一鄰一曱 苯胺（trif lumizole)、嘉賜黴素（kasugamycin)、井岡黴素 (validamycin)、3 —烯丙氧基一1，2—苯并異噻唑一 1,1 一二氧化 物（probenazole)、二異丙基一1, 3 —二噻茂烷一2—基叉一丙二酸 酯（isoprothiolane)、5—曱基一1，2, 4 —三唑并[3, 4 —b]苯并噻 唑（tricyclazole)、1，2, 5, 6 —四氫一4H —吡咯并[3, 2,1 —i j]喹 啉一4 —酮（pyroquilon)、5—乙基一5, 8 —二氫一8 —側氧基[1，3] 二側氧[4,5 —ghi:琳一7 —叛酸(oxolinic acid)、（Z) —2，一甲基 笨乙酮=4, 6 —二甲基〇密°定一2— 基腙（ferimzone)、3 —（3, 5 —二 氯笨基）一 N —異丙基一2, 4 —二侧氧基味唾咬一1 —甲醯胺 (iprodione)、（E) —2—曱氧基亞胺基一N—甲基一2 —(2 —笨氧基 苯基）乙醞胺(metominostrobin)等。此等可以單獨使用或併用2 種以上。 上述殺蟲劑’例如：0,0 —二曱基一〇—(3—曱基一4一硝基笨 基)硫填酸S旨（MEP)、0,0 —二曱基一〇—[3 —曱基—4 —(曱硫基）苯 基硫磷酸酯（MPP)、二曱基二硫填醯基笨基乙酸乙酯（pap)、（2 — 異丙基一4 一甲基嘧啶基一 6 —基）一二乙基硫磷酸酯 (diazinon)、1 一萘基一N—曱基胺曱酸酯（NAC)、0,0 —二乙基一〇 —(3 —侧氧基一2—苯基一2H—嗒啡一6 —基）硫代磷酸酯 (pyridafenthion)、0,0 —二曱基一〇 —3,5, 6— 三氯一2 —吡咬基 硫代填酸酯（chlorpyrifos—methyl)、〇,〇— 二曱基一s —二乙氧 叛基乙基二硫石粦酸S旨（malathon)、0, 0~~二曱基—s—(N—甲基胺 10 200922467 曱醯基曱基）二硫石粦酸g旨（dimethoate)、0, 0_二丙基一〇 — 4~甲 硫基苯基罐酸酯（propaphos)、0, S—二曱基一Ν—乙醯基硫代鱗醯 胺（acephate)、0 —乙基一 0 —（4 一硝基苯基）硫幾基苯鱗酸酉旨 (EPN)、2—第2 丁基苯基一N—曱基胺曱酸酯（BPMC)、2,3 —二氫 一2, 2 —二曱基一7—苯并[b]n夫喃基=N—二丁基胺基硫一N —曱基 胺曱酸酯（carbosulfan)、乙基=N—[2,3 — 二氫一2,2 — 二甲基苯 并吱喃一7 —基氧幾基（甲基）胺基硫]—N —異丙基一/3丙胺酸酉旨 (benfuracarb)、（RS) — 氰基一3— 苯氧基节基^(RS) — 2, 2 — 二氯一 1 — (4—乙氧基苯基）環丙烧羧酸酯（cycloprothrin)、2 — (4 一乙氧基苯基）一 2—曱基丙基=3 —苯氧基苄基=趟 (etofenprox)、1，3 —雙（胺曱醯基硫）一2 —（N，N—二曱基胺基）丙 烷鹽酸鹽（cartap)、5 —二甲基胺基一1，2,3 —三噻卩山草酸鹽 (thiocyclam)、S，S’一 2 —二曱基胺基三亞曱基=二（苯硫磺酸 酯）（bensuli:ap )、2—第3 丁基亞胺基一3 —異丙基一5 —苯基— 1，3, 5, 6 —四氫一2H — 1，3, 5 —噻二卩并一4 —酮（buprofezin)、 spinosynA與spinosynB之混合物（spinosad)等。此等可以單獨使 用或併用2種以上。 上述植物成長調節劑’例如：4’一氯一2’一（α—經基苄基）異於 鹼醯苯胺（inabenfide)、（2RS，3RS) —1 —（4一氣苯基）一4,4 —二 曱基一 2 — (1H — 1，2,4 —三唑一1 —基）戊—3 —醇 (paclobutrazol)、（E) — (S) — 1 一（4 —氯笨基）一4, 4一 二曱基一2 (1H—1，2, 4一二峻一1 —基）戊一1 —稀—3 —醇(uniconaz〇ie p) 等。此等可以單獨使用或併用2種以上。 並且，前述農藥製劑，藉由同時含上述農藥活性成分及界面 活性劑，能在水面使農藥製劑崩壞，並擴散到水中。 丄上述界性劑，可使用一般使用在農藥製劑中者，具體而 s，聚乙二醇咼級脂肪酸酯、聚氧化乙烯院基醚、聚氧化乙浠烧 基芳基醚、聚氧化乙烯芳基苯醚、山梨糖醇酐單烷基化物、炔醇 (acetylene alcohol)及炔二醇及該等之氧化烯烴加成物等非離子 11 200922467 面活性劑、烷基芳基磺酸鹽、二烷基磺酸鹽、木質磺酸鹽、 =½¾鹽及其縮合物、烧基硫酸酯鹽、燒基碟酸酯鹽、烧基芳基 ，酸酯鹽、烷基芳基磷酸酯鹽、聚氧化乙烯烷基醚硫酸酯鹽、& 二化乙烤烷基芳基醚硫酸酯鹽、聚氧化乙烯芳基苯基醚硫酸酯 羧酸型高分子活性鮮_子性界面活性鮮，再者糊 =面活性劑、氟系界面活性劑。此等可以單獨使用或併用2種 體i體S界面活性劑，可以使吸附在白碳、石夕藻土、尿素 可援藥製劑為漂浮在水面後、崩壞並擴散者，因此 為了使辰藥製劑漂浮在水面之賦予漂浮性的各種方法。 *真面ΐ浮性之方法，舉—例有，使農藥製劑中含有： 、石或…、曜石構成之波來鐵（pearlite)、白砂構成之發泡白 鹽系，成之千枚岩(phymte)、石夕酸鋼或使石朋砂發 太於:ίf，CrC)ball〇Gn)、輕石、粒狀石夕藻土、粒狀活性碳、 ===^_產出之飛灰、飛灰 性物繼碳等撥水 法。 八甲华乂佳為3上述獨立或多數氣室之物質之方 限定，狀.狀態’只要是能封入袋狀物即不特別 〜1〇刪，尤#真Γ千均粒 _以上較佳，更佳為ι2 値，1測定係;I足母雜^1。並且’上述平均粒徑’例如指短徑平均 短徑並計算出之俊群出任意數量，並使麟標尺測絲狀物 作為ii料刖係藉由使以聚乙烯醇_)系樹脂⑷ 、並於其中含炔二醇系界面活性劑⑻而成之樹脂組成 12 200922467 物形成膜狀而得。 又’ P奶Η系意指PVOfi本身，咬 ^又，上述主原料係在形成水溶質 全體之60重量具體而S，係指佔水溶性膜形成材料 上述醜，系樹脂(A)，不特別限定 稀基_合物聚合得到之峨旨=以 顧己例'乙酸乙烯醋、三 耽乙&乙烯基、㈣乙烯g旨、了酸乙獅、癸酸 二 乙烯酯、新癸酸乙烯酯（versatic vinyl)、棕櫚酸乙烯 = 酸乙_旨等單獨或併用2種以上，實用上以乙酸乙湘旨為日妥。月曰 人之脂可以為和能與上述乙稀基醋系化合物共聚 體，、伞s者，在不妨礙本發明效果之範圍，能在 為10莫耳％以下、更佳為7莫耳％以下之顧，與其他單體共聚合。 上述使共聚合之其他單體，例如：乙稀、丙烯、異丁稀、“— ΐ稀缺α it二^、α—十八稀等稀烴類、丙稀酸、曱基丙烯酸、 巴政、馬來ι、馬來贿、衣康料不飽和賴或其鹽或 -烧基g旨等、㈣腈、曱基丙烯腈等腈類、丙烯醯胺、曱基 醯胺等醯胺類、乙烯續酸、烯丙罐酸、曱基烯丙續酸等稀煙續酸 或其鹽、烷基乙烯基醚類、聚氧化乙烯（甲基）烯丙醚、聚氧化丙 烯（曱基)烯丙醚等聚氧化烯烴（甲基）烯丙醚、聚氧化乙烯（甲美） 丙稀酸醋、$氧化丙稀（甲基）丙烯酸酉旨等聚氧化烯烴（甲基）丙土稀 酸醋:聚氧化乙烯（曱基）丙烯醯胺、聚氧化丙烯（曱基）丙稀醯胺 等聚氧化稀烴（曱基）丙烯醯胺、聚氧化乙烯π—(曱基）丙烯醯胺 一l’l —二曱基丙基]g旨、聚氧化乙烯乙烯基醚、聚氧化丙烯乙烯 基=、聚氧化乙烯烯丙胺、聚氧化丙烯烯丙胺、聚氧化乙烯乙烯 基胺、聚氧化丙烯乙烯基胺、二丙烯酸基乙醯胺、N—丙烯醯胺曱 基二曱基氯化铵、烯丙基三曱基氣化I安、二曱基二烯丙基氣化鍵、 13 200922467 - 一曱基烯丙基乙烯基酮、N—乙烯基π比略咬酮、氣化乙桷、傯惫7 稀等。此等其他之單體，可以單并用2種^。乙席偏乳乙 又’本發明中’（甲基)烯丙基，意指烯丙基或甲基烯丙基，（ ㈣丙_ ’ (甲基)丙騎基意指 -入:t上ffiL或共聚合)時，不特別限制，可任意使用公知 溶i聚二”曱醇、乙醇、異丙基醇等醇作為溶劑之 可V 口〆，上述溶液聚合法以外，乳化聚合、懸浮聚合亦 f :氧化i甲ii聚月、過氧化乙醯基、過 聚合反應溫度，擇自』合觸=于:該 貌^佳為即〜阶之範圍。則C之扼圍，更佳為40〜 系聚合體溶於醇中將上述乙烯基酯 醇、乙醇、丁醇等。 士子在下貫施。上述醇例如：甲 定為20〜50重量％之範圍較=中之乙烯基醋系共聚合體濃度以 乙醇===屬納、氯氧化鉀、甲醇納、 鹼性觸之使料，相對物^^等驗_媒。上述 莫耳;酸定為1〜1〇0毫 2種以上Ρ贿她旨^使^糊視需要可以與4化度不同之 耳%較佳，更佳為^〜樹脂⑷之平均矣化度以70〜98莫 化度若落於上述範圍以外^即’ _系樹脂(A)之平均專 礙内包之農藥擴散，結果會有水之溶解性遲延，妨 又，上述平均卷介=成為枭害4原因之傾向。 又’ _ _月身‘重:二“726測定。 重里/冰溶液於2Qt之平均黏度，以1〇 14 200922467 '70mPa · s 較佳、15 :_ra · S牧佳、i5〜6〇mPa · s更佳。原因為亦即， f之平均黏度過低之情形，農藥包裝純度不足 ；= 因之，’又，膜製造時發生斷裂有製膜困難之傾向 =外則!if ί性遲延，妨礙内包農藥之擴散成為 因，此外，由於黏度尚，會有製膜困難之傾向。 。” 又’上述平均黏度依照JIS K 6726測定。 並十，上述炔二醇系界面活性劑（β)，例如下述 士炔二醇系化合物，亦即例如快二醇及块二醇衍生物巾其中^ 者0。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Prior Art Conventionally, a pesticide used in a paddy field or the like has been used in a granular, powder, or liquid form, and has various shapes and states. Among them, from the viewpoint of the completeness of the pesticide and the uniform distribution in the paddy field, the grainy shape of the farm music is effective and often used.之方五述=The use of the drug t, for example, in addition to the original shape 11 scattered in the paddy field, the idea of easy distribution of the paddy field, the current mining = the composition of the water secret film to seal the grain money and Dispersed in the paddy field = water surface to dissolve the bag and spread the enclosed pesticide to the patent document 1). (4) In the case of the invention, the problem of the invention is to be solved. ; Iff solution, the remaining agricultural crops in the dome-shaped part, the M-injury is not completely dissolved. The invention has the above problems. The water-soluble film for packaging. The purpose is to provide water-soluble pesticides in the United States (the way to solve the problem) Improved the water-soluble step-by-step improvement for the sealing of pesticides, and for the purpose of not focusing on the water-soluble water-soluble film - the main raw material of the polyvinyl alcohol-based resin itself, and; 200922467 In order to improve the water solubility due to the combination of the additives, it was found that the time was shortened by the combination of the fast _ interface activity and the use of the compound to form 1 water = that is, the present invention relates to a farmer Hua = Γ (Α) and block diol system interface activity = = = (the effect of the invention) Resin two ': two of the boundaries of the agricultural two = ^ = use of the above two water-film, can dissolve at the second speed. Therefore, the enclosed ^ single ^ In the dome part formed on the surface of the water, the pesticide spreading effect is also improved. It will not be eaten into a block shape. It can be diffused in the paddy field and (A) two and the weight (8)' her air bulge (empty, in the water surface, if above) Polyvinyl alcohol tree ~, is 10 ~ 70 coffee. 3 and polyethyl alcohol (AH) = reset % aqueous solution viscosity, at 20t ear %, you can get the average saponification degree as agricultural A) 70~98 It has better water solubility, good strength and difficulty in making clothes, and the water-soluble film rate is 10% to 100%, which is excellent in mechanical strength. The water solubility of 7 water is improved, and good system efficiency is obtained. 200922467 Formability and excellent solubility in water. [Embodiment] The best mode for carrying out the invention is a water-soluble film for forming a bag-like material in which a water-soluble film for agricultural chemical packaging of the present invention is sealed and packaged. Pesticides that are the target of private packaging (4), do not produce mosquitoes, such as pesticides, such as herbicides, fungicides, insecticides, plant growth regulators, etc., which can be diffused into water by their own collapse. Formulation of ingredients. The above herbicides are, for example, 2, 4, 6-trichlorophenyl-4,-nitrophenyl ether (CNp), 2 fluorenyl- 4 thiophenoxythioacetic acid-s-ethyl phenothiol, α- (2 - naphthyloxy) propyl amide (naproanilide), 5-(2,4-dioxaphenoxy)- 2 nitrobenzoic acid methyl ester (bi fenox), S — (4 - benzyl benzyl N, N~ diethyl thiamin citric acid S (benthiocarb), S-benzyl 1,2-dimercaptopropyl (ethyl) thiamine phthalate (esprocarb), S-ethyl six Hydrogen-1H-azepine-i-thioformate, S-1-mercapto-1-stupylethyl=派0定-1, thiophthalate, adjacent 3-t-butylphenyl=6-methoxy-2-pyridyl (methyl) thiamine phthalate (pyributicarb), 2-gas-2,6,-diethyl-N- Oxymethyl)butachlor,2-gas-2,6,diethyl-N-(2-propoxyethyl)acetamididine, (RS)-2 Bromo-N-(α,α-dimercaptobenzyl)-3,3-dimercaptobutylamine (bromobutide), 2-benzindole σ-2-yloxy- N-mercaptoacetamide (mefenacet), 1-(α,α-dimercaptobenzyl)-3-(p-phenylene)urea (dymron), fluorenyl=α-(4,6-dioxin Oxypyrimidine-2-ylamine decylamine sulfonyl)bensulfuron-methyl, 1-(2-imidazole[1,2-a]pyridin-3-yl Sulfhydryl)-3-(4,6-dimethoxy, bita-2-yl) urea (imazosulfuron), ethyl =5 -(4,6-dimethoxypyrimidine-2-aminoamine胺 醯 ) ) 一 1 1 1 4 4 4 4 4 4 4 4 4 4 pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr pyr ), 2 - thiol- 4, 6-bis (isopropyl 200922467 amine)-S - two wells (prometryn), 2-mercaptothio- 4-ethylamino group - 6 - (1, 2-dimercaptopropylamino)-S-dimethametryn, 2,4-dichlorophenyl- 3'-methoxy- 4'-monosylphenyl SiKchlormetoxinyl, 5 - third Butyl-3-(2,4-dinitro-5-isopropoxyphenyl)-1,3,4-, 2 ketone (oxadiazon), 4 2, 4 — Diphenyl benzoyl)-1,3 —Dimercapto-5 — 0 to 0 sitting base = pyrazolate, 2—[4一(2, 4 — 2 gas Benzopyridinyl)-1,3-diindole-based pyrazoxyfen, (RS)-2-(2,4-dichloro-p-phenylene oxide) Clomeprop, 2-[4 — [2, 4-dichloro-p-benzoquinone]-1,3-dimercaptopyrazole-5-yloxy]-4'-mercaptophenylene Benzofenap, S, S'-monomethyl = 2 - difluoroindolyl 4-isobutyl-6-trifluorodecyl group, 0 to 5, dithiopyr ), 2-gas-N-(3-decyloxy- 2-thenyl)- 2,6'-diethylphosphonium (nenylchlor), n-butyl-(R)-2 - [4 —(2-Fluoro-4-cyanophenoxy)phenoxy]propionate (cyhalofop-butyl), 3-[1 - (3,5-diphenyl)-1 monomethylethyl] —2,3—dihydro-6-methyl-5-phenyl-4H-1,3—, oxaziclomefone, 3—(4-chloro-5-cyclopentyloxy-2 - defeated base) a 5-isopropyl fork _1, 3 - Slogan 〇 sit 0, 2, 4 - diketone (pentoxazone), 1 - (diethylamine methyl ketone) _3 - (2, 4, 6 - tridecyl phenyl fluorenyl) - 1,2, 4 —cafenstrole, N— {[(4, 6 —dimethoxypyrimidin-2-yl)amino)] —1 —indolyl—4 —(2-methyl-2H—four0 Sit 5 - base) - 1H - 〇 〇 ― - 5 - azylsulfonamide (azimsulfron), methyl = 2 - [(4,6 - dimethoxy t»密0定 - 2~~ base) Oxygen]-6-[(E)-l-(decyloxyimino)ethyl]benzoic acid (pyriminobac-methyl), 2,3-dihydro-3,3-dimercaptobenzox Flumemonyl = benfuresate, (RS) - 2'-[(Dou-Dimethoxy-sniffing ^^-yl) (trans)methyl]-1,1-difluoro- 6'-(methoxymethyl) hydrazine pyrimisulfan, 3-(2- gas-tetramethylsulfonylphenyl)- 2-phenylthiobicyclo[3. 2. 1 ] Benzene 2 - benzobicyclon and the like. These may be used alone or in combination of two or more. The above bactericide, for example: 0,0-diisopropyl-S-benzyl thiophosphoric acid 2009200922467 (IBP), 0-ethyl-S, S'-diphenyldithiophosphate (EDDP), 3 '-Isopropoxy-2-indenylbenzene tompronil, a, a, α-trifluoro-3'-isopropoxy-l-fluorenylil, 3, 4 , 5, 6 - tetrachloro-anthracene - (2, 3-diphenyl) phthalic acid (tecloftalam), 1-(4-carbobenzyl)- 1 -cyclopentyl- 3 -phenyl Urea (pencycurOn), 6 - (3, 5 - two gas - 4 - fluorenyl base) - 3 (2H) -. Diclomezine, methyl (2-methoxyethenyl)- 1^-(2,6-diphenylene)- 01^-alanate (1116 7 & 18 parent 71) , (£) — 4—gas-α,α,α—three defeats one-N—(1—mouth 〇 〇 1 1 — — 2 2 2 2 2 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一Kasugamycin, validamycin, 3-allyloxy-1,2-benzisothiazole-1,1-dioxide (probenazole), diisopropyl-1, 3 - dithiamethane-2-ylidene-malonate (isoprothiolane), 5-mercapto-1,2,4-triazolo[3,4-b]benzotriazole, 1,2 , 5, 6 - tetrahydro- 4H-pyrrolo[3,2,1-ij]quinoline-pyroquilon, 5-ethyl-5,8-dihydro-8-sideoxy[1 , 3] two sides of oxygen [4,5 —ghi: Lin Yi 7 — oxolinic acid, (Z) — 2, monomethyl acetophenone = 4, 6 — dimethyl 〇 ° ° 2 - ferimzone, 3-(3,5-dichlorophenyl)-N-isopropyl- 2,4-dioxy sulphate, 1 - formazonone, (E) -2 Yue oxyalkylene group a N- methyl-2 - (2 - Ben-methoxyphenyl) ethyl amine brew (metominostrobin) and the like. These may be used alone or in combination of two or more. The above insecticides are, for example, 0,0-dimercapto-indenyl-(3-indolyl-4-indolyl)sulfuric acid S (MEP), 0,0-dimercapto-indole-[ 3 — fluorenyl — 4 —(indolylthio)phenylthiophosphate (MPP), dimercapto disulfide-filled phenylacetate (pap), (2-isopropyl-4-methylpyrimidine) 1,2-diethylthiophosphate (diazinon), 1-naphthyl-N-decylamine decanoate (NAC), 0,0-diethyl-anthracene-(3-sideoxy 2-2-phenyl-2H-indolyl-6-yl) phosphorothioate (pyridafenthion), 0,0-dimercapto-indolyl-3,5,6-trichloro-2-pyridylthiolate (chlorpyrifos-methyl), hydrazine, hydrazine - dimercapto-s-s-diethoxy-oxoethyl disulfide phthalic acid S (malathon), 0, 0~~ dimercapto-s-(N- Methylamine 10 200922467 曱醯 曱 ) ) 二 di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di Dimercapto-indole, acephate, 0-ethyl-O-(4-nitrophenyl)thiol benzoic acid (EPN) 2—2 butylphenyl-N-decylamine decanoate (BPMC), 2,3-dihydro-2,2-dimercapto-7-benzo[b]nf- ylyl=N- Dibutylamino thio-N-nonylamino phthalate (carbosulfan), ethyl = N-[2,3-dihydro-2,2-dimethylbenzopyran-yl-7-yloxy (methyl)aminothio]-N-isopropyl-1,3-alanine (benfuracarb), (RS) - cyano-3-phenoxy group (RS) - 2, 2 - dichloro 1-(4-Ethylphenyl)cyclopropthrin, 2-(4-ethoxyphenyl)-2-methoxypropyl = 3 -phenoxybenzyl = hydrazine (etofenprox), 1,3 - bis(amine sulfhydryl)-2-(N,N-didecylamino)propane hydrochloride (cartap), 5-dimethylamino-1,2, 3 - thiocyclam, S, S'-2-dinonylaminotriazinyl = bis(phenylthiosulfonate) (bensuli: ap), 2 - butyl butyl imine a mixture of buprofezin, spinosynA and spinosynB, 3-1,3-isopropyl-5-phenyl-1,3,5,6-tetrahydro-2H-1,3,5-thiadiindol-4-one (buprofezin) (spinosad) and so on. These may be used alone or in combination of two or more. The above plant growth regulator 'for example: 4'-chloro-2'-(α-carbylbenzyl) is different from inabenfide, (2RS, 3RS)-1 - (4-monophenyl)-4. 4 —dimercapto- 2 —(1H — 1,2,4-triazol-1-yl)penta-3-ol (paclobutrazol), (E) — (S) — 1 (4-chlorophenyl) A 4, 4, 12, 2, 2, 2 (1H-1, 2, 4, 2, 2, 1 - 1), a 1 -, a, a, a, a, a, a, a, a These may be used alone or in combination of two or more. Further, in the above-mentioned pesticide preparation, by simultaneously containing the above-mentioned agricultural chemical active ingredient and the surfactant, the agricultural chemical preparation can be collapsed on the water surface and diffused into the water.丄The above boundary agent can be used generally in pesticide preparations, specifically s, polyethylene glycol sulfonate fatty acid ester, polyoxyethylene propylene ether, polyoxyethylene aryl aryl ether, polyethylene oxide Nonionic 11 200922467 surfactant, alkyl aryl sulfonate, etc., such as aryl phenyl ether, sorbitan monoalkylate, acetylene alcohol and acetylene glycol, and the like. Dialkyl sulfonate, lignosulfonate, =1⁄23⁄4 salt and condensate thereof, alkyl sulphate salt, alkyl sulphate salt, alkyl aryl salt, acid ester salt, alkyl aryl phosphate salt, Polyoxyethylene alkyl ether sulfate salt, & dialkyl bake alkyl aryl ether sulfate salt, polyoxyethylene aryl phenyl ether sulfate carboxylic acid type polymer active fresh _ sub-interface activity fresh, and then Paste = surfactant, fluorine surfactant. These can be used alone or in combination with two kinds of body i body S surfactants, so that the adsorption of white carbon, Shixiazao, and urea can be used to float on the surface of the water, collapse and spread, so The various methods in which the drug formulation floats on the surface of the water to impart floatability. *The method of true surface floating, for example, the pesticide preparation contains:, stone or..., pearlite composed of vermiculite, foamed white salt system composed of white sand, and phyllite (phymte), ishixi acid steel or make Shipen sand too much: ίf, CrC) ball 〇 Gn), pumice, grainy Shixia, soil, activated carbon, ===^_ Ash, fly ash, water, etc. Bajia Huajia is limited to 3 of the above-mentioned independent or majority of the gas chamber, and the state 'as long as it can be sealed into the bag is not particularly ~1〇, especially #真Γ千均粒_ is better, More preferably ι2 値, 1 determination system; I full mother mixed ^1. And 'the above average particle diameter' is, for example, a short-diameter average short-path diameter and is calculated as an arbitrary number, and the nano-scale ruler is made into a polyvinyl alcohol-based resin (4), Further, the resin composition 12 200922467 containing the acetylene glycol-based surfactant (8) is formed into a film. 'P milk Η means PVOfi itself, bite ^, the main raw material is 60% of the total amount of water solute formed, and S means the above-mentioned ugly, resin (A), not special限定 稀 = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = (versatic vinyl), palmitic acid ethylene = acid B, etc., alone or in combination of two or more, practically, the use of ethyl acetate is suitable for daily use. The sulphate can be a copolymer of the above-mentioned ethylene-based vinegar-based compound, and the umbrella can be 10 mol% or less, more preferably 7 mol%, without impairing the effects of the present invention. The following considerations are copolymerized with other monomers. The other monomers which are copolymerized as described above, for example, ethylene, propylene, isobutylene, "- ΐ ΐ α α it 二 ^, α - octadecene and other rare hydrocarbons, acrylic acid, methacrylic acid, Bazheng, Malay ι, Malay bribe, Yikang unsaturated lysine or its salt or calcined g, etc., (iv) nitrile such as nitrile, mercapto acrylonitrile, decylamine such as acrylamide, decyl decylamine, ethylene a thin acid or a salt thereof, an alkyl vinyl ether, a polyoxyethylene (meth) allyl ether, a polyoxypropylene (mercapto) allylic acid, such as a continuous acid, an acrylic acid, a mercaptopropionic acid Polyalkylene oxide (meth) propylene vinegar such as polyalkylene oxide (meth) allyl ether, polyethylene oxide (methyl methacrylate), acrylic acid acrylate, and propylene oxide (meth) acrylate. Polyoxyethylene (fluorenyl) acrylamide, polyoxypropylene (mercapto) acrylamide, polyoxyalkylene (mercapto) acrylamide, polyoxyethylene π-(mercapto) acrylamide-l' l —Dimercaptopropyl]g, polyoxyethylene vinyl ether, polyoxypropylene vinyl=, polyoxyethylene allylamine, polyoxypropylene allylamine, polyoxyethylene Ethyl vinylamine, polyoxypropylene vinylamine, diacrylamide, N-propylene amidoxime decyl ammonium chloride, allyl tridecyl vaporized Ian, dimercapto propylene Base gasification bond, 13 200922467 - monodecyl allyl vinyl ketone, N - vinyl π than singular ketone, gasified acetonitrile, hydrazine 7 thin, etc. These other monomers can be used together 2 Type B. Partial milk B and 'in the present invention' (meth)allyl, meaning allyl or methallyl, ((4)C-' (methyl)-propyl riding meaning-in When ffL or copolymerization is carried out, it is not particularly limited, and an alcohol such as a known polydihydrofurfuryl alcohol, ethanol or isopropyl alcohol may be used as a solvent, and the emulsion polymerization may be carried out in addition to the above solution polymerization method. Suspension polymerization also f: oxidation of i- ii poly-month, ethoxylated ruthenium, per-polymerization temperature, selected from the "contact" =: the appearance of ^ is the range of ~ ~. Further, in the case of C, it is more preferred that the polymer is dissolved in an alcohol such as the above-mentioned vinyl ester alcohol, ethanol, butanol or the like. The gentleman is doing the next thing. The above alcohol is, for example, a range of 20 to 50% by weight in the range of =============================================================================== ^ Waiting for the test - media. The above-mentioned Molar; acid is set to 1~1〇0 22 or more, and the amount of the ear is better than that of the 4 degree, and the average degree of deuteration of the resin (4) is better. If the degree of methylation of 70 to 98 falls outside the above range, that is, the average of the '_ resin (A) interferes with the spread of the pesticide contained in the package, and as a result, there is a delay in the solubility of water, and the above average volume becomes 枭The tendency to harm 4 reasons. Also ' _ _ month body 'heavy: two "726 determination. The average viscosity of heavy / ice solution at 2Qt, to 1 〇 14 200922467 '70mPa · s better, 15 : _ra · S Mu Jia, i5 ~ 6 〇 mPa · s is better. The reason is that the average viscosity of f is too low, the purity of the pesticide packaging is insufficient; = because of this, 'again, the film breaks when manufacturing has a tendency to make film difficult = outside! if ί sexual delay, It is a hindrance to the spread of the pesticide in the package, and the film is difficult to form due to the viscosity. "The average viscosity is measured in accordance with JIS K 6726. Further, the above acetylene glycol-based surfactant (β) is, for example, a compound of the following acetylene glycol, that is, for example, a fast diol and a block diol derivative towel.
千（R2 ) —C三 C —C (R3 ) rO | Γ Ο 、 CHa 1 1 CHa 1 CHK - η ^CHa m OH OH •Μ (1) A相n 中门及2各為f數1〜20之院基或烤丙基，彼此可 ^目同或不同。又’ r2及為碳數卜3之烧基，彼此可為相 同或不同。再者，m&n各為〇或3〇以下之正數。] ’、、 乂?々气式(山υ，如上所述，R2& r3各為碳數1〜3之烧基，又， 及R各為碳數1〜20之烷基或烯丙基。並且， R4’彼此可相同或不同。 /' 广舌Λ且，上述通式（1)表示之炔二醇系化合物中，氧化乙烯單位 早位/+η)之加成莫耳數L+n，（莫耳)較佳。原因 =P，祕乙烯單位之加成莫耳總數若過多，縣二醇系化合 勿本身對水之溶解性提高，膜之溶解性有降低傾向。 通式⑴表示之诀二料、化合物巾，氧化乙烯單位之加成 莫耳數為〇之炔二醇，具體而言例如：2,5,8，η —四〒基一6一十 ^5’8~二醇、5,8 —二甲基—6 —十二块—5,8-二醇、 ’，’9-四甲基—5 —癸炔—4,7—二醇、4,7—二甲基—5_癸炔 j 7-二醇、2, 3, 6, 7-四甲基—4-辛块—3, 6-二醇、3, 6-二 甲土 一4 —辛炔—3, 6 —二醇、2, 5一二甲基—3一己炔一2, 5_二醇 15 200922467 块二基 ^氧化乙婦加成莫耳總數;)、2，仍: 數:⑼、2,4,7,9-四—甲，Γ-t 化體Ϊ化乙婦加成料 基化體(氧化乙烯加i莫耳^·4)“：^快:3,6 —二醇之乙氧 及R3為甲基、m+n=i.3)、2,4,7 9__四甲其^ Hf異丁基、11 2氧基化，化乙烯加成莫耳總數通式[中1及二g Git併甲基、·3·5)。此等炔二醇系化合物，可 ⑷對於簡系樹脂 所=性以“， 分散=差1表面有見到渗出而產生結=以面活性劑⑻之 系樹脂(A)為主原料，於其中含，，係以則Η 脂組成物中，但除上述配/成=；卜生劑⑻而成之樹 二醇上=s::r:二甘 丙院等。該等可單難耻—_或三經甲基 (Α)10^*^Γ1!]4^^^ 佳為7〜38重量㈣即，上述可塑劑之含量若::重= 16 200922467 果低’有成為膜斷裂原因之傾向， 安定性差，製作—定尺寸之袋子 ^傾=製袋加讀之尺寸 水溶性膜之製膜裝置之滚筒或傳送帶等擔’為了提升 不含上 化乙说丨利k二〗酉曰t乳化乙稀山梨糖醇酐硬脂酸酯、聚氧 鹽、聚氧化_基嘛心乙^ =氧化稀烴__單乙醇胺鹽、、 虱化乙烯山梨糖醇酐單月桂酸酯為妥。 土 重量i述限定，相對於_咖。 會ί^ΙΠί量份。亦即’若上述界面活性劑之含量過少，則 制離性而或ί送，等金屬表面與已製膜之膜間的 有結塊之傾向，若過多，則滲出膜表面，捲繞時膜會 水溶=膜之農藥包裝用水溶性膜之形成材料，在不妨礙其 系踩的翻内，亦可添加抗氧化劑（苯盼系、胺 防銹劑、^^%酸醋類等）、著色料、香料、增量劑、消泡劑、 他水溶性i 體(if物或錢物），又亦可添加其 ϊ/丁聚糖m基齡素、錄乙基纖維素3。 為主包裝用水溶性膜，可將以上述p丽系樹脂⑷ 成物含綠二料、界面活軸⑻而成之樹脂組 予以ι膜（膜化）的到。上述製膜時，不特別限定，可採用产 17 200922467 y 延法等公知之方法。 對於上述流延法具體説明。 脂：分圭 為15〜35重量％)之樹脂組成物之水分今 重里％ (更佳 =表面4錢，此制本㈣之pv jThousands (R2) - C3 C - C (R3) rO | Γ 、 , CHa 1 1 CHa 1 CHK - η ^CHa m OH OH • Μ (1) A phase n gate and 2 are f numbers 1~20 The base or baking propyl can be the same or different from each other. Further, 'r2 and the base of carbon number 3 may be the same or different from each other. Furthermore, m&n is each a positive number of 〇 or less. ] ', 乂 々 々 ( υ υ υ υ υ υ υ υ υ υ υ υ υ υ υ ( ( R R R R R R R R R R R R R R R R R R R R R R R R R R R R R Further, R4' may be the same or different from each other. /' The tongue of the acetylene glycol compound represented by the above formula (1), the molar number of the ethylene oxide unit early/+η) is L+n (mole) is preferred. Reason = P, if the total number of additions of the ethylene unit is too large, the county diol system does not have a solubility in water, and the solubility of the film tends to decrease. The oxime diol of the ruthenium oxide unit represented by the formula (1), the compound towel, and the oxirane diol of the oxirane unit, specifically, for example, 2,5,8,η-tetradecyl-6-10^5 '8~diol, 5,8-dimethyl-6-twelve-5,8-diol, ','9-tetramethyl-5-decyne- 4,7-diol, 4, 7-Dimethyl-5-decyne j 7-diol, 2, 3, 6, 7-tetramethyl-4-octene-3,6-diol, 3,6-dimethylene-4 Octyne- 3,6-diol, 2,5-dimethyl-3-hexyne- 2,5-diol 15 200922467 Block II-based oxidized ethyl ester addition to the total number of moles;), 2, still: number :(9), 2,4,7,9-tetra-A, Γ-t Ϊ化乙化乙妇成成基化体(ethylene oxide plus i 莫 ^·4) ":^ fast: 3,6 — The ethoxylate of the diol and R3 are methyl, m+n=i.3), 2,4,7 9__tetramethyl, Hf isobutyl, 11 2 oxylated, ethylene addition molar number Formula [Medium 1 and 2 g Git and methyl, ·3·5). These acetylene glycol compounds can be (4) for the simple resin = ", dispersion = difference 1 surface sees bleed out Knot = the resin (A) of the surfactant (8) as the main raw material, which is contained therein, Η lipid composition in addition to the above but with / = to; ⑻ agent from the Ibsen tree glycol = s :: r: two galanin homes. The content of the above plasticizer is:: weight = 16 200922467 low 'There is a tendency to become a film breakage, and the stability is poor. The bag is made to be sized. The tilting = the bag or the reading of the water-soluble film of the film-making device, the drum or the belt, etc.利克二〗 酉曰t Emulsified Ethylene sorbitan stearate, polyoxygen salt, polyoxidation _ base 乙 乙 ^ = Oxide dilute __ monoethanolamine salt, bismuth ethylene sorbitan The laurate is suitable. The soil weight is defined as relative to _ coffee. Will ί^ΙΠί quantity. That is, if the content of the above surfactant is too small, the separation property or the sputum is sent, and the surface between the metal surface and the film to be formed tends to agglomerate. If too much, the surface of the film oozes out and the film is wound. Water-soluble = film forming material for water-soluble film for pesticide packaging, and it is also possible to add an antioxidant (bean expectant, amine anti-rust agent, ^^% acid vinegar, etc.) and coloring material without hindering the stepping of it. , perfume, extender, defoamer, his water-soluble i body (if or money), can also add its ϊ / butanose m gemin, recorded ethyl cellulose 3. The water-soluble film for the main package can be obtained by coating the resin group containing the green material and the active axis (8) with the p-based resin (4). The film formation is not particularly limited, and a known method such as the production method of 2009 2009 467 y can be employed. The casting method described above is specifically described. Lipid: 15% to 355% by weight of the resin composition of the moisture of the current weight % (better = surface 4 money, this system (four) pv j
，帶_膜第i滾筒將膜剝輸捲取為以之 通it表面溫度50〜140t：之墨花處理輥。又，於製偏為 2散液時’可適當選擇:將PV0H系 “曰界J =)、可塑劑、界面活性劑等各成分一次混合 化合二，可轉任意成的聽與水混合好，再混合_:分T序 傳送帶4，且之 跨越—對_多行之無端狀 乂：巧從T杈4流出之原液(樹脂組成物之水 二 /^上政同時乾燥者。前述無端狀傳送帶，例如由不―摄專达 且其外周表面經鏡面加工者較佳。导^ _由不銹鋼構成， 之馬ttf製膜第1滾筒’係一滾筒型輥，位於將從T槿心Φ 之原液(M脂組成物之水溶液)在i 出 並乾燥之製膜機的最上游側。 的知型輥上流延With the _ film ith roller, the film is stripped and wound into a photographic processing roller with a surface temperature of 50 to 140 t. In addition, when the partial dispersion is 2, the liquid can be appropriately selected: the PV0H system, the plasticizer, the surfactant, and the like are mixed and combined at one time, and the mixture can be mixed with water and mixed with water. Remixing _: sub-Tune conveyor belt 4, and spanning - _ multi-row endless 乂: the original liquid flowing out from T杈4 (resin composition of water two / ^ Shangzheng dry. The aforementioned endless conveyor belt For example, it is preferred that the outer surface of the outer surface is mirror-finished. The guide _ is made of stainless steel, and the first roller of the ttf film is a roller-type roller, which is located at the center of the Φ. (Aqueous solution of the M-fat composition) is cast on the most upstream side of the film forming machine which is i-dried and dried.
之Μ二從ί述製膜傳送帶或製膜第1滾筒將膜剝離後至捲m U =二Tfr，之原液(樹脂組成物之水以= 笛I，:=料㈣上乾燥成為膜狀，並從製膜傳#C 佳為之^里條^ ’於5G〜靴進行較佳，更 處理之溫度若過高，則膜 f巧不良的傾向，熱 有降低傾向。上輕處實際使㈣水溶性 I處理，通讀續在為了膜乾燥之乾 18 200922467 ^ 於分開的壓花輥實施。 並且，本發明之農藥包裝用水溶性臈之 a 依上述流延法説明，但是本發明之農藥包^ :刖斤述，已 製法。例如，本發明之農藥包裝用水溶性不限於此 用塗布機’將樹脂組成物之水分散液澆鑄在聚=Then, from the film forming belt or the film forming first roll, the film is peeled off to the roll m U = two Tfr, and the raw liquid (the water of the resin composition is dried on the flute I, := material (4) to form a film shape, And from the film-making pass #C 佳为^里条^' is better in the 5G~boots, if the temperature of the treatment is too high, the film f is in a bad tendency, and the heat tends to decrease. The upper part is actually made (4) The water-soluble I treatment is continuously carried out in a separate embossing roll for drying of the film. The water-soluble hydrazine of the present invention is described in the above-described casting method, but the pesticide package of the present invention is For example, the water solubility for the pesticide packaging of the present invention is not limited to the use of a coating machine to cast an aqueous dispersion of the resin composition in the poly =
醋膜或聚乙_等塑膠基材或金屬基材上子&甲^乙二= 系膜水溶性膜。 上從钇岛亦可侍PV0H 依此方式得到之本發明之水溶性膜 類、特性、目的等可適當設定，例如 〜9_。亦即若水溶性膜之厚度過薄 1 降低之傾向，反之若過厚，則於冷 、械強度有 傾向，又製膜時效率也有降低之傾向。、奋、又有大幅減慢的 又，得到之水溶性膜之表面可為平滑的，但 膜之=或^面施以魔花在述 再者，本發明之水雜财，在不妨礙本發明目H σ 3有其他水溶性高分子（聚_酸納 聚 咯侧、葡聚糖、幾丁聚糖、幾♦乙縣吼 維素等）、防_、著色^ /了負甲基、_素、減乙基纖 大變上ίΓί制之水雜膜，較佳為不使水分率產生 =吊濕包裝，並於1〇〜饥之溫度條件下 系樹ϋί 谷性膜，就膜材料而言，可藉由將以前述_ ^樹月:μ物+^於其中含有炔二醇系界面活⑽⑻而成 ί ，但是上述水溶性膜中所含之 、严體層析⑽等，實施膜之成分分析來確認。此時 液U、为辨列如將本發明之農藥包裝用水溶性膜以70肝醇水溶 P , ±}，以附FID檢測器之氣體層析儀5890A (Hewlett 〜kard製）、使用内徑〇. 53刪長度-之肥触⑽犯管柱 19 200922467 (Hewlett Packard 製），將管柱溫度從 ι〇〇。^ 升到280°C之升溫分析，藉此測定本發明之農=速度3°C/min 所含炔二醇系界面活性劑（B)。 μ匕凌用水溶性膜中 以此方式得到之水溶性膜，水溶性優異， 或分散於5(TC以下、較佳為3(Tc以下、更&為解性，係溶解 並且，前述農藥藥劑之包裝（單元包 之水者。 膜有用，再者，亦能利用於作為例如（水壓作，溶性 紙尿布等生理用品、造口術用袋(。st〇m =? · 吸血片等醫療用品、育苗片•刺繡用基布等暫、 。其中，在上述農藥之藥劑包伽 以下舉實施例對本發明進—步具體説明，但本 八要曰之下，不限於以下實施例。又，以下記述中，「八° 如無特別指明，係指重量基準。 」伤」， [實施例1] 於4%水溶液黏度15mPa.s(2(rc)、平均皂化 ^改^聰系樹脂(細G份中，加人甘油15份、作為界莫面^J 巧之4氧化烯烴烷基醚磷酸酯單乙醇胺鹽2份、水、及 醇系化合j勿⑻之Surfynol 44G(2,4,7,9-四甲基-5-癸伊: 4,7一二酵之乙氧基化體）（Air Products Japan K.K.製）4、份， 得到固體成分濃度35%樹脂組成物之水分散液。 將設在加熱板上之SUS之表面調整為舭後，使上述樹脂組 成物水分散液流延在經加熱之sus板上，之後以8〇〜卯它進行 2分鐘乾燥’並從SUS基材將膜剥離，得到厚度40#m之PV〇H系 [實施例2] ,將炔二醇系化合物 Surfynol 440(Air Products Japan K. K. 製）之配合量改變為〇. 5份。除此以外，與實施例丨同樣進行，得 到厚度40 /z m之PV0H系膜。 20 200922467 [實施例3] 將炔二醇系化合物 Surfynol 440(Air Products Japan Κ. K. 製）之配合量改變為10份。除此以外，與實施例1同樣進行，得 到厚度40/zm之PV0H系膜。 [實施例4] 使用4%水溶液黏度28mPa · s(20°C)、平均皂化度96莫耳％、 改質量2莫耳％之馬來酸改質pv〇H系樹脂。除此以外，與實施例j 同樣進行，得到厚度40am之PV0H系膜。 [實施例5] 就块二醇化合物而言，將 Surfynol 440(Air Products Japan K. K.製）改為使用 Surfynol420(2, 4, 7, 9一四甲基一5-癸炔—4, 7 —二醇之乙氧基化體）（Air Products Japan K.L製）5份。除此 以外’與實施例1同樣地進行，得到厚度40^之pv〇H系膜。 [實施例6] ' 使用4%水溶液黏度28mPa · s(20°C)、平均皂化度96莫耳％、 改質量2莫耳％之馬來酸改質pV〇H系樹脂，且炔二醇化合物使用A vinegar film or a polyethylene substrate or the like, or a metal substrate, a neutron & The water-soluble film, characteristics, purpose, and the like of the present invention obtained in this manner can be appropriately set, for example, ~9_. That is, if the thickness of the water-soluble film is too thin, the tendency is lowered. On the other hand, if it is too thick, there is a tendency for cold and mechanical strength, and the efficiency of film formation tends to decrease. The water-soluble film obtained on the surface of the water-soluble film can be smooth, but the film of the film or the surface of the film is used to describe the magic flower, and the water of the present invention does not hinder this. Inventive H σ 3 has other water-soluble polymers (poly-sodium sulphate side, dextran, chitosan, several ♦ 吼 吼 吼 等), anti- _, coloring ^ / negative methyl, _ 素, 乙 纤 纤 Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ 制 制 制 制 制 制 制 制 制 制 制 制 制 制 制In the above, the acetylene glycol-based interface (10) (8) may be contained in the above-mentioned water-soluble film, and the above-mentioned water-soluble film may be subjected to strict chromatography (10). The composition of the membrane was analyzed to confirm. At this time, the liquid U is a gas chromatograph 5890A (manufactured by Hewlett-Kard) equipped with an FID detector, and the inner diameter 〇 is used to distinguish the water-soluble film for the pesticide packaging of the present invention from 70 heparin water, P. 53 cut length - the fat touch (10) guilty column 19 200922467 (manufactured by Hewlett Packard), the column temperature from ι〇〇. ^ The temperature rise analysis was carried out at 280 ° C, whereby the acetylene glycol-based surfactant (B) contained in the agricultural speed = 3 ° C / min of the present invention was measured. The water-soluble film obtained in this manner in a water-soluble film is excellent in water solubility, or is dispersed in 5 (TC or less, preferably 3 (Tc or less, more & is decomposable, is soluble, and the aforementioned pesticide agent) Packing (the unit packs the water. The membrane is useful, and it can also be used as, for example, (hydraulic pressure, soluble paper diapers and other physiological products, ostomy bags (.st〇m =? · blood-sucking tablets, etc.) The article, the seedling sheet, the base fabric for embroidery, etc., wherein the invention is further described in the following examples of the pesticide package, but the present invention is not limited to the following examples. In the following description, "eight degrees" means the basis of weight unless otherwise specified. "Injury", [Example 1] Viscosity of 15 mPa.s in 4% aqueous solution (2 (rc), average saponification ^ Cong resin (fine In the G part, 15 parts of glycerin is added, 2 parts of 4 oxidized olefin alkyl ether phosphate monoethanolamine salt, water, and alcohol compound j (8) of Surfynol 44G (2, 4, 7) , 9-tetramethyl-5-anthracene: 4,7-diethanol ethoxylated) (made by Air Products Japan KK) 4 parts, obtained solid An aqueous dispersion of a resin composition having a body composition concentration of 35%. After adjusting the surface of the SUS provided on the hot plate to 舭, the aqueous dispersion of the above resin composition is cast on a heated sus plate, followed by 8 〇. ~ 卯 It was dried for 2 minutes' and the film was peeled off from the SUS substrate to obtain a PV〇H system having a thickness of 40 #m [Example 2], and the acetylene glycol-based compound Surfynol 440 (manufactured by Air Products Japan KK) was blended. In the same manner as in Example ,, a PVOH film having a thickness of 40 /zm was obtained in the same manner as in Example 20. 20 200922467 [Example 3] An acetylene glycol-based compound Surfynol 440 (Air Products Japan Κ. A PV0H film having a thickness of 40/zm was obtained in the same manner as in Example 1 except that the amount of the mixture was changed to 10 parts. [Example 4] Using a 4% aqueous solution viscosity of 28 mPa·s (20 ° C) In the same manner as in Example j, a PVOH film having a thickness of 40 mm was obtained, except that the average saponification degree was 96 mol%, and the mass of 2 mol% of the maleic acid-modified pv〇H-based resin was changed. 5] For the block diol compound, change Surfynol 440 (manufactured by Air Products Japan KK) to Surfynol 420 (2, 4, 7, 9-tetramethyl-5-decyne- 4, 7-diol ethoxylated) (manufactured by Air Products Japan KL) 5 parts. Other than Example 1 The same procedure was carried out to obtain a pv〇H film having a thickness of 40 μm. [Example 6] 'A maleic acid modified pV〇H-based resin having a viscosity of 28 mPa·s (20 ° C) of 4% aqueous solution, an average degree of saponification of 96 mol%, and a mass of 2 mol%, and an acetylene glycol Compound use
Surfynol 420(Air Products Japan K. K.製）5 份。除此以外，與 實施例1同樣進行，得到厚度4〇μπι之pV〇H系膜。 [比較例] 於4%水溶液黏度i5mpa · s(2〇°c)、平均皂化度88. 〇莫耳％之 未改質PV0H系樹脂中，加入甘油15份、作為界面活性劑之聚氧 化烯烴烧基_酸I旨單乙醇胺鹽2份及水，得到固體成分濃度35% 樹脂組成物之水分散液。 將置於加熱板上之SUS表面調整為9(rc後，將上述樹脂組成 物之水^散液流延在經加熱之sus板上，之後於8〇〜9(rc乾燥2 分鐘Μ足SUS基材將膜剝離，得到厚度4_之pv〇H系膜。 對於以此方式得到之實施例品及比較例品之各PV0H系膜，進 行以下§平價。結果如後表1所示。 [空氣圓頂消失時間] 21 200922467 敎封ϋ 5_氛圍下，使用經1週調濕之_祕，使用 …、、态匕波圓柱狀除草劑（平均粒徑5麵、組合化學工業公司製 =unjace L Jumb〇)25g ’製作成80χ90_大小的三向密封的包 ㈣二寬5°鹽高度1〇Cm之容器中，加水到5弧高，於 ^ί 水面上，使包裝有除草劑之上述包裝袋從高度70cm in:洛下麻面之上述包裝袋之膜’若吸水剌並開始溶 早’則内包的樂劑（除草劑）往水面上擴散，且同時與水面不接觸 上方）之_脹韻微地含空氣的狀態。狼此膨潤、溶 行，直到上述空氣圓頂部分崩潰為止的時間。並且，依昭 述基準評價各膜之性能。 …、 0:空氣圓頂消失時間小於400秒 χ:空氣圓頂消失時間大於等於4〇〇秒 [表1 ] 圓頂消 1 180 #ί(ο)~~~~ 實 2 350 #(〇)~~~ 施 3 例 4 ~~Ϊ50#(^)— 5 ~200 #(^— 6 170 #(〇y— 比較例 85〇%j^xy 袁且結果’由於實施例品較氣圓頂消泡時間短，故可知 i ίίί容性者。因此，經包裝之除草劑，不會結塊而堵住， 例如使用在水田等時能良好地擴散。 相=此’比較例品由於空氣圓頂消泡時間長，因此水溶性 * ^，在空氣圓頂之圓頂狀部分除草劑結塊，例如使用 水田等時’除草劑不擴散而堵住，僅在此領域的除草劑濃度增高， 22 200922467 對於稻子造成不利影響。 【圖式簡單說明】 無 【主要元件符號說明】 無Surfynol 420 (manufactured by Air Products Japan K. K.) 5 parts. Otherwise, in the same manner as in Example 1, a pV〇H-based film having a thickness of 4 μm was obtained. [Comparative Example] In a 4% aqueous solution viscosity i5mpa · s (2〇 °c), an average degree of saponification 88. 〇 mol% of the unmodified PV0H resin, 15 parts of glycerin, a polyalkylene oxide as a surfactant The alkyl group-acid I was used as 2 parts of monoethanolamine salt and water to obtain an aqueous dispersion of a resin composition having a solid concentration of 35%. After adjusting the surface of the SUS placed on the hot plate to 9 (rc, the aqueous dispersion of the above resin composition was cast on a heated sus plate, and then dried at 8 〇 9 (rc dried for 2 minutes). The substrate was peeled off to obtain a pv〇H-based film having a thickness of 4%. The PV0H-based films of the examples and comparative examples obtained in this manner were subjected to the following § parity. The results are shown in Table 1 below. Air dome disappearing time] 21 200922467 敎封ϋ 5_ Under the atmosphere, use 1 week to adjust the humidity, use ...,, state chopper cylindrical herbicide (average particle size 5, combined chemical industry company = Unjace L Jumb〇) 25g 'Make a three-way sealed bag of 80χ90_ size (4) Two containers with a width of 5° and a height of 1〇Cm, add water to 5 arcs high, on the water surface, so that the herbicide is packaged. The above-mentioned packaging bag is from the height of 70 cm in: the film of the above-mentioned packaging bag of the lower jaw pockmarks, if the squeegee is squeezing and begins to dissolve early, the inner agent (herbicide) spreads to the surface of the water and does not contact the water surface at the same time) _Inflated, the ground contains air. The wolf swells and dissolves until the air dome partially collapses. Time. Also, evaluate the performance of each film according to the reference. ..., 0: Air dome disappearance time is less than 400 seconds χ: Air dome disappearance time is greater than or equal to 4 〇〇 seconds [Table 1] Dome elimination 1 180 #ί (ο)~~~~ Real 2 350 #(〇)~~~ Shi 3 Example 4 ~~Ϊ50#(^)— 5 ~200 #(^— 6 170 #(〇y—Comparative Example 85〇%j^ Xy Yuan and the result 'Because the embodiment has a shorter defoaming time than the gas dome, it is known as i ίί 容. Therefore, the packaged herbicide will not block and block, for example, when used in paddy fields, etc. Diffusion. Phase = this 'comparative example because the air dome defoaming time is long, so the water solubility * ^, in the dome of the air dome, the herbicide agglomerates, for example, when using paddy fields, etc., the herbicide does not diffuse. Blocking, only the concentration of herbicides in this field is increased, 22 200922467 adversely affecting rice. [Simplified illustration] No [Main component symbol description] None