TW200814923A - Low-foam preparations for crop protection - Google Patents
Low-foam preparations for crop protection Download PDFInfo
- Publication number
- TW200814923A TW200814923A TW096121664A TW96121664A TW200814923A TW 200814923 A TW200814923 A TW 200814923A TW 096121664 A TW096121664 A TW 096121664A TW 96121664 A TW96121664 A TW 96121664A TW 200814923 A TW200814923 A TW 200814923A
- Authority
- TW
- Taiwan
- Prior art keywords
- ether sulfate
- water
- weight
- salt
- glycol ether
- Prior art date
Links
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Classifications
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
- A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G5/00—Fertilisers characterised by their form
- C05G5/10—Solid or semi-solid fertilisers, e.g. powders
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G5/00—Fertilisers characterised by their form
- C05G5/10—Solid or semi-solid fertilisers, e.g. powders
- C05G5/12—Granules or flakes
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24C—DOMESTIC STOVES OR RANGES ; DETAILS OF DOMESTIC STOVES OR RANGES, OF GENERAL APPLICATION
- F24C15/00—Details
- F24C15/006—Arrangements for circulation of cooling air
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24C—DOMESTIC STOVES OR RANGES ; DETAILS OF DOMESTIC STOVES OR RANGES, OF GENERAL APPLICATION
- F24C15/00—Details
- F24C15/02—Doors specially adapted for stoves or ranges
- F24C15/023—Mounting of doors, e.g. hinges, counterbalancing
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24C—DOMESTIC STOVES OR RANGES ; DETAILS OF DOMESTIC STOVES OR RANGES, OF GENERAL APPLICATION
- F24C15/00—Details
- F24C15/02—Doors specially adapted for stoves or ranges
- F24C15/04—Doors specially adapted for stoves or ranges with transparent panels
Landscapes
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
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200814923 九、發明說明 【發明所屬之技術領域】 本發明有關農藥製劑(調配物)之技術領域,諸如於保 護作物領域中之活性成份(農藥活性成份、肥料),尤其是 水溶性或部分水溶性活性作物保護劑成份(亦稱爲「作物 ^ 保護中之活性成份」)之調配物,特別是似鹽活性作物保 護劑成份之調配物,尤其是固殺草(glufosinate)鹽類,諸 如固殺草銨鹽,根據ISO亦稱爲固殺草銨。本發明亦有關 可與所述農藥及其調配物倂用之佐劑的混合物。 - 【先前技術】 由例如 EP-A-0048436 、 EP-A-00336151 與 EP-A- 1 0 93 722已習知固殺草銨之水性調配物。此處,較佳係使 用烷鏈長度爲C 1 2 · C 1 6並具有1至1 〇個伸乙氧基單位的 烷基醚硫酸鹽,其適於加強施用於植物綠色部分之固殺草 φ 的生物作用。內文中並不知烷基醚硫酸鹽的特定作用機制 。與所提出之烷基醚硫酸鹽相較,包括其他陰離子界面活 性劑之具有與之相當界面活性劑性質(噴灑附著性、對標 的植物上的散佈作用)的其他添加劑會降低活性。具有溶 . 劑特性的物質,諸如聚醚二醇、甘油、礦物油、礦物油濃 縮劑、聚合物、緩衝劑與其他物質任一均無法顯示任何與 之相當的活性。 由於所提出之C12-c16烷基醚硫酸鹽類型存在調配物 中,於施用前以水稀釋時以及在施用期間噴灑時,除非添 -5- 200814923 加消泡劑’否等此等調配物顯示出不當的起泡行爲。 其結果則是經常溢出噴灑裝置、污染環境、於作物上 噴灑沉積不均勻以及作物保護劑成份殘留物在噴灑裝置中 〇 就水性液態作物保護劑成份而言,EP-A-0407874提 & 出來自全氟烷基亞膦酸或膦酸之消泡劑。此類消泡劑(例 如得自Clariant之⑧Fluowet PP)突出之處係結合高消泡劑 0 活性與相當低之施用率,即使在不同溫度下長期貯存以及 調配物受到機械應力作用情況下,仍維持消泡劑活性。此 . 外,所調配作物保護劑成份的生物活性未受消泡劑含量影 • 響。 然而,習知氟化消泡劑不完全適用於所有應用領域。 許多此等調配物實例中,例如消泡活性受到用以製備噴灑 液體的水質硬度(鈣與鎂鹽含量)左右。亦由一般環境慣性 考量來看,希望減少環境中氟化烴之數量。 【發明內容】 基於前述理由,因此需要可製造例如活性作物保護劑 成份(諸如固殺草)或肥料之低泡調配物的替代解決方法, _ 此等低泡調配物具有良好技術性質,例如良好貯存安定性 與均勻之高生物活性。 本發明提出農藥農藥製劑,較佳係液態水性農藥製劑 ,諸如活性作物保護劑成份及/或肥料,其包含 (a ) —或更多種水溶性或部分水溶性農藥,較佳係活性 -6 - 200814923 作物保護劑成份及/或肥料((a)型活性成份), (b )視需要包含一或更多種非水溶性或大部分非水溶性 農藥’較佳係活性作物保護劑成份及/或肥料((b)型活 性成份), (c)烷鏈中具有1至9個碳原子且醚部分中具有1至20 個伸烷氧基單位之烷基醚硫酸鹽,較佳係具有1至20 個相同或不同Κ4伸烷氧基單位之(聚)伸烷氧基, 該基團含有末端以硫酸根酯化之伸乙氧基, (d )視需要包含陰離子、非離子、陽離子及/或兩性離子 界面活性劑, (e )視需要包含水,以及 (f )視需要包含其他慣用調配輔藥。 本發明含有消泡劑之調配物較佳係適用於似鹽(含鹽) 水溶性活性成份之(a)型活性成份,諸如固殺草(鹽)、嘉磷 塞(glyphosate)(鹽)、巴拉刈(paraquat)與大刈(diquat)等, 尤其是固殺草銨。適用之活性成份通常爲製備水性噴灑液 期間完全或部分溶解於水相者,以該噴灑液中之活性成份 重量(較佳係於實務慣用之活性成份濃度下)爲基準,通常 溶解1至1 0 0重量百分比,較佳係5至1 00重量百分比, 更佳係10至100重量百分比,特別是20至1〇〇重量百分 比,相當的是3 0至1 0 0重量百分比。除了上述活性作物 保護劑成份之外,此等活性成份實例係除草劑、殺黴菌劑 、殺蟲劑、殺蟎劑、驅蠕蟲劑與其他活性成份,諸如植物 -7- 200814923 生長調節劑與除草劑解毒劑(safener),較佳活性成份係諸 如例如碘甲磺隆鈉(iodosulfuron-methyl-sodium)、益達胺 (imidacloprid)、賽果培(thiacloprid)、丙硫菌口坐 (prothioconazole)與三泰隆(triadimenol)。 此處較佳者係於水中之溶解度在室溫下每公升水溶解 多於l〇mg活性成份的活性成份,較佳係多於20mg/i,特 別是多於3 0 m g /1。 適用之(a)型活性成份亦包括部分水溶性肥料,較佳係 葉肥(由植物葉片吸收之肥料),諸如脲或葉片主要元素或 微量元素肥料,包括螯合劑。 亦者係活性作物保護劑成份之組合,諸如除草劑、殺 蟲劑與殺黴菌劑,以及視需要包括肥料,作爲(a)型活性成 份。 本發明之調配物可另外包含(b )型活性成份,其大部分 不溶於水中,實例爲下列組成之除草劑:二苯醚,諸如復 祿芬(oxyfluorfen)、胺基甲酸酯、硫代胺基甲酸酯、三苯 錫化合物與三丁錫化合物、鹵代替苯胺、苯氧基苯氧基烷 竣酸衍生物及雜芳基氧苯氧基院羧酸衍生物,諸如喹啉基 氧基-、喹吗啉基氧基-、吡啶基氧基-、苯草醯基氧基-與 苯並噻唑基氧基苯氧基烷羧酸酯,其實例爲禾草靈-甲基 (diclofop-methyl),分殺草-乙基(fenoxaprop -ethyl)與芬殺 草-P-乙基。此處,應暸解「大部分不溶於水中」意指在 水性噴灑液中,較佳係於實務上慣用之活性成份濃度下, 相對於噴灑液中活性成份重量,通常溶解低於1重量百分 -8- 200814923 比,較佳係低於0.5重量%,特別是低於0.1重量百分比 。此處,較佳係於水中之溶解度係每公升水少於1 〇 m g活 性成份之活性成份,較佳係每公升水少於2 m g活性成份。 亦適用者係來自通常包括不同溶解度活性成份之物質 種類的相當不可溶活性成份,其實例係來自環己二酮衍生 物、咪唑酮、嘧啶氧基吡啶羧酸衍生物、嘧啶氧基苯酸衍 生物、磺醯脲、三唑嘧啶磺醯胺衍生物與S-(N-芳基_N-烷 基胺基甲醯)二硫代磷酸酯之活性成份。 熟悉之技術人士已知所述活性成份俗名諸如固殺草、 嘉磷塞、復祿芬、禾草靈-甲基,芬殺草- (P-)乙基等等; 詳見例如·’The Pesticide Manual” British Crop Protection Council,第13或第14版,分別爲於2003與2006年;或 ’’The Compendium of Pesticide Common Names”(尤其是可 由網際網路取得);此等俗名包括習知之衍生物,諸如固 殺草與嘉磷塞之鹽,尤其是市售習用形式。 亦相當可能以來自除草劑解毒劑(safener)、生長調 節劑、殺蟲劑與殺黴菌劑之活性成份適於作爲組份(b),及 /或在既定良好水溶性下適於作爲組份(a)。 所使用之(a)型與(b)型活性成份性質決定農藥調配物 的領域,較佳係作物保護劑成份或肥料。許多作物保護劑 成份係例如導向有害生物體防治。在除草劑情況當中,不 想要的植物即爲該種有害生物體,可藉由使用作物保護劑 成份或農藥調配物加以控制;在殺蟲劑情況中,有害生物 體係害蟲,而在殺黴菌劑情況中,有害生物體備有害黴菌 -9- 200814923 。此處亦適用的是此等成份之混合物,因此適用施用領域 之組合。 較佳者係來自一或更多種包含式(1)之化合物或其鹽類 之(a)型活性成份的調配物,
II 11 H3C—P—CHj-CHj-CH-C—Z1 (1)
NK
OH 其中
Zi 係式-OM、-NHCH(CH3)C0NHCH(CH3)C02m 或 NHCH(CH3)C0NHCH[CH2CH(CH3)2]C02M 之基團,其中 M = H或形成鹽之陽離子, 及/或一或更多種式(2)之化合物或其鹽類,
Ω IIR.O-P-CH^NH-CH—ζ2 (2)
其中 Ζ2係式CN或 之陽離子,且Q == 芳基,其係未經取 選自院基、院氧基 者取代,且R2、R
C〇2R!之基團’其中Rl = Q或形成鹽 ^纟兀基、儀基、院氧基院基或C 6 义 1 0 _ 代或經取代,而且較佳係未經取代戌終 、鹵素、CF3、N02與CN其中〜或更多 3各者彼此獨立爲H、烷基、(VCig、芳 -10 - 200814923 基,其係未經取代或經取代,而且較佳係未經取代$ _ _ 自烷基 '烷氧基、鹵素、CF3、N〇2與CN其中〜或更多者 取代,或是爲聯苯或形成鹽之陽離子。 較佳情況係,連同Q、R2或R3之含碳基團具有g # 1 〇個碳原子,特別是至多6個碳原子。 式(1)之化合物包括非對稱碳原子。L鏡像異構% $ 視爲生物活性異構。因此式(1)包括其所有立體異構物m宜 混合物,特別是各實例中之消旋物與生物活性鏡像異_ _ 式(1)之活性成份實例如下: •固殺草及其消旋形式之銨鹽,即,2-胺基-4-[羥基(甲基) 膦醯基]丁酸及其鹽類,諸如銨鹽或鈉鹽, •固殺草之L鏡像異構物與其鹽類,諸如銨鹽或鈉鹽, •畢拉草(bilanafos/bialaphos),即,L-2-胺基-4-[經基(甲 基)膦醯基]丁醯基-L-胺基丙醯基-L-丙胺酸與其鈉鹽 固殺草-銨鹽之消旋物自身輸送劑量通常係在介於200 與1 0 0 0 g a · i · / h a (即,每公頃活性成份克數)。此等劑量下 ,當固殺草-銨鹽被植物之綠色部分吸收時特別有效;詳 見"The Pesticide Manual”第 13 或第 14 版,British Crop Protection Council,分別爲於 2003 與 2006 年。固殺草-銨鹽係定期使用以控制農田與未耕種土地之闊葉與禾本科 雜草,亦使用特殊施用技術,例如諸如玉米、棉花等耕種 作物之行間控制。其用處亦明顯提高基因轉殖作物中之顯 -11 - 200814923 著性,其可耐或抗活性成份,例如於耐固殺草作物中,諸 如®LibertyLink 油采、®LibertyLink 玉米或⑧LibertyLink 棉花。 式(2)之化合物包含N-(亞磷羧基烷基)甘油,因此包 含胺基酸甘油之衍生物。N-(亞磷羧基甲基)甘油(嘉磷塞) 的除草性質描述於例如美國專利第3 7 9 9 7 5 8號。 在保護作物調配物中,嘉磷塞通常以水溶性鹽形式使 用,關於本發明方面,以異丙銨鹽特別重要;詳見’’The Pesticide Manual” 第 13 或第 14 版,British Crop Protection Council,分別爲於 2003與 2006年。與固殺 草-銨鹽相似的是,嘉磷塞-異丙銨鹽係用以控制農田與未 耕種土地之闊葉與禾本科雜草。其用處亦明顯提高基因轉 殖作物中之顯著性,其可耐或抗活性成份,例如於耐嘉磷 塞作物中,諸如㊣Roundup-Ready 玉米、®R〇undup-Ready 大丑、®Roundup-Ready 油采與 ®R〇undup-Ready 棉花。 本發明之組份(C)有關烷鏈中具有1至9個碳原子且醚 部分中具有1至2 0個伸烷氧基單位,較佳係1至1 2個伸 烷氧基單位的烷基醚硫酸鹽,烷基醚硫酸鹽一辭係指來自 (Ci-Cg)院基(聚)二醇醚硫酸鹽之化合物,通常具有末端硫 酸根。 (聚)伸烷氧基可含有相同或不同伸烷氧基單位,例 如Ci-CU伸烷氧基單位,諸如1,2-伸乙氧基[-CH2CH2-0-] ,亦簡稱爲「伸乙氧基」或「EO」、1,2-伸丙氧基[-CH(CH3)CH2-0-]、2,3-伸丙氧基[_〇112€11(0:113)-〇-]、152- -12^ 200814923 伸 丁氧基[-CH2CH(C2H5)-0_] 、 2,3-伸丁氧基卜 CH(CH3)CH(CH3)-0-]、3,4-伸 丁氧基[-CH(C2H5)CH2-0-]、 1,1-二甲基-1,2-伸乙氧基[-(:(0:113)20^2-〇-]與2,2-二甲基-1,2-伸乙氧基[-CH2C(CH3)2-0-]。此處較佳者係末端含有 以硫酸根酯化之1,2-伸乙氧基的(聚)伸烷氧基,即,該 聚伸烷氧基中帶有硫酸根之最後一個伸烷氧基單位,較佳 係EO單位。 特佳之組份(c)係具有1至20個EO,較佳係1至1〇 個EO之(Ci-Cd烷基(聚)乙二醇醚硫酸鹽。 在具有3或更多個碳原子之基團情況下,烷基 之烷基基團可爲直鏈或支鏈。 烷基醚硫酸鹽係陰離子界面活性劑。此等陰離子化合 物中之適用相對離子通常係適用於農業之所有陽離子,例 如鹼金屬陽離子,諸如鈉或鉀、鹼土金屬陽離子,諸如鎂 或鈣、銨或有機取代銨離子,諸如烷基銨、二烷基銨、三 烷基銨,例如三甲銨、異丙銨。其他陽離子基亦適用,諸 如三甲硫鹽離子(習知爲硫復松(sulfosate))或烷氧基化銨 離子。 適用之烷基醚硫酸鹽係例如甲基(聚)二醇醚硫酸鹽、 乙基(聚)二醇醚硫酸鹽、 丙基(聚)二醇醚硫酸鹽,諸如正丙基或異丙基(聚)二醇醚 硫酸鹽、 丁基(聚)二醇醚硫酸鹽,諸如正丁基、異丙基、第二丁基 或第三丁基(聚)二醇醚硫酸鹽、 -13- 200814923 戊基(聚)二醇醚硫酸鹽,諸如正戊基或異戊基(聚)二醇醚 硫酸鹽、 己基(聚)二醇醚硫酸鹽,諸如正己基、卜甲基戊或異己基( 聚)二醇醚硫酸鹽、 庚基(聚)二醇醚硫酸鹽,諸如正庚基或1-甲基己基(聚)二 醇醚硫酸鹽、 辛基(聚)二醇醚硫酸鹽,諸如正庚基或2-乙基己(聚)二醇 醚硫酸鹽,以及 壬基(聚)二醇醚硫酸鹽,諸如正壬基(聚)二醇醚硫酸鹽, 各者均含有1至20個烷二醇單位,其中以上述較佳(聚)烷 二醇基爲佳。更佳者係,具有1至個伸乙氧基單位(更 特別是1,2-伸乙氧基單位)之(聚)二醇醚部分。相對離子較 佳係鈉、鉀與銨離子。組份(C)之特定實例列於下表A1
下表A1中,列出式(A1)烷基(聚)乙二醇醚硫酸鹽 Ο R-O—(CH2CH20)n —S—0«MW (A1) Ο 其中 R係院基’ η係1至10之整數,並且意指該(聚)伸乙氧基橋中之伸乙 氧基單位數,且 -14- 200814923 M( + )係陽離子,較佳係H( + )或金屬離子或銨離子,其 中在個別化合物命名中,特別表示各化合物的R與η。 表A1 :特定乙二醇醚硫酸鹽 甲基乙二醇醚硫酸鹽, 甲基二乙二醇醚硫酸鹽, 甲基三乙二醇醚硫酸鹽, 甲基四乙二醇醚硫酸鹽, 甲基五乙二醇醚硫酸鹽, 甲基六乙二醇醚硫酸鹽, 甲基七乙二醇醚硫酸鹽, 甲基八乙二醇醚硫酸鹽, 甲基九乙二醇醚硫酸鹽, 甲基十乙二醇醚硫酸鹽, 乙基乙二醇醚硫酸鹽, 乙基二乙二醇醚硫酸鹽, 乙基三乙二醇醚硫酸鹽, 乙基四乙二醇醚硫酸鹽, 乙基五乙二醇二醇醚硫酸鹽, 乙基六乙二醇醚硫酸鹽, 乙基七乙二醇醚硫酸鹽, 乙基八乙二醇醚硫酸鹽, 乙基九乙二醇醚硫酸鹽, 乙基十乙二醇醚硫酸鹽, -15- 200814923 正丙基乙二醇醚硫酸鹽, 正丙基二乙二醇醚硫酸鹽, 正丙基三乙二醇醚硫酸鹽, 正丙基四乙二醇醚硫酸鹽, 正丙基五乙二醇醚硫酸鹽, 正丙基六乙二醇醚硫酸鹽, 正丙基七乙二醇醚硫酸鹽, 正丙基八乙二醇醚硫酸鹽, 正丙基九乙二醇醚硫酸鹽, 正丙基十乙二醇醚硫酸鹽, 異丙基乙二醇醚硫酸鹽, 異丙基二乙二醇醚硫酸鹽, 異丙基三乙二醇醚硫酸鹽, 異丙基四乙二醇醚硫酸鹽, 異丙基五乙二醇醚硫酸鹽, 異丙基六乙二醇醚硫酸鹽, 異丙基七乙二醇醚硫酸鹽, 異丙基八乙二醇醚硫酸鹽, 異丙基九乙二醇醚硫酸鹽, 異丙基十乙二醇醚硫酸鹽, 正丁基乙二醇醚硫酸鹽, 正丁基二乙二醇醚硫酸鹽, 正丁基三乙二醇醚硫酸鹽, 正丁基四乙二醇醚硫酸鹽, -16 200814923 正丁基五乙二醇醚硫酸鹽, 正丁基六乙二醇醚硫酸鹽, 正丁基七乙二醇醚硫酸鹽, 正丁基八乙二醇醚硫酸鹽, 正丁基九乙二醇醚硫酸鹽, 正丁基十乙二醇醚硫酸鹽, 異丁基乙二醇醚硫酸鹽, 異丁基二乙二醇醚硫酸鹽, 異丁基三乙二醇醚硫酸鹽, 異丁基四乙二醇醚硫酸鹽, 異丁基五乙二醇醚硫酸鹽, 異丁基六乙二醇醚硫酸鹽, 異丁基七乙二醇醚硫酸鹽, 異丁基八乙二醇醚硫酸鹽, 異丁基九乙二醇醚硫酸鹽, 異丁基十乙二醇醚硫酸鹽, 第二丁基乙二醇醚硫酸鹽, 第二丁基二乙二醇醚硫酸鹽, 第二丁基三乙二醇醚硫酸鹽, 第二丁基四乙二醇醚硫酸鹽, 第二丁基五乙二醇醚硫酸鹽, 第二丁基六乙二醇醚硫酸鹽, 第二丁基七乙二醇醚硫酸鹽, 第二丁基八乙二醇醚硫酸鹽, -17 - 200814923 第二丁基九乙二醇醚硫酸鹽, 第二丁基十乙二醇醚硫酸鹽, 第三丁基乙二醇醚硫酸鹽, 第三丁基二乙二醇醚硫酸鹽, 第三丁基三乙二醇醚硫酸鹽, 第三丁基四乙二醇醚硫酸鹽, 第三丁基五乙二醇醚硫酸鹽, 第三丁基六乙二醇醚硫酸鹽, 第三丁基七乙二醇醚硫酸鹽, 第三丁基八乙二醇醚硫酸鹽, 第三丁基九乙二醇醚硫酸鹽, 第三丁基十乙二醇醚硫酸鹽, 正戊基乙二醇醚硫酸鹽, 正戊基二乙二醇醚硫酸鹽, 正戊基三乙二醇醚硫酸鹽, 正戊基四乙二醇醚硫酸鹽, 正戊基五乙二醇醚硫酸鹽, 正戊基六乙二醇醚硫酸鹽, 正戊基七乙二醇醚硫酸鹽, 正戊基八乙二醇醚硫酸鹽, 正戊基九乙二醇醚硫酸鹽, 正戊基十乙二醇醚硫酸鹽, 異戊基乙二醇醚硫酸鹽, 異戊基二乙二醇醚硫酸鹽, -18- 200814923 異戊基三乙二醇醚硫酸鹽, 異戊基四乙二醇醚硫酸鹽, 異戊基五乙二醇醚硫酸鹽, 異戊基六乙二醇醚硫酸鹽, 異戊基七乙二醇醚硫酸鹽, 異戊基八乙二醇醚硫酸鹽, 異戊基九乙二醇醚硫酸鹽, 異戊基十乙二醇醚硫酸鹽, 正己基乙二醇醚硫酸鹽, 正己基二乙二醇醚硫酸鹽, 正己基三乙二醇醚硫酸鹽, 正己基四乙二醇醚硫酸鹽, 正己基五乙二醇醚硫酸鹽, 正己基六乙二醇醚硫酸鹽, 正己基七乙二醇醚硫酸鹽, 正己基八乙二醇醚硫酸鹽, 正己基九乙二醇醚硫酸鹽, 正己基十乙二醇醚硫酸鹽, 正庚基乙二醇醚硫酸鹽, 正庚基二乙二醇醚硫酸鹽, 正庚基三乙二醇醚硫酸鹽, 正庚基四乙二醇醚硫酸鹽, 正庚基五乙二醇醚硫酸鹽, 正庚基六乙二醇醚硫酸鹽, -19- 200814923 正庚基七乙二醇 正庚基八乙二醇 正庚基九乙二醇 正庚基十乙二醇 正辛基乙二醇醚 正辛基二乙二醇 正辛基三乙二醇 正辛基四乙二醇 正辛基五乙二醇 正辛基六乙二醇 正辛基七乙二醇 正辛基八乙二醇 正辛基九乙二醇 正辛基十乙二醇 2-乙基己基乙二 2-乙基己基二乙 2-乙基己基三乙 2-乙基己基四乙 2-乙基己基五乙 2-乙基己基六乙 2-乙基己基七乙 2-乙基己基八乙 2-乙基己基九乙 2-乙基己基十乙 醚硫酸鹽, 醚硫酸鹽, 醚硫酸鹽, 醚硫酸鹽, 硫酸鹽,
醚硫酸鹽, 醚硫酸鹽, 醚硫酸鹽, 醚硫酸鹽, 醚硫酸鹽, 醚硫酸鹽, 醚硫酸鹽, 醇醚硫酸鹽, 二醇醚硫酸鹽, 二醇醚硫酸鹽, 二醇醚硫酸鹽, 二醇醚硫酸鹽, 二醇醚硫酸鹽, 二醇醚硫酸鹽, 二醇醚硫酸鹽, 二醇醚硫酸鹽, 二醇醚硫酸鹽, -20- 200814923 正壬基乙二醇醚硫酸鹽, 正壬基二乙二醇醚硫酸鹽, 正壬基三乙二醇醚硫酸鹽, 正壬基四乙二醇醚硫酸鹽, 正壬基五乙二醇醚硫酸鹽, 正壬基六乙二醇醚硫酸鹽, 正壬基七乙二醇醚硫酸鹽, 正壬基八乙二醇醚硫酸鹽, 正壬基九乙二醇醚硫酸鹽, 正壬基十乙二醇醚硫酸鹽, 其中,各實例中以其任何鹽與混合物爲佳,更佳係具有 M( + )=鹼金屬作爲相對離子之鹼金屬鹽,或較佳具有 M( + ) = NH4 +作爲相對離子之銨鹽,其中以其鈉鹽' 鉀鹽或 銨鹽,特別是其鈉鹽尤佳。 然後此等特殊鹽類構對應相當於表A1之個別化合物 詳細清單,其中,爲供參考,鈉鹽構成對應於表A1之表 A2(並非個別重複),鉀鹽構成對應於表A1之表A3,銨鹽 構成對應於表A 1之表A4,列出醚硫酸之鈉鹽或醚硫酸鉀 鹽或醚硫酸銨鹽取代醚硫酸鹽。 特佳者亦可爲上述表A2、A3與A4之鈉與鉀及/或銨 鹽混合物。 上述添加劑(〇當中,較佳者係烷基基團中具有4至8 個碳原子之化合物,特別是6至8個碳原子,以及1至1〇 -21 - 200814923 個伸乙氧基單位。較佳者亦爲具有直鏈烷基基團之添加劑 〇 該等化合物係新穎化合物及/或可以類似用於製備具 有相當長烷鏈之烷基醚硫酸鹽的習知方法製備。因此,本 發明亦提出組份(C)之新穎化合物。 至於組份(d),視情況需要,其製劑可包括陰離子、非 離子、陽離子及/或兩性離子界面活性劑。此等化合物有 助於將表面活性提高或調整至希望水準,特別是若所使用 之烷基醚硫酸鹽含有非常短烷基基團時。 適於作爲組份(d)之界面活性劑係例如下列(其中,關 於該製劑或表面活性劑分子中之個別伸烷氧基單位,各實 例中EO =伸乙氧基單位,P〇 =伸丙氧基單位,且BO =伸丁 氧基單位): d 1)陰離子界面活性劑,諸如例如: dl-Ι)具有10-24個碳原子之脂肪醇與0-60個EO及/或0-20個PO及/或0-15個BO(任何順序)之陰離子衍生物 ,其呈醚羧酸鹽、磺酸鹽、硫酸鹽與磷酸鹽形式,及 其無機鹽(例如鹼金屬與鹼土金屬)與有機鹽(例如以胺 或烷醇胺爲基底者),諸如得自Clariant之 Genapol®LRO、Sandopan®級、Hostaphat/Hordaphos® 級; dl-2)由分子量爲400至108之EO、PO及/或BO單位組成 之共聚物的陰離子衍生物,其呈醚羧酸鹽、磺酸鹽、 硫酸鹽與磷酸鹽形式,及其無機鹽(例如鹼金屬與鹼 -22- 200814923 土金屬)與有機鹽(例如以胺或烷醇胺爲基底者); 醇之伸烷氧加成物的陰離子衍生物,除非結構 包括在組份(Ο烷基醚硫酸鹽之定義當中,否則其呈其 呈醚羧酸鹽、磺酸鹽、硫酸鹽與磷酸鹽形式,及其無 機鹽(例如鹼金屬與鹼土金屬)與有機鹽(例如以胺或烷 醇胺爲基底者); dl-4)脂肪酸烷醇醚(alkoxylate)之陰離子衍生物,其呈其 呈醚羧酸鹽、磺酸鹽、硫酸鹽與磷酸鹽形式,及其無 機鹽(例如鹼金屬與鹼土金屬)與有機鹽(例如以胺或烷 醇胺爲基底者)。 較佳陰離子界面活性劑係烷基聚乙二醇醚硫酸鹽,尤 其是脂肪醇二乙二醇醚硫酸鹽(例如 Genapol LRO®, Clariant)或烷基聚乙二醇醚羧酸鹽(例如2-(異十三基氧基 聚伸乙氧基)乙基羧基甲基醚,Marlowet 4538®,Hills), 其中適當地選用另外陰離子界面活性劑之數量與種類以免 形成調配結果中無法接受之起泡性。 d2)陽離子或兩性離子界面活性劑,諸如例如: d2-1)脂肪胺之伸烷氧加成物、具有8至22個碳原子(C8-C22)之四級銨化合物,諸如例如得自Clariant之 Genamin®C、L、Ο 與 T 等級; d2-2)界面活性兩性離子化合物,諸如例如牛膽鹼、甜菜鹼 與磺基甜菜驗,其呈得自G ο 1 d s c h m i d t之T e g 〇 t a i η ® -23- 200814923 級、得自 Clariant 之 Hostapon®與 Arkopon®級。 d3)非離子界面活性劑,諸如例如·· d3-l)具有8至24個碳原子並以任何順序具有0-60個EO 及/或0-20個PO及/或0-15個BO之脂肪醇。此等化 合物之實例係得自Clariant之Genapol®C、L、Ο、T 、UD、UDD與X級、得自BASF之Plurafac⑧與 Lutensol®A、AT、ON 與 TO 級、得自 Condea 之 Marlipal⑧24 與 013 級、得自 Henkel 之 Dehypon⑧級 ,以及得自 Akzo-Nobel 之 Ethylan®級,諸如 Ethylan CD 120 ; d3-2)脂肪酸烷醇醚與三甘油酯烷醇醚,諸如得自Condea 之 Serdox®NOG 級或得自 Clariant 之 Emulsogen⑧級 d3-3)脂肪酸醯胺院醇醚,諸如得自Henkel之Comperlan® 級或得自R h 〇 d i a之A m a m ®級; d3-4)炔二醇之伸烷氧加成物,諸如得自Air Products之 Surfynol®級;糖衍生物,諸如得自Clariant之胺基 糖及醯胺糖; d3-5)得自Clariant之葡糖醇; d 3 - 6)聚矽氧及/或矽烷爲底質界面活性劑化合物,諸如得 自 Goldschmidt 之 Tegopren'lg:與得自 Wacker 之 SE⑧ ,以及得自 Rhodia 之 Bevaloid®,Rhodorsil®,與 Silcolapse®級(Dow Corning,Reliance,GE,Bayer), d3-7)界面活性磺醯胺,例如,得自Bayer ; •24- 200814923 d3-8)界面活性聚丙烯酸與聚甲基丙烯酸衍生物,諸如得自 BASF 之 Sokalan®級; d3-9)界面活性聚醯胺,諸如得自Bayer之經改質明膠或衍 生之聚天冬胺酸,及其衍生物, d3-10)界面活性劑聚乙烯基化合物,諸如經改質PVP,諸 如得自BASF之Luviskol®級與得自ISP之Agrimer® 級,或衍生之聚醋酸乙烯酯,諸如得自Clariant之 Mowilith®級,或聚丁酸乙烯酯,諸如得自BASF之 Lutonal®,Wacker 之 Vinnapas®與 Pioloform®級,或經 改質聚乙烯醇,諸如得自Clariant之Mowiol®級, d3 -1 1)以順式丁烯二酸酐及/或順式丁烯二酸酐之反應產物 以及順式丁烯二酸酐共聚物及/或含有順式丁烯二酸 酐之反應產物的共聚物爲底質的界面活性聚合物,諸 如得自 ISP 之 Agrimer® VEMA 級, d3-12)褐煤蠟、聚乙烯蠟與聚丙烯蠟之界面活性衍生物, 諸如得自 Clariant 之 Hoechst®鱲或 Licowet®級, d3-13)多元醇爲底質之伸烷氧加成物,諸如得自Clariant 之 Poly glycol®級; d3-14)得自Clariant之界面活性聚甘油酯與其衍生物。 d3-15)烷基多醣及其混合物,例如得自Uniqema之 ®Atplus 級,較佳係 Atplus 43 5, d3-16)烷基糖苷,呈得自Henkel之APG®級,其實例係 ®Plantaren APG 225 (脂肪醇 C8-C1()糖苷), d3-17)山梨糖醇酯,呈得自Uniqema之Span®或Tween® -25- 200814923 級形式, d3-18)環糊精酯或醚,得自Wacker’ d3-19)界面活性纖維素衍生物與褐澡膠、蛋白質與關華豆 膠衍生物,諸如得自Clariant之Tylose®級、得自 Kelco之Manutex®級與得自Cesalpina之關華豆膠衍 生物, (13-2 0)以C8-C1G脂肪醇爲底質之烷基聚糖苷-烷基多醣混 合物,諸如 ®Glucopon 225 215 CSUP (Cognis) 至於組份(e),視情況需要,本發明之製劑可包含水。 較佳者係水性、液態、濃縮、具有貯存安定性調配物。待 用水性噴灑液亦可視爲本發明調配物。 同樣地,根據本發明的是無水或低水調配物,諸如粉 劑或粒劑或可乳化濃縮物,用水稀釋彼以形成僅供施用之 噴灑液。 至於組份(f),視情況需要,本發明製劑包含其他慣用 調配物輔藥,諸如溶劑、惰性材料,諸如膠黏劑、濕潤劑 、分散劑、乳化劑、滲透劑、防腐劑與抗凍劑、塡料、載 劑與色料、蒸發抑制劑與pH値改質劑(緩衝劑、酸與鹼) 或黏度改質劑(例如增稠劑),並視情況需要,亦包含消泡 劑’即使使用的話,後者僅適合少量使用。慣用調配物活 性成份(f)係例如上述惰性材料、抗凍劑、蒸發抑制劑、防 腐劑 '色料等;較佳調配物輔藥(f)係 -26- 200814923 •抗凍劑與蒸發抑制劑,諸如甘油或乙二醇,其用量例如 自2至1 〇重量%,及 •防腐劑,例如 Mergal K9N⑧(Riedel)或 Cobate C⑧。 可能之組份(f)係例如有機溶劑或無機溶劑或其混合物 。於液態製劑中’其通常包含水(組份(e))作爲溶劑。不過 ,就特殊應用而言,亦可能不粉劑或粒劑。甚至亦可能爲 以有機溶劑(諸如非極性或極性有機溶劑)爲底質之無水製 劑。 本發明範圍內之相當非極性溶劑實例係 •脂族或芳族烴,諸如例如礦物油或甲苯、二甲苯與萘衍 生物, •鹵化脂族或芳族烴,諸如二氯甲烷或氯苯, •油’例如植物油,諸如玉米胚芽油與油菜好油,或油衍 生物,諸如油菜籽油甲酯。 本發明內容中,「極性有機溶劑」一辭係惜例如極性 質子或非質子極性溶劑與其混合物。本發明範圍內之極性 溶劑實例係 „ •脂族醇’諸如例如低碳院醇,諸如甲醇、乙醇、丙醇、 異丙醇與丁醇,或多元醇,諸如乙二醇、甘油, •極性醚,諸如四氫呋喃(THF)、二噚烷、烷二醇一院基 醚與烷二醇二烷基醚,諸如例如丙二醇一甲醚、丙二醇 一乙醚、乙二醇一甲醚或乙二醇一乙醚,二乙二醇二甲 -27- 200814923 醚與四乙二醇二甲醚; •醯胺,諸如二甲基甲醯胺(DMF)、二甲基乙醯胺、二甲 基丙醯胺、二甲基癸醯胺(®Hallcomide)與N-烷基吡咯 B定酮; •酮,諸如丙酮; •以甘油及羧酸爲底質之酯,諸如一醋酸甘油酯、二醋酸 甘油酯與三醋酸甘油酯, •內醯胺, •酯部分中鏈長爲1至10個碳原子之乳酸酯, •碳酸二酯; •腈,諸如乙腈、丙腈、丁腈與苯甲腈; •亞颯與颯,諸如二甲亞礪(DMSO)與環丁颯。 亦經常適用的是額外包含醇之不同溶劑的組合,此等 醇係諸如甲醇、乙醇、正丙醇與異丙醇、正丁醇、異丁醇 、第三丁醇與2-丁醇。 適用於單相水性有機溶液者係完全或大部分可與水互 混溶劑或溶劑混合物。 在單相情況下,完全或大部分可與水互混之水性有機 溶液、溶劑或溶劑混合物爲宜。 本發明範圍內之較佳有機溶劑係極性有機溶劑,諸如 N·甲基吡咯酮與Dowanol® PM(丙二醇一甲酸)。
製備上述調配物必需之活性成份(特別是諸如界面活 性劑)原則上已習知,並描述於例如 MeCutche〇n,S -28- 200814923 '’Detergents and Emulsifiers Annual",MC Publ. Corp·, Ridgewood N. J. ; Sisley and Wood, ’’Encyclopedia of Surface Active Agents”,Chem. Publ· Co. Inc·,Ν·Υ· 1964 ;Sch6nfeldt, nGrenzflachenaktlve Athylenoxidaddukte’’ [ 界面活性氧化乙烯加成物],Wiss· Verlagsgesellschaft, Stuttgart 1 9 7 6 ; WinnackerKiichler , ’’Chemische
Technologie'1 [化學技術],第 7 卷,C. HanserVerlag, Munich,第4版,1 986年,此等文獻各者係以引用方式 參考之。 本發明亦提出烷基醚硫酸鹽之用法,視情況需要,與 其他界面活性劑倂用,作爲加強農藥活性之低泡添加劑, 該農藥較佳係水溶性或部分水溶性活性作物保護劑成份及 /或肥料,較佳係上述活性成份(a)。此包括本發明用於噴 灑液或希望用於製備噴灑液之製劑的用法,噴灑液中之活 性成份較佳係完全或部分水溶性,即,相對於噴灑液中之 活性成份重量(較佳係在實務上慣用之活性成份濃度下), 其數量通常爲1至100重量百分比,較佳係5至100重量 百分比,更佳係10至100重量百分比,特別是20至100 重量百分比,特佳係3 0至1 〇〇重量百分比。較佳情況係 上述活性成份(a)與在本文中提及之較佳活性成份。 此處,化合物可以單一化合物調配物及活性成份之共 調配物製備,或是可作爲桶混中之添加劑。 由於界面活性劑性質之故,烷基醚硫酸鹽(c)促進植物 吸收(a)型與(b)型活性成份,特別是經由植物葉片的吸收 -29- 200814923 作用,因此有助於改善活性成份之活性。令人驚訝的是, 本發明所使用之烷基醚硫酸鹽(C)的界面活性劑性質導致有 利活性改善並大幅降低製劑或噴灑液的起泡傾向。 適當選用製劑中之烷基醚硫酸鹽數量,使得製備噴灑 液時噴灑液不會起泡或形成相當少量起泡。此數量通常視 所選用之烷基部分的鏈長以及醚硫酸鹽部分中伸烷氧基單 位或EO單位數量而定。 活性成份(a)(以100%活性成份爲基準)對烷基醚硫酸 鹽(Ο (以清漂劑物質爲基準)的重量比可在廣泛範圍內變化 ,較佳係在1 : 〇 · 1至1 : 1 0,特別是1 : 0.5至1 : 5。 借組份混合物之助,可能製備農藥的濃縮低泡製劑, 較佳係濃縮低泡液態水性製劑,該農藥較佳係似鹽作物保 護劑成份,諸如固殺草-銨鹽,其包含 (a ) 1至40重量%,較佳係2至3 0重量%,特別是5至 20重量%之水溶性或部分水溶性農藥,較佳係活性作 物保護劑成份或肥料((a)型活性成份), (b ) 0至40重量%,較佳係〇至20重量%,特別是0至 1 0重量%非水溶性或大部分非水溶性農藥,較佳係活 性作物保護劑成份及/或肥料((b)型活性成份) (c ) 0.1至9 9重量%,較佳係1至8 0重量%,特別是2 至7 0重量%,特佳係5至6 0重量%之烷鏈中具有1 至9個碳原子且醚部分中具有1至20個伸烷氧基單 位之烷基醚硫酸鹽, (d ) 0至2 5重量%、較佳係〇至2 0重量%,特別是1至 -30- 200814923 20重量%,特佳係3至15重量%之陰離子、非離子、 陽離子及/或兩性離子界面活性劑, (e ) 0至9 5重量%,較佳係0 · 1至9 0重量%,更佳係5 至8 5重量%之水,特別是1 0至6 0重量%的水,以及 (f ) 〇至5 0重量%,較佳係0至2 0重量%,較佳係〇至 ^ 1 5重量%之其他慣用調配物輔藥。 φ 此處之「重量%」於各實例中係意指「重量百分比」 ,即,組份之重量與製劑之重量的百分比比値。亦較佳之 調配物當中,該等組份數量構成二或更多種上述較佳組份 部分的組合物。 本發明之液態調配物可以基本上慣用之方法製備,即 ,以攪拌或搖動混合組份,或藉由靜態混合方式製備。製 得之液態調配物穩定並具有良好貯存性質。 本發明另外提供低泡液態佐劑調配物,其可用於製備 φ 所述濃縮農藥調配物,較佳係作物保護劑成份調配物或肥 料,或用於製備具有農藥之桶混物,較佳係活性作物保護 劑成份調配物或肥料,或者可獨立施用、同時或依序與活 性成份施用(較佳係所述活性成份(a))施用於植物或土壌或 ^ 種植植物的土壤。 此種佐劑調配物包含 (c )烷鏈中具有1至9個碳原子且醚部分中具有1至20 個伸烷氧基單位之烷基醚硫酸鹽; -31 - 200814923 (d )視情況需要,包括陰離子、非離子、陽離子及/或兩 性離子界面活性劑, (e )水,以及 (f)視情況需要,包括其他慣用調配物輔藥, 成份(c)、(d)、(e)、(f)如上述包含活性成份之作物保護劑 成份調配物所界定。 較佳佐劑調配物包含 (c ) 〇·1至99.9重量%,更佳係0.1至99重量%,較佳係 1至8〇重量%,特別是2至70重量%,特佳是5至 60重量%烷鏈中具有1至9個碳原子與1至20個伸 烷氧基單位之烷基醚硫酸鹽, (d ) 0至5 0重量%,較佳係〇至3 0重量%,特別是1至 25重量%,特佳是5至20重量%之陰離子、非離子、 陽離子及/或兩性離子界面活性劑, (e ) 0 · 1至9 9 · 9重量%,更佳係〇 · 1至9 5重量%,較佳係 5至90重量%的水,較佳係1 〇至75重量%水, (Π ) 0至60重量%,較佳係〇至40重量%,特別是0至 3 0重量%之極性有機溶劑,以及 (f ) 0至2 0重量%,較佳係0至1 5重量%之其他慣用調 配物輔藥。 包含活性成份與佐劑調配物之液態調配物係具有良好 貯存性質之低泡調配物。其許多情況下均具有施用方面的 -32- 200814923 良好技術性質。例如,此等調配物突出之處係以水稀釋一 例如製備桶混物或以噴灑方式施用之調配物時,其起泡傾 向低。與習知包含長鏈烷基醚硫酸鹽之調配物相比,具有 活性成份與佐劑調配物之調配物和活性成份/活性成份調 配物同時使用時,亦顯示相當良好的生物作用。 本發明之調配物特別適用於保護作物,其中若情況適 當的話,以水稀釋之後將調配物施用於植物、植物某些部 分或耕種區。 在除活性成份(a)及/或(b)實例中,調配物相當適於控 制未耕種土地與耐除草劑作物中之不想要植物的生長情形 〇 當所使用(a)型活性成份係選擇性除草劑或殺蟲劑、殺 黴菌劑或肥料時,可使用本發明製劑本身或與低泡且有效 調配物合倂用於單子葉與雙子葉作物慣用活性成份中,例 如用於經濟作物,諸如穀類(小麥、大麥、黑小麥、裸麥 、稻、玉米、粟)、甜菜、甘蔗、油菜、棉花、葵花、豌 豆、豆類與大豆。本文中特別重要的是施用於單子葉作物 ,諸如穀類(小麥、大麥、裸麥、黑小麥、高梁),包括玉 米與稻,以及單子葉蔬苯作物,但亦施用於雙子葉作物, 諸如例如大豆、油菜、棉花、葡萄藤、蔬菜、水果與裝飾 用植物。 較佳活性成份a)實例中,製劑可單獨使用或與其他活 性成份a)及/或肥料倂用於未耕種土地、有益植物之畸零 地或用於適當耐除草劑作物。此處,除了上述耐除草劑有 -33- 200814923 用植物作物,諸如用於產生農戰作物的®LibertyLink或 ®Roundup-Ready作物、裝飾區與有用區作物(諸如草皮)亦 相當重要。例如’包含固殺草(_銨鹽)之具有或不具肥料的 本發明調配物適於控制裝飾草皮與有用草皮上之有害植物 ,尤其是黑麥草、早熟禾或百慕達草,特佳係用於耐固殺 草草皮。 【實施方式】 下列實施例中,除非另外指示,否則所述數量係以重 量爲基準(b.w. =以重量計)。表丨與2之實施例係關於本發 明之安定組成物。 表1 :調配物(根據本發明) 實施例編號 1 2 3 4 5 6 7 8 9 10 11 12 13 — Λ Λ 活性成份υ 1Η [%b.w.] 15 25 15 25 15 25 25 25 25 25 25 25 25 25 AES ---- (類型2)) C9 C9 C8 C8 C7 C7 C6 C6 C5 C5 C4 C3 C2 Cl AES [%b.w.] 40 30 40 30 40 30 30 40 30 40 40 40 40 40 濕潤劑3) -—-— [%b.w.l 0 0 0 0 0 0 5 0 5 5 5 5 5 5 有機溶劑4) 10 15 10 15 10 15 10 10 10 10 10 10 10 1 Π 水[%1^.] 35 30 35 30 35 30 30 25 30 20 20 20 20 20 表1之縮寫 活性成份」係指活性成份固殺草·銨鹽; -34- 200814923 2) 「AES」意指烷基醚硫酸鹽,其中r C9」意指烷鏈, 即,「C9型AES」係指具有1至1〇個E〇之壬基聚乙二 醇醚硫酸鹽混合物;「C8」、「C7」、「C6」、「C5」 ★ 、「C4」、「C3」、「C2」、「C1」相應地分別表示對 應羊基、庚基、己基、戊基、丁基、丙基、乙基與甲基聚 乙二醇醚硫酸鹽; 3) 「濕潤劑」係指具有1 5個EO之非離子濕潤劑十三烷 φ 醇乙醇鹽;以其他非離子濕潤劑(諸如醇烷醇鹽或烷基糖 苷)取代上述非離子濕潤劑時,可獲得相當之調配物;當 所使用之濕潤劑係離子濕潤劑,諸如磺酸琥珀酸二烷酯之 陰離子或諸如烷基胺基烷醇鹽之陽離子濕潤劑時,可獲得 替代性調配物。 4) 「有機溶劑」係指有機溶劑Dowanol® PM(丙二醇一 甲醚)
例編號 15 16 17 18 19 20 21 22 23 24 25 26 活性成份D 5 5 10 10 33 1 1 10 10 1 5 10 AES 型2)) C9 C9 C9 C9 C9 C6 C6 C6 C6 C4 C4 C4 AES _i%b.w.l 25 2.5 2 50 27 8 0.5 5 50 4 40 40 濕潤劑3) 3 3 0 0 0 0 3 0 0 2 3 5 溶劑4) 5 5 10 10 0 0 0 10 10 5 5 10 62 84.5 78 40 30 91 95.5 75 30 88 50 35 -35· 200814923 表2之縮寫:詳見表丨起泡試驗之縮寫 起泡試驗 藉由攪拌將表1與2所提及的濃縮液態作物保護劑調 配物稀釋成1 %濃度溶液,並於1分鐘、3分鐘與12分鐘 後,以體積ml測量所形成之泡沬體積(詳見(:1?八0^4丁 47.2之泡沬評估)。或者,將提及的添加劑本身溶解成 2g/l,並於1分鐘、3分鐘與12分鐘後,以體積ml測量 所形成之泡沬體積。 與以C12/C14脂肪醇二乙二醇醚硫酸鹽取代烷基醚硫 酸鹽之調配物相較之下,包含表1與表2之烷基醚硫酸鹽 的調配物形成的泡沬少很多。 實質上避免形成泡沬,即,就表1與2之調配物而言 ,於水中混合〇·2至5 g/Ι烷基醚硫酸鹽期間,各實例於3 分鐘後的泡沫體積均低於1 5 ml,於1 2分鐘後之泡沫體積 係0 ml,然而包含C12/C14脂肪醇二乙二醇醚硫酸鹽作爲 AES之對應調配物於3分鐘及10分鐘後的最大泡沬體積 均爲100 ml。該試驗中,單獨使用2g/l之C12/C14脂肪醇 二乙二醇醚硫酸鹽甚至於1 2分鐘後的最大泡沫體積仍爲 100 ml,然而表1與2之烷基醚硫酸鹽實例中,於12分 鐘後測得的泡沬體積均爲〇 ml,甚至於3分鐘後即低於 1 0 ml 〇 此泡沬試驗中,於3分鐘後,包含c12/C14脂肪醇二 乙二醇醚硫酸鹽與聚矽氧爲底質消泡劑(例如Rhodorsil㊣ -36- 200814923 級)之調配物的泡沬體積仍爲100 ml。反之,包含本發明 烷基醚硫酸鹽之調配物即使不添加額外消泡劑,其僅在3 分鐘後實質上即不再有泡沬。 生物實例 1) 施用固殺草以控制雜草 以水稀釋表1之調配物,並以200 Ι/ha之水施用率施 用於含有在自然條件上長出之有害植物的未耕種土地。4 週後之評估顯示出有害植物的綠色部分已死去,因此達到 有效控制有害植物。 2) 施用固殺草控制雜草 以水稀釋表1與2之調配物,獲得施用於含有在自然 條件上長出之單子葉與雙子葉有害植物的未耕種土地的固 殺草慣用施用率(300- 1 000 g/ha)的200-400 Ι/ha水施用率 。5週後的效果評估顯示出有害植物的綠色部分已死去, 因此達到有效控制有害植物。例如,與包含C12/C14脂肪 醇二乙二醇醚硫酸鹽作爲AES之調配物相比,表1第1至 8欄與1至9欄的調配物顯示出,於固殺草對AES相同比 率下,在控制單子葉與雙子葉有害植物方面,其生物作用 具有同等良好結果。 3) 水溶性葉肥(諸如脲)的葉部穿透性 在將脲(於噴灑液中0.1至2%)葉部施用於單子葉作物 -37- 200814923 (諸如玉米)以及雙子葉作物(諸如蘋果)的實例中,於存在 0.05至1%本發明烷基醚硫酸鹽其中之一時,若干天內葉 部吸收率提高至少兩個係數。 4)殺蟲劑之吸收 於葉部施用氯菸醯基殺蟲劑(諸如益達胺)且益達胺: 烷基醚硫酸鹽比自4:1至1:4之實例中,穿透蘋果葉達 到的活性成份吸收率比不包含任何烷基醚硫酸鹽之益達胺 調配物(諸如例如⑧confid〇r SL200或SC3 5 0)實例快2至5 倍。
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Claims (1)
- 200814923 十、申請專利範圍 1 · 一種農藥製劑,其包含 (a ) —或更多種水溶性或部分水溶性農藥((a)型活性成份 ), /w (b )視需要包含一或更多種非水溶性或大部分非水溶性 一 農藥((b)型活性成份), (c )烷鏈中具有1至9個碳原子且醚部分中具有1至20 0 個伸烷氧基單位之烷基醚硫酸鹽, (d )視需要包含陰離子、非離子、陽離子及/或兩性離子 界面活性劑, (e )視需要包含水,以及 (f)視需要包含其他慣用調配輔藥。 2 ·如申請專利範圍第1項之製劑,其中包含 (a)自1至40重量%之水溶性或部分水溶性農藥((a)型 活性成份), φ ( b )自0至4 0重量%之非水溶性或大部分非水溶性農藥 ((b)型活性成份), (c)自0.1至99重量%之烷鏈中具有1至9個碳原子並 具有1至2 0個伸烷氧基單位之烷基醚硫酸鹽, _ ( d)自〇至25重量%之陰離子、非離子、陽離子及/或兩 性離子界面活性劑’ (e )自〇至9 5重量%之水,以及 (f)自〇至50重量%之其他慣用調配輔藥。 3 .如申請專利範圍第1項之製劑,其中包含 -39- 200814923 (a)自2至30重量%之水溶性或部分水溶性農藥((a)型 活性成份), (b )自0至2 0重量%之非水溶性或大部分非水溶性農藥 ((b)型活性成份), (c )自1至80重量%之烷鏈中具有1至9個碳原子並具 有1至20個伸烷氧基單位之烷基醚硫酸鹽, (d)自0至20重量%之陰離子、非離子、陽離子及/或兩 性離子界面活性劑, (e )自5至8 5重量%之水,以及 (f )自〇至2 0重量%之其他慣用調配輔藥。 4·如申請專利範圍第1項之製劑,其中包含一或更多 種來自固殺草(鹽)、嘉磷塞(鹽)、巴拉刈與大刈之活性成 份作爲組份(a)。 5. 如申請專利範圍第1項之製劑,其中包含固殺草-銨 鹽作爲組份(a)。 6. 如申請專利範圍第2項之製劑,其中包含一或更多 種來自固殺草(鹽)、嘉磷塞(鹽)、巴拉刈與大刈之活性成 份作爲組份(a)。 7·如申請專利範圍第2項之製劑,其中包含固殺草-銨 鹽作爲組份(a)。 8.如申請專利範圍第3項之製劑,其中包含一或更多 種來自固殺草(鹽)、嘉磷塞(鹽)、巴拉刈與大刈之活性成 份作爲組份(a)。 9·如申請專利範圍第3項之製劑,其中包含固殺草-銨 -40- 200814923 鹽作爲組份(a)。 I 0 · —種製備如申請專利範圍第1項之製劑的方法, 其包括混合組份(a)至(f),視情況需要,調配物中存在其 他組份。 II · 一種佐劑調配物,其包含 (c)烷鏈中具有1至9個碳原子且醚部分中具有1至20 個伸烷氧基單位之烷基醚硫酸鹽; (d )視情況需要,包括非離子、陽離子及/或兩性離子界 面活性劑, (e )水,以及 (f )視情況需要,包括其他慣用調配物輔藥。 12·—種烷鏈中具有1至9個碳原子且醚部分中具有1 至2 0個伸烷氧基單位的烷基醚硫酸鹽。 1 3 · —種加強水溶性或部分水溶性農藥活性之方法, 其中烷鏈中具有1至9個碳原子且醚部分中具有1至20 個伸烷氧基單位之烷基醚硫酸鹽作爲與農藥一同施用之低 泡添加劑,視情況需要倂用界面活性劑。 1 4 ·如申請專利範圍第1 3項之方法,其中該農藥係選 自活性作物保護劑成份與肥料。 1 5 ·如申請專利範圍第1 3項之方法,其中該農藥係選 自固殺草(鹽)、嘉磷塞(鹽)、巴拉刈與大刈以及肥料。 1 6 .如申請專利範圍第1 3項之方法,其中該農藥係選 自活性作物保護劑成份固殺草-銨鹽。 1 7. —種控制不要之植物生長的方法,其包括施用有 -41 - 200814923 效量之申請專利範圍第1項之製劑,其1 草劑活性成份(a) ’以及視情況需要包含 ,以水稀釋之後,施用於植物、植物某I 或耕種區。 1 8 .如申請專利範圍第1 7項之方法 一或更多種來自固殺草(鹽)、嘉磷塞(鹽 之活性成份作爲組份U)。 1 9 .如申請專利範圍第1 8項之方法, 銨鹽作爲組份(a)。 2含一^或更多種除 (b),若情況適當 ^部分、植物種籽 ’其中該製劑包含 )、巴拉刈與大刈 其中包含固殺草-广 -42 - 200814923 七、指定代表圖 (一) 、本案指定代表圖為:無 (二) 、本代表圖之元件代表符號簡單說明··八、本案若有化學式時,請揭示最能顯示發明特徵的化學 式:無-4-
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| DE102004026937A1 (de) | 2004-06-01 | 2005-12-22 | Bayer Cropscience Gmbh | Konzentrierte wäßrige Formulierungen für den Pflanzenschutz |
| JP2006117650A (ja) * | 2004-09-27 | 2006-05-11 | Kao Corp | 除草剤組成物 |
| JP5323523B2 (ja) | 2009-02-10 | 2013-10-23 | 株式会社パイロットコーポレーション | 複合筆記具用の振出式シャープペンシル体 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI561170B (en) * | 2010-12-21 | 2016-12-11 | Meiji Seika Pharma Co Ltd | Stabilized liquid aqueous crop protection composition |
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