TW200412852A - Diphenyl ether and N-(phosphonomethyl)glycine herbicidal compositions and methods of use - Google Patents

Diphenyl ether and N-(phosphonomethyl)glycine herbicidal compositions and methods of use Download PDF

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TW200412852A
TW200412852A TW92123050A TW92123050A TW200412852A TW 200412852 A TW200412852 A TW 200412852A TW 92123050 A TW92123050 A TW 92123050A TW 92123050 A TW92123050 A TW 92123050A TW 200412852 A TW200412852 A TW 200412852A
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herbicide
composition
salt
item
solution
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TW92123050A
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Chinese (zh)
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Charles W Finch
Donna Zormeier
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Basf Corp
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N57/00Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/20Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
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  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The present invention describes herbicidal compositions, including their methods of use. The compositions include (a) a N-phosphonomethylglycine or homoalaninylmethyl-phosphinate herbicide or a salt or acid thereof; (b) a diphenyl ether herbicide or a salt or ester thereof; (c) a glycol; (d) an amine source; and (e) a carrier. The present compositions are formulated as solutions. Such compositions are useful in methods to inhibit the growth of unwanted plants by contacting the plant with an herbicidally effective amount of the composition. The present invention further describes method of making such compositions.

Description

200412852 玖、發明說明: 【發明所屬之技術領域】 本發明有關新穎之除草組合物及其使用方法,尤其本發 明有關一種調配為溶液之除草組合物,其包括至少一種苯 酸除草劑及至少一種N-(膦甲基)甘胺酸或均膦酸丙胺酸甲 基酯除草劑。 【先前技術】 嘉磷塞(glyphosate)亦稱為N-(膦甲基)甘胺酸,一般使用 作為寬廣草譜之萌發後除草劑。該除草劑係施加至不利植 物之葉面,藉由葉面組織吸收該除草劑並傳遞至整個植 物。一旦嘉塞磷吸收於植物内,其可抑制生化路徑中之胺 基合成’該生化路控對幾乎所有植物為普遍現象但不存 在於動物中。 嘉磷塞之各種鹽、製備嘉磷塞之鹽類之方法、嘉磷塞或 其鹽之調配物及嘉磷塞或其鹽之使用方法揭示於Sat〇等人 之美國專利號5,998,332、Burval等人之美國專利號5,468,718 ;Franz之美國專利號4,405,531 ;及”嘉磷塞:一種獨特之全 球除草劑” ACS專題論文189,第27-64頁(1997);其均併入 本文供參考。 雖然嘉磷塞廣泛作為除草劑,但其效果之可見徵狀出現 在相當後期階段。有些除草劑組合物可藉組合該嘉磷塞與 其他除草劑如苯醚(經常用以控制年生闊葉雜草及牧草)而 解決此問題。雖然此組合物可加速除草劑作用之可見徵狀 出現’但組合嘉磷塞及苯醚除草劑伴隨有溶解度問題。就 87453 200412852 此’該等除草劑典型上以低劑量劑型組合及/或調配為乳液 態以避免該溶解度問題。例如,Sato等人之美國專利號 5,565,409描述一種包含嘉磷塞及苯醚之微乳液。 類似地,均膦酸丙胺酸曱基酯亦稱為固殺草(gluf〇sinate) 當與苯醚除草劑組合時有溶解度問題。 因此,需要一種包含苯醚及嘉磷塞及固殺草之溶液態除 草組合物。 【發明内容】 如前及後文廣泛所述,本發明一方面有關一種除草組合 物’其包括a)N-膦甲基甘胺酸或均膦酸丙胺酸甲基酿除草 劑或其鹽或酸;b)苯醚除草劑或其鹽或g旨;e)二醇;句胺源; 及e)載劑。本發明之組合物係調配為溶液。又包含混合該 成分a)、b)、c)、d)及e)之產物。 再者’本發明有關抑制不利植物生長之方法,包含使該 植物與除草有效量之上述除草組合物接觸。 再者’本發明描述一種製造此組合物之方法,係使上述 組合成分混合在一^起形成溶液。 本發明之優點將部分述於下列說明中,且部分將可由該 說明顯而易見或可藉操作本發明而了解。需了解前述_般 說明及下列詳細說明僅為舉例及說明而非用以限制本發明 之範圍。 【實施方式】 本發明可由下列本發明具體實例及其中包含之實例之詳 細說明而變得顯而易見。 87453 200412852 本化合物之如,先褐示組合物及方法,需了解本發明不 限於其製造之特疋合成方法,當然其可多變。亦需了解本 文所用之名詞僅用以描述特定具體例且不用以限制。 此說明書及後述申請專利範圍中,有關之數種名詞具有 下列足義· 本文所用之”烯類”意指含至少一個雙键之分支或未分支 不飽和烴基,如乙缔、丙缔、^丁烯、孓丁烯等。婦基可具 有一或夕個氫原子經官能基置換,如幾基、南基、烷氧基、 及/或芳基。 本文所用之’,$克基”代表分支或未分支之飽和烴基,如甲 基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基 等。烷基可藉有一或多個氫原子經官能基置換,如羥基、 鹵基、烷氧基、及/或芳基。 本文所用之”炔類”意指含至少一個參鍵之分支或未分支 不飽和烴基,如乙炔、丙炔、I丁炔、2_丁炔等。炔基可具 有一或多個氫原子經官能基置換,如羥基、卣基、烷氧基、 及/或芳基。 用以意指至少例如將至少一種植物細 ,係使用本技藝任何方法施加該除草200412852 发明 Description of the invention: [Technical field to which the invention belongs] The present invention relates to a novel herbicidal composition and a method for using the same. In particular, the present invention relates to a herbicidal composition formulated as a solution, which includes at least one benzoic acid herbicide and at least one N- (phosphonomethyl) glycine or homophosphonic acid alanine methyl ester herbicides. [Prior art] Glyphosate is also called N- (phosphonomethyl) glycine, and is generally used as a post-emergent herbicide with a broad grass spectrum. The herbicide is applied to the leaf surface of the unfavorable plant, and the herbicide is absorbed by the leaf surface tissue and transmitted to the entire plant. Once the carbazide is absorbed in the plant, it can inhibit the amine synthesis in the biochemical pathway '. The biochemical pathway is common to almost all plants but does not exist in animals. Various salts of Carfosin, methods of preparing Carfosin salts, formulations of Carfosin or its salt, and methods of using Carfosin or its salt are disclosed in U.S. Pat. No. 5,998,332, Burval et al. U.S. Pat. No. 5,468,718; Franz U.S. Pat. No. 4,405,531; and "Carfosin: A Unique Global Herbicide" ACS Monograph 189, pages 27-64 (1997); all of which are incorporated herein by reference. Although glyphosate is widely used as a herbicide, visible signs of its effect appear at quite a later stage. Some herbicide compositions can solve this problem by combining the carbohydrate plug with other herbicides such as phenyl ether (often used to control annual broadleaf weeds and pastures). Although this composition can accelerate the appearance of visible signs of the effect of the herbicide, the combination of glyphosate and phenyl ether herbicides is accompanied by solubility problems. As for 87453 200412852, these 'herbicides are typically combined in low-dose formulations and / or formulated as emulsions to avoid this solubility problem. For example, U.S. Patent No. 5,565,409 to Sato et al. Describes a microemulsion comprising carbohydrate plug and phenyl ether. Similarly, phosphonium aluminophosphonate is also known as glufosinate, which has solubility problems when combined with phenyl ether herbicides. Therefore, there is a need for a solution-type herbicidal composition comprising phenyl ether and carfosin and a solid herbicide. [Summary of the Invention] As described in the foregoing and in the following, one aspect of the present invention relates to a herbicidal composition 'comprising a) N-phosphine methylglycine or homophosphonic acid alanine methyl brewed herbicide or its salt Acids; b) phenyl ether herbicides or salts or salts thereof; e) diols; amine sources; and e) carriers. The composition of the present invention is formulated as a solution. It also includes products obtained by mixing the components a), b), c), d) and e). Furthermore, the present invention relates to a method for inhibiting the growth of an unfavorable plant, which comprises contacting the plant with a herbicidally effective amount of the above-mentioned herbicidal composition. Furthermore, the present invention describes a method for manufacturing the composition, in which the above-mentioned combined ingredients are mixed together to form a solution. The advantages of the present invention will be described in part in the following description, and part of them will be obvious from the description or can be understood by operating the present invention. It should be understood that the foregoing general description and the following detailed description are merely examples and descriptions, not intended to limit the scope of the present invention. [Embodiment] The present invention will become apparent from the following detailed description of specific examples of the present invention and examples contained therein. 87453 200412852 As for the present compound, the composition and method are shown first. It should be understood that the present invention is not limited to the special synthetic method for its production, and of course, it can be varied. It should also be understood that the terms used in this article are only used to describe specific examples and are not intended to be limiting. In this specification and the scope of the patent application described below, the relevant terms have the following meanings. As used herein, "olefins" means branched or unbranched unsaturated hydrocarbon groups containing at least one double bond, such as ethylene, propylene, ^ Butene, butadiene, etc. Alkyl may have one or more hydrogen atoms replaced by a functional group, such as several groups, south groups, alkoxy groups, and / or aryl groups. As used herein, ", gram" represents a branched or unbranched saturated hydrocarbon group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, third butyl, etc. The alkyl group can be borrowed One or more hydrogen atoms are replaced with a functional group, such as a hydroxyl group, a halo group, an alkoxy group, and / or an aryl group. As used herein, "alkynes" means branched or unbranched unsaturated hydrocarbon groups containing at least one para-bond, Such as acetylene, propyne, I-butyne, 2-butyne, etc. The alkynyl group may have one or more hydrogen atoms replaced by a functional group, such as a hydroxyl group, a fluorenyl group, an alkoxy group, and / or an aryl group. Means at least, for example, at least one plant, which is applied by any method of the art

再生抑制作用、增殖作用及移除、 本文所用之”接觸”用 胞暴露於本組合物中, 劑0 %I、生長抑制作用、 破壞或者消除植物發生 及活性之效果。熟知本技藝者將了解本發明所用之各種組 87453 200412852 合物之效力為可變且因此’’除草有效量π亦可變。 本文所用之’’植物’’意指陸地植物及水生植物。陸地植物 包含萌芽種子、萌芽幼苗及草本植物包含根及地面上部分 以及確立之草本植物。水生植物包含水藻、植物有機體自 由漂浮及浸沒物種,其一般根植入土壤中。植物之非排外 之例舉包含下列種(但非限於):芎麻屬(Abutilon)、莧屬 (Amaranthus)、艾草(Artemisia)、馬利筋(Asclepias)、燕麥 屬(Avena)、地毯草屬(Axonopus)、Borreria、巴拉草 (Brachiaria)、油菜(Brassica)、雀麥(Bromus)、小葉黎 (Chenopodium)、小薊(Cirsium)、竹葉菜(Commelina)、甕菜 (Convolvulus)、狗牙根(Cynodon)、伞草(Cyperus)、馬唐 (Digitaria)、稗草(Echinochloa)、牛筋草(Eleusine)、披驗草 (Elymus)、筆管草(Equisetum)、槐牛兒苗(Erodium)、向曰葵 (Helianthus)、白茅(Imperata)、番薯(Ipomoea)、地膚(Kochia) 、黑麥草(Loium)、錦葵(Malva)、水稻(Oryza)、Ottochloa、 糠稷(Panicum)、雀稗(Paspalum)、草蘆(Phalaris)、蘆葦 (Phragmites)、篇蓄(Polygonum)、半支蓮屬(Portulaca)、蕨 菜屬(Pteridium)、葛藤屬(Pueraria)、苺屬(Rubus)、豬毛菜 屬(Salsola)、狗尾草屬(Setaria)、黃花屬(Sida)、白齐屬 (Sinapis)、高梁屬(Sorghum)、小麥屬(Triticum)、浦菜屬 (Typha)、Ulex、蒼耳屬(Xanthium)及玉米屬(Zea)。 闊葉物種舉例包含(但不限於)下列:絨毛葉(芎麻 (Abutilon theophrasti))、藜(Amaranthus spp.)、艾(Artemisia SPP )、乳草(Asclepias spp·)、buttonweed (Borreria spp.)、油 200412852 麻菜子、棕橺(canola)、印度芬菜等(Brassica spp.)、加拿大 薊(Cirsium arvense)、竹葉菜(竹葉菜屬(Commelina spp·))、 田間旋花(Convolvulus arvensis)、太陽花(Erodium spp·)、向 日葵(Helianthus spp.)、牵牛花(蕃薯屬(Ipomoea spp·))、地 膚(Kochia scoparia)、錦葵(錦葵屬(Malva spp.))、野生驀麥、 水寥等(篇蓄屬(Polygonum spp·))、馬齒莧(半支蓮屬 (Portulaca spp·))、葛(葛屬(Pueraria spp·))、蘇俄薊(豬毛菜 屬(Salsolaspp·))、黃花(黃花屬(Sidaspp·))、野生芥菜(白齐 (Sinapis arvensis))及牛蒡(蒼耳屬(Xanthium spp·))。 窄葉物種舉例如(但不限於)下列:野生燕麥(Avena fatua)、粟米草(地毯草屬(Axonopus spp·))、巴拉草(巴拉草 屬(Brachiaria spp·))、雀麥(Bromus tectorum)、狗牙根 (Cynodon dactylon)、油莎草(Cyperus esculentus)、紫莎草(C. rotundus)、馬唐(馬唐屬(Digitaria spp·))、裨子(Echinochloa crus-galli)、牛筋草(Eleusine indica)、菖浦(Elymus repens)、 白茅根(Imperata cylindrica)、年牲毒麥(Lolium multiflorum) 、多年生毒麥(Lolium perenne)、稻(Oryza sativa)、奥圖草 (Ottochloa nodosa)、大黍(Panicum maximum)、毛花雀稗 (Paspalum dilatatum)、雀裨(Paspalum notatum)、草蘆(Phalaris spp.)、茅草(蘆葦屬(Phragmites spp·))、狐尾草(狗尾草屬 (Setaria spp·))、阿拉伯高梁(Sorghum halepense)、小麥 (Triticum aestivum)、香浦(Typha spp.)及玉米(Zea mays)。 其他植物物種舉例如(但不限於)下列:馬尾草(荊屬 (Equisetum))、羊齒(蕨菜(Pteridium aquilinum))、黑苺(苺屬 87453 •10- 200412852 (Rubus spp·))及金雀花(uiex eur〇paeus)。 本文所用之’’鹽”包含可與例如胺、鹼金屬鹼及鹼土金屬 驗或四級銨鹼所形成之鹽,包含兩性離子。作為鹽形成劑 之適宜驗金屬及鹼土金屬氫氧化物包含鋰、鈉、鉀、鎂或 約之氫氧化物。適用於形成銨陽離子以及一級、二級及三 級C1-C18燒基胺、C1-C4羥基烷基胺及C2-C4烷氧基烷基胺 之適宜胺包含甲胺、乙胺、正丙胺、異丙胺、四種異構之 丁胺、正戊胺、異戊胺、己胺、庚胺、辛胺、壬胺、癸胺、 十五碳燒基胺、十六碳烷基胺、十七碳烷基胺、十八碳烷 基胺、甲基乙基胺、甲基異丙基胺、甲基己基胺、甲基壬 基胺、甲基十五碳烷基胺、甲基十八碳烷基胺、乙基丁基 胺、乙基庚基胺、乙基辛基胺、己基庚基胺、己基辛基胺、 二甲基胺、二乙基胺、二_正_丙基胺、二異丙基胺、二_正_ 丁基胺、二·正-戊基胺、二異戊基胺、二己基胺、二庚基胺、 一辛基胺、乙醇胺、正丙醇胺、異丙醇胺、N,N-二乙醇胺、 N_乙基-丙醇胺、丁基乙醇胺、烯丙基胺、正·丁·2_烯基 胺、正_戊-2-埽基胺、2,3-二甲基丁_2_烯基胺、二丁_2_烯基 胺、正-己-2-埽基胺、丙埽基二胺、三甲基胺、三乙基胺、 二-正-丙基胺、三異丙基胺、三_正_ 丁基胺、三異丁基胺、 一-第一丁基胺、三-正-戊基胺、甲氧基乙基胺及乙氧基乙 基胺;雜環胺如吡啶、喳啉、異喹啉、嗎啉、派啶、吡咯 啶、吲哚啉、喹寧環及吖庚因;一級芳基胺如苯胺、甲氧 基苯胺、乙氧基苯胺、鄰一間_及對-甲苯胺、伸苯二胺、 聯苯胺、蓁甲胺及鄰_、間_及對_氯苯胺。 87453 -11- 200412852 本發明之除草組合物包含a) N-膦甲基甘胺酸或均膦酸丙 胺酸甲基酯除草劑或其鹽或酸;b)苯醚除草劑或其鹽或 酯,c)二醇;d)胺源;及e)載劑;其中該組合物係調配為溶 液。 該N-膦甲基甘胺酸除草劑較好為下式⑴之嘉磷塞·· 〇Regeneration inhibition, proliferation and removal, as used herein, "contact" cells are exposed to the composition, agent 0% I, growth inhibitory effect, effect of destroying or eliminating plant genesis and activity. Those skilled in the art will understand that the potency of various groups used in the present invention 87453 200412852 is variable and therefore the '' herbicidally effective amount π is also variable. As used herein, '' plant '' means land plants and aquatic plants. Terrestrial plants contain germinating seeds, germinating seedlings and herbs including roots and above-ground parts as well as established herbs. Aquatic plants include algae, plant organisms that are free-floating and immersed species, whose roots are generally embedded in the soil. Non-exclusive examples of plants include the following (but not limited to): Abutilon, Amaranthus, Artemisia, Asclepias, Avena, Carpet Grass Axonopus, Borreria, Brachiaria, Brassica, Bromus, Chenopodium, Cirsium, Commelina, Convolvulus, Cynodon, Cyperus, Digitaria, Echinochloa, Eleusine, Elymus, Equisetum, Sophora seedlings ( Erodium, Helianthus, Imperata, Ipomoea, Kochia, Loium, Malva, Oryza, Ottochloa, Panicum , Paspalum, Phalaris, Phragmites, Polygonum, Portulaca, Pteridium, Pueraria, Rubus , Salsola (Salsola), Setaria, (Sida), Alba (Sinapis), Sorghum, Triticum, Typha, Ulex, Xanthium, and Zea. Examples of broad-leaved species include (but are not limited to) the following: villous leaves (Abutilon theophrasti), Amaranthus spp., Artemisia SPP, Asclepias spp., Buttonweed (Borreria spp.) , Oil 200412852 hemp seed, canola, Brassica spp., Canadian thistle (Cirsium arvense), bamboo leaf vegetable (Commelina spp ·), field convolvulus (Convolvulus arvensis ), Erodium spp ·, Sunflower (Helianthus spp.), Morning Glory (Ipomoea spp ·), Kochia scoparia, Mallow (Malva spp.) , Wild barley, water sparse, etc. (Polygonum spp ·), purslane (Portulaca spp ·), kudzu (Pueraria spp ·), Soviet Russian thistle (pig Sorbus (Salsolaspp.)), Yellow flower (Sidaspp.)), Wild mustard (Sinapis arvensis) and burdock (Xanthium spp.)). Examples of narrow-leaf species include, but are not limited to, the following: wild oats (Avena fatua), cornweed (Axonopus spp.), Paragrass (Brachiaria spp.), Brome ( Bromus tectorum), Cynodon dactylon, Cyperus esculentus, C. rotundus, Matang (Digitaria spp.), Echinochloa crus-galli, Eleusine indica, Elymus repens, Imperata cylindrica, Lolium multiflorum, Lolium perenne, Oryza sativa, Ottochloa nodosa), Panicum maximum, Paspalum dilatatum, Paspalum notatum, Phalaris spp., thatch (Phragmites spp.), foxtail (dogtail) (Setaria spp.)), Sorghum halepense, Triticum aestivum, Typha spp., And Zea mays. Other plant species include, for example, but are not limited to, the following: Horsetail (Equisetum), Fern (Pteridium aquilinum), Blackberry (Raspberry 87453 • 10- 200412852 (Rubus spp ·)), and Gorse (uiex europaeus). As used herein, "salts" include salts that can be formed with, for example, amines, alkali metal bases and alkaline earth metal or quaternary ammonium bases, and include zwitterions. Suitable metal test and alkaline earth metal hydroxides as salt forming agents include lithium , Sodium, potassium, magnesium or about hydroxides. Suitable for the formation of ammonium cations and primary, secondary and tertiary C1-C18 alkylamines, C1-C4 hydroxyalkylamines and C2-C4 alkoxyalkylamines Suitable amines include methylamine, ethylamine, n-propylamine, isopropylamine, four isomeric butylamines, n-pentylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecyl Alkylamine, hexadecylamine, heptadecanylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methylnonylamine, methylamine Pentadecanyl amine, methyl octadecyl amine, ethyl butyl amine, ethyl heptyl amine, ethyl octyl amine, hexyl heptyl amine, hexyl octyl amine, dimethyl amine, Diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-n-pentylamine, diisopentylamine, dihexylamine, diheptylamine, One Methylamine, ethanolamine, n-propanolamine, isopropanolamine, N, N-diethanolamine, N-ethyl-propanolamine, butylethanolamine, allylamine, n-but-2-enylamine, N-pent-2-fluorenylamine, 2,3-dimethylbut-2-enylamine, dibut-2-enylamine, n-hex-2-fluorenylamine, propanyldiamine, Trimethylamine, triethylamine, di-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, mono-first butylamine, tri-n- Amylamine, methoxyethylamine, and ethoxyethylamine; heterocyclic amines such as pyridine, perylene, isoquinoline, morpholine, pyridine, pyrrolidine, indolinoline, quinine ring, and azepine Because; primary arylamines such as aniline, methoxyaniline, ethoxyaniline, o-m-toluene and p-toluidine, phenylenediamine, benzidine, benzylamine and o-, m- and p-chlorine 87453 -11- 200412852 The herbicidal composition of the present invention comprises a) N-phosphonomethylglycine or homophosphonic acid alanine methyl ester herbicide or its salt or acid; b) phenyl ether herbicide or its salt Or an ester, c) a diol; d) an amine source; and e) a carrier; wherein the composition is formulated as a solution. The N-phosphonomethyl Alanine herbicides ⑴ preferably of the formula Ka · square plug P

IIII

Z —CH2—NH—CH。 P 其中冗為 COOH、COSH、COC卜 COBr、COF、COI或 COR3 ; I、R2及R3各獨立為OH或〇R4 ;及R4為式(II)之形成醚胺鹽 之陽離子: H4N-R5-〇.R6 (II) 其中R5及R6各獨立為^·^燒基、C2-C6婦或C2-C6炔;其中 該嘉磷塞為酸或鹽態。 一具體例中,Z、COOH且Ri&R2為OH。較好,該嘉磷塞 以異丙基胺鹽存在。其他具體例包含嘉磷塞之苯均三酸 鹽、三甲基磺酸鹽及鈉倍半鹽。再者,該酸嘉磷塞可與適 當酸受體組合,包含(但不限於)銨、乙酸銨、乙酸鈉、乙酸 鉀、碳酸銨、碳酸鈉等。 該均膦酸丙胺酸甲基酯除草劑較好為下式之固殺草 (glufosinate): ΝΗ2 οZ —CH2 —NH—CH. Where P is COOH, COSH, COC, COBr, COF, COI, or COR3; I, R2, and R3 are each independently OH or OR4; and R4 is a cation that forms an etheramine salt of formula (II): H4N-R5- 〇 R6 (II) wherein R5 and R6 are each independently ^ ^ alkyl, C2-C6 or C2-C6 alkyne; wherein the carbohydrate plug is in acid or salt state. In a specific example, Z, COOH and Ri & R2 are OH. Preferably, the carbohydrate plug is present as an isopropylamine salt. Other specific examples include trimesate, trimesylate, and sodium sesquidium. Furthermore, the acid carbohydrate plug may be combined with a suitable acid acceptor, including (but not limited to) ammonium, ammonium acetate, sodium acetate, potassium acetate, ammonium carbonate, sodium carbonate, and the like. The methyl phosphonic acid alanine herbicide is preferably a glufosinate of the formula: ΝΗ2 ο

I II z-chch2ch2p-ch3 α») R1 87453 -12-I II z-chch2ch2p-ch3 α ») R1 87453 -12-

I 200412852 其中 Z為 COOH、COSH、C〇a、COBr、COF、COI或 COR3 ; Ri、R2及R3各獨立為OH或OR4 ;及R4為式(π)之形成醚胺鹽 之陽離子: H4N-R5-O-R6 (IV) 其中R5及R6各獨立為(^-(:6烷基、C2-C6烯或C2-C6炔;其中 該固殺草為酸或鹽態。 苯醚除草劑不僅包含除草劑,亦包含其代謝物、鹽及酯。 通常,苯醚除草劑為本技藝悉知具有兩個一般經取代之苯 基藉由氧原子键結。該等除草劑典型上在苯環之位置2及 4,位置3,位置3及5 ;或位置2、4及6上經取代。特定舉例 之苯醚除草劑包含亞喜芬(acifluorfen)、亞喜芬-鈉、亞喜芬 -钟、氟績胺草醚(fomesafen)、5-[2-氯·4·(三氟曱基)-苯氧 基]-2-硝基苯乙酮肪-鄰-(乙酸)、及5-[2-氯-4-(三氟甲基)·苯 氧基]-2-硝基·α -甲氧基苯乙酮辟-鄰-(乙酸)。一具體例中, 該苯醚除草劑為亞喜芬或氟磺胺草醚。 本組合物之除草劑成分之酸/鹽特性可因該成分在溶液 中而改變。例如,混合異丙基胺嘉磷塞及亞喜芬鋼後,與 嘉磷塞聯合之異丙基胺可變成與亞喜芬聯合,因而產生異 丙基胺亞喜芬。所得組合物在本發明範圍内,因其為除草 劑成分之衍生物。 可用於本發明之二醇可為任何可相容之二醇、多元醇或 聚二醇。舉例之適宜二醇包含乙二醇、丙二醇、〗,3-丙二醇、 1,2-丁二醇、二乙二醇、二丙二醇、己二醇、甘油、低分子 量聚乙二醇極低分子量聚丙二醇。再者,展現水溶解度之 87453 -13- 200412852 二醇醚如乙二醇單甲醚、乙二醇二甲醚、乙二醇單乙醚、 乙二醇二乙醚、乙二醇單丁醚、單異丁基醚、二丙二醇單 甲醚均在本發明範圍内。 可使用表面活性劑如環氧乙烷與環氧丙烷之嵌段共聚 物0 本發明組合物包含胺源,其可為任何可相容之胺。適宜 之胺可包含烷基胺如單甲基胺、二甲基胺、三甲基胺、二 乙基胺、三乙基胺、丙基胺、二_正_丙醇胺、正丁基胺、正 -二丁基胺、正-三丁基胺、異丁基胺、二異丁基胺、第二丁 基胺、單-正-丁基胺、正_戊基胺、二戊基胺、三戊基胺、 己基胺、2-乙基丁基胺、正-庚基胺、2_乙基己基胺、環己 基胺。又烷醇胺如單乙醇胺、二乙醇胺、三乙醇胺、單異 丙醇胺、二異丙醇胺、三異丙醇胺、二甘醇胺、2_胺基_2_ 甲基-1-丙醇、2_胺基_2_甲基_ΐ53·丙醇、2_胺基_2_乙基—n 丙醇、一(羥基甲基)胺基甲烷。適宜之醯胺可包含曱醯胺。 N-膦甲基甘胺酸除草劑對苯醚除草劑之比例可廣泛變 化。例如,N-膦甲基甘胺酸除草劑對苯醚除草劑之比例可 自1:1莫耳比例至約10:05莫耳比例之間。—具體例中,沁 膦甲基甘胺酸除草劑對苯_除草劑之比例自約2: ^莫耳比 例至約4:0.5莫耳比例。 本組合物較好包括載劑。可利用任何適宜載劑包含水、 水溶液、N_甲基吡咯啶酮、甲醇、乙醇、異丙醇、丙酮、 丁基I纖素、2·乙基小己醇、環己酉同、煙類及其他水不溶 混之醚類、酯類及酮類,及其組合。 87453 -14- 200412852 通常,習&嘉磷塞鹽組合物含有一或多表面活性劑以 增加活性成分 < 生物效果。表面活性劑在形成本發明溶液 態之除草組合物中未必需要。然而,水性組合物中表面活 性劑之存在具有許多有利效益··⑴表面活性射改變喷霧 滴液之尺寸分布以增加小尺寸滴液之數量,其似乎較不易 自植物表相彈;(2)表面活性射增進噴霧滴液之黏著性 以減少組合物自植物表面掉n(3)表面活性劑可增進植 物表面之滲透性。 有利地,本發明之該載劑及/或形成鹽之陽離子可選擇成 增加活性成分之生物活性;因而可消除表面活性劑之需 要然而,若需要,一或多種表面活性劑可添加至組合物 中。適罝表面活性成分包含表面活性劑、乳化劑及濕潤劑。 可利用廣泛之表面活性劑且可易於由熟知本技藝者自,, 工業表面活性劑手冊,,第2版,G〇wer 〇997)加以選擇,其併 本文供參考。可用之表面活性劑之種類或化學類別並無 限制。特定狀態下均可使用非離子性、陽離子性及兩性類 型、或該等類型之一種以上之組合。 非離子表面活性劑中,例舉類別包含聚氧乙烯烷基、炔、 炔基或烷芳基醚如聚氧乙缔一級或二級醇、烷基酚或乙炔 醇邊,I氧乙婦燒基或決基酯如乙氧化脂肪酸;山梨糖 醇酐k基酯,無論乙氧基化與否;甘油基烷基酯;蔗糖酯; 及烷基聚糖咁。例舉之陰離子表面活性劑類別包含醇類、 烷基酚、聚氧乙稀醇及聚氧乙埽烷基酚之脂肪酸、硫酸鹽、 磺酸鹽及磷酸鹽單-及二酯、及聚氧乙烯醇及聚氧乙烯烷基 87453 -15 - 200412852 紛之叛酸鹽。該等可以其酸態使用但更典型上係以鹽使用 例如#9、_或铵鹽。 陽離子表面活性劑類別包含聚氧乙缔三級烷基胺或烯基 胺如乙氧化脂肪酸胺、四級銨表面活性劑及聚氧乙烯烷基 酸胺。此陽離子表面活性劑之代表性特定實例包含聚氧乙 婦(5)可可胺、聚氧乙烯(15)牛脂胺、氯化二硬脂基二甲基 銨、氯化N_十二碳烷基吡啶及氯化聚氧丙婦(8)乙氧基三甲 基銨。各種結構之許多陽離子銨表面活性劑為本技藝已知 可用於與嘉磷塞組合使用且可用於本文所欲之組合物中。 本發明組合物亦可含其他活性成分例如多種义膦甲基甘 胺酸除草劑及/或苯醚除草劑;肥料如硝酸銨、鹼水及超磷 酸鹽;植物毒性劑及植物生長調節劑;及殺蟲劑。該等额 外成分可依序使用或與上述組合物組合使用。例如,該植 物可在以其他活性成分處理之前、後,以本發明組合物噴 霧。 其他視情況之成分可與本發明組合物混合以加速活性成 分足塗佈及/或效力。據此,可添加之視情況成分包含消泡 劑(包含矽氧為主之消泡劑);增稠劑(如發煙氧化矽”抗微 生物muc劑,·緩衝劑;染料,·香科,·安定劑;及防 凍劑。防凍劑實例包含(但不限於)二醇如丙二醇及乙二醇、 N-甲基吡咯啶酮、環己酮及醇類如乙醇及甲醇。 本發明溶液可為液體濃縮物及稀釋溶液。通常,濃縮溶 液為商業&供且可由末端使用者以水混合,因而產生透明 溶液。該濃縮溶液亦可為不透明使得活性成分不會自溶液 87453 -16 - 200412852 ά殿出且並非乳液。 一具體例中,該組合物包括約2 wt%至约2〇 wt%之—或多 種1^-膦曱基甘胺酸除草劑;自約1 wt%至約30 wt%之—或多 種本醚除草劑,自約10 wt%至約50 wt%之一或多種甘★ · 自約10 wt%至約50 wt%之一或多種胺類;而其餘為載劑, 如N_甲基吡咯啶酮及/或水。另一具體例中,溶液中該队膦 甲基甘胺酸除草劑濃度自約1.0磅/加崙至約1.5磅/加崙。 當依據本發明製備時,不利植物之生長可藉使植物與除 草有效量之本發明組合物接觸而抑制。此除草組合物施用 至陸地植物可藉習知方法進行如機械噴霧器及手動噴霧器 及噴塵器。該組合物亦可自飛機上噴霧施用因為其在低劑 量下亦有效之故。除草組合物對水生植物之施用一般藉由 將組合物噴霧在水生植物期望控制該水生植物之處。 對標的植物施用除草有效量之本發明組合物將隨植物所 需反應以及如植物物種及其發展階段、下雨量及所用特定 希磷塞鹽等因素而異。在控制陸地植物之葉面處理中,該 活性成分較好之施加量自每英敌約〇 至約或以上镑數 或更好每英敌0.2至約5或以上碡數。就控制萌芽之水生植物 之施用而言,該活性成分典型以每英畝〇 2至約5或以上镑數 施加至植物上。 本發明組合物亦可於許多農作物中使用作為收割助劑。 因此’例如該農作物可以本發明組合物噴霧以降低不利物 質之結塊且使農作物收割更容易。此農作物為例如花生、 大豆及根類農作物如馬铃薯、甜菜、紅甜菜等。 87453 -17- 200412852 本發明組合物可用於栽種區域之種子播種而不犁田或以 機械準備育苗床。該農作物種子可為條播或在施加本發明 組合物之前或之後播種以殺死不利生長之植物,但該組合 物係在農作物萌芽前施加。因噴霧之植物枯萎及死亡,其 作用為蠖根及其中種子可發芽之保濕層或維持該土壤溫暖 及保濕。 本發明組合物提供廣泛之雜草控制草譜且亦極可用作為 一般除草劑以及用以控制果園、樹原及各種農作物中之不 利植物。例如已發現對不利植物直接噴霧本發明組合物同 時基本上避免此噴霧與樹木葉子接觸,則此不利植物可經 控制同時對樹木無明顯損害。此直接噴霧中,該噴霧可落 在果树或八他树木之木材部分而無任何明顯影響。因此, 直接噴霧之控制方法可用於經濟型農作物如橡膠、咖徘、 香蔑、茶等且可用於果園如檸檬樹、蘋果樹、梨子、桃子、 l果橄視m於葡萄園及樹苺農作物及苗圃農作物以控 制不利植物及料如棉、大豆、甘麟農作物。該直接喷 霧可或不需以保護裝置使用以避免噴霧劑與此農作物植物 之葉面接觸。 Λ月、.且口物可易於使用有機合成化學領域悉知之技術 口成4組合物可藉混合a)至少一種^^,甲基甘胺酸或均 膦酸丙胺酸甲_除草劑或其鹽或酸;b)至少—種苯酸除 草劑或其鹽或自旨;啦少—種二醇;d)至少—種胺源;及e) 至少一種載劑而製備,形成溶液。 實驗 87453 -18- 200412852 下列實驗用以提供熟知本技藝者如何製造及評估所申請 之該化合物、組合物、物件、裝置及/或方法之更完全揭示 及描述,且僅欲用以說明本發明而非用於限制本發明範圍 之目的。已作各種努力以確使數值之精確度(如量、溫度等) 但有些誤差及偏差需加以考慮。除非另有指示,否則百分 比為既定成分與組合物總重之重量百分比,溫度為°C或為 周圍溫度,且壓力係在或接近大氣壓。 實例1 產生嘉磷塞之異丙基胺鹽、亞喜芬鈉及水之混合物以測 定混合物之溶解度及安定性。結果示於表1。 表1:嘉嶙塞之異丙基胺鹽與亞喜芬鈉混合物 活性成分(莫耳比) 總活性 物理觀察/ 成分濃度 安定性 (克/升) 嘉磷塞之異丙基胺鹽 540 透明溶液 (IPA 嘉磷塞)(100%) 亞喜芬之鈉鹽(亞喜芬鈉)(100%) 530 透明溶液 IPA嘉磷塞+亞喜芬鈉(3:1) 432 白色沉澱 IPA嘉磷塞+亞喜芬鈉(3··1) 240 白色沉澱 IPA嘉磷塞+亞喜芬鈉(3:1) 120 白色沉澱 IPA嘉磷塞+亞喜芬鈉(3:1) 50 白色沉澱 IPA嘉磷塞+亞喜芬鈉(3:1) 43 透明溶液 實例2 產生嘉磷塞之異丙基胺鹽、亞喜芬鈉及水之混合物以測 定混合物之相互作用。該混合物以0.45微米膜過濾且測量過 87453 -19- 200412852 滤溶液中知亞喜芬鈉之量。結果示於表2。 表2:嘉磷塞之異丙基胺鹽與亞喜芬鈉混合物 變數 混合物1 混合物2 混合物3 嘉磷塞:亞喜芬莫耳比 2:1 1:1 1:2 亞喜芬鋼(Wt°/o) 5.00 5.00 5.00 嘉磷塞鈉(wt%) 4.67 2.33 1.16 過滅溶液中之亞喜芬鋼(wt%) 5.16 5.14 5.07 物理溶液觀察 透明 霧濁 霧濁 溶液 物理過滤液觀察 透明 霧濁- 霧濁- 溶液 膠體 膠體 實例3 產生嘉磷塞之異丙基胺鹽、亞喜芬鈉、輔溶劑及水之混 合物以觀察溶液。成份量示於表3 a且特定辅溶劑及所得溶 液示於表3b。 表3a :實例3之混合物成分 成分 含量 (wt%) 亞喜芬鈉TGA1 (44% A1) 16.3 IPA 嘉磷塞(45.72% A1) 43.3 辅溶劑(見於表3b) 4.5 載劑(水) 45.1 合計 100.0 87453 -20- 200412852 表3b :輔溶劑及溶液評估 輔溶劑 化學分類 物理觀察 乙二醇 多元醇 最初溶液’ 24小時内結晶 丙二醇 最初溶液,24小時内結晶 己二醇 最初溶液,24小時内相分離 Pluracol E-400 聚乙二醇 容器底部有2-相凝膠 Pluracol E-300 容器底部有2-相凝膠 Iconol TDA-3 燒基驗乙氧化物 容器底部有2-相凝膠 Tetronic 90R4 嵌段共聚物 表面活性劑 容器底部有2-相凝膠 Tetronic 150R1 容器底部有2-相凝膠 Tetronic 701 容器底部有2_相凝膠 Tetronic 704 容器底部有2-相凝膠 Tetronic 901 容器底部有2-相凝膠 Pluronic L62 攸段共聚物 表面活性劑 容器底部有2-相凝膠 Pluronic L92 容器底部有2-相凝膠 APG 2067 燒基糖咁 容器底部有2-相凝膠 Tween 20 山梨糖醇酐 表面活性劑 容器底部有2-相凝膠 Tween 80 容器底部有2-相凝膠 實例4 產生嘉磷塞之異丙基胺鹽、亞喜芬鈉、乙二醇、胺源及 水之混合物以觀察溶液。成份量示於表4a且特定胺源及所 得溶液示於表4b。 87453 -21- 200412852 表4a:實例4之混合物成分 成分 含量(wt%) 亞喜芬鈉TGA1 (44% A1) 11.21 IPA嘉磷塞(76% A1) 17.93 胺源(見於表4b) 20.0 乙二醇 40.0 載劑(水) 10.86 合計 100.0 表4b :胺源及溶液評估 胺源 物理觀察 異丙基胺 結晶 單異丙醇胺 透明溶液 二異丙醇胺 透明溶液 三異丙醇胺 透明溶液 二甘醇胺 兩相分離 乙基乙醇胺 透明溶液 乙基二乙醇胺 透明溶液 二乙醇胺 透明溶液 三乙醇胺 透明溶液 二乙二醇胺 兩相分離 實例5 產生嘉磷塞、亞喜芬、辅溶劑系統及水之混合物以觀察 亞喜芬溶解度。所得溶解度示於表5。 87453 -22- 200412852 喜芬溶解度 輔溶劑 嘉磷塞 亞喜芬鈉/亞喜芬胺在20°C之溶解度 系統 濃度 (混合物%〜/\\〇 (酸為主) Afi醇/水比例 0.0 0.5 1.0 2.0 異丙醇胺 0% >44.0%* >29.2%* >23.0%* >17.8%* 與乙二醇 6% 0.0% 0.0% 1.4% 9.7% 12% 0.0% 0.0% 0.0% 9.7% 18% 0.0% 0.0% 0.0% 0.0% 二異丙醇 0% >44.0%* >29.2%* >23.4%* >17.8%* 胺與乙二 6% 0.0% 0.1% 9.2% 9.8% 醇 12% 0.0% 0.0% 0.24% 9.8% 18% 0.0% 0.0% 0.0% 0.9% 最大值受TGA1濃度所限制。 實例6 產生嘉磷塞、亞喜芬、輔溶劑系統及水之混合物以觀察 儲存對;表液之影響。產生溶液及儲存一個月,結果示於表 6a及6b。 惠6a ··各種儲存條件之物理試驗結果 組成 亞喜芬:嘉鱗塞比例 1:2 1:3 1:4 1:6 1:8 亞喜芬鈉(40.5%) 13.46 8.97 6.73 4.49 3.36 二異丙醇胺(99%) 10.67 10.67 10.67 10.67 10.67 嘉磷塞酸(0.76%) 14.34 14.34 14.34 14.34 14.34 水 26.53 31.02 33.26 35.50 36.62 乙二醇 35.00 35.00 35.00 35.00 35.00 合計 100.00 100.00 100.00 100.00 100.00 87453 -23 - 200412852 物理儲存條件 1個月後物理觀察 冷凍/解凍5次循環 溶液 溶液 溶液 溶液 溶液 5°C 溶液 溶液 溶液 溶液 溶液 25〇C 溶液 溶液 溶液 溶液 溶液 50°C 溶液 溶液 溶液 溶液 溶液 溶液=含亞喜芬之溶液樣品維持透明 表6b:各種儲存條件之物理試驗結果 組成 亞喜芬:嘉磷塞比例 1:2 1:3 1:4 亞喜芬鈉(40.5%) 13.46 8.97 6.73 二異丙醇胺(99%) 10.67 10.67 10.67 嘉磷塞酸(0.76%) 14.34 14.34 14.34 水 26.53 31.02 33.26 乙二醇 35.00 35.00 35.00 合計 100.00 100.00 100.00 物理儲存條件 1個月後物理觀察 冷凍/解凍5次循環 溶液 溶液 溶液 5°C 溶液 溶液 溶液 25〇C 溶液 溶液 溶液 50°C 溶液 溶液 溶液 實例7 產生嘉磷塞、氟磺胺草醚、亞喜芬及水之混合物以測定 混合物之相互作用。結果示於表7。 87453 -24- 200412852 塞、氟磺胺草醚及亞喜芬混合物 成分 氟磺胺草醚 混合物(wt%) 亞喜芬 混合物(wt%) 嘉磷塞 16.5 16.5 亞喜芬鈉 0.0 4.1 氟續胺草_ 4.1 0.0 水 79.4 79.4 總計 100.0 100.0 物理觀察 透明溶液 透明溶液 實例8 產生嘉磷塞-三甲基硫鹽、亞喜芬鈉、氟磺胺草醚、胺、 一醇及水之混合物以測定混合物之相互作用。結果示於表 成分 氟磺胺草醚調配物 亞喜芬調 (wt%) (wt%) 嘉磷塞-三甲基硫鹽 16.5 16.5 16.5 亞喜芬鈉 --~------ 0.0 4·1_ 氟績胺草酸 --—-- 4.1 二異丙醇胺 -------- 0·0 j^O 乙二醇 0.0 40.0 0.0 水 79.4 29.4 —. 79.4 合計 100.0 100.0 100.0 物理觀察 結晶 透明溶液 結晶 16.5 4.1 0.0 10.0 40.0 29.4 100.0 透明溶液 該 •' 少 11¾ 等公報之整個揭示因此並於本文供參考 87453 -25- 200412852 對熟知本技藝者將了解在不脫離苯發明之範圍及精神下 可作各種改良及變化。本發 而言將可由本文揭示之說明 及實例僅視為舉例,兒本發 申請專利範園加以界定。 明其他具體例對熟知本技藝者 及操作變得顯而易見。說明書 明之確實範園及精神可由下列I 200412852 where Z is COOH, COSH, Coa, COBr, COF, COI or COR3; Ri, R2 and R3 are each independently OH or OR4; and R4 is a cation forming an etheramine salt of formula (π): H4N- R5-O-R6 (IV) wherein R5 and R6 are each independently (^-(: 6 alkyl, C2-C6 ene or C2-C6 alkyne); wherein the solid herbicide is in acid or salt state. The phenyl ether herbicide not only Contains herbicides, as well as their metabolites, salts, and esters. Generally, phenyl ether herbicides are known in the art to have two generally substituted phenyl groups bonded via an oxygen atom. These herbicides are typically in the benzene ring Positions 2 and 4, positions 3, 3 and 5; or positions 2, 4, and 6. Substituted phenylene ether herbicides include acifluorfen, axifen-sodium, and axifen- Bell, fomesafen, 5- [2-chloro · 4 · (trifluorofluorenyl) -phenoxy] -2-nitroacetophenone-o- (acetic acid), and 5- [2-Chloro-4- (trifluoromethyl) · phenoxy] -2-nitro · α-methoxyacetophenone-o- (acetic acid). In a specific example, the phenyl ether herbicide It is axifen or sulfafen. The acid / salt characteristics of the herbicide component of the composition can be attributed to this. It can be changed in solution. For example, after mixing isopropylamine carfosin and axifen steel, the isopropylamine combined with carbosulfan can be combined with axifen, thus producing isopropylamine Fen. The resulting composition is within the scope of the present invention because it is a derivative of a herbicide component. The diols useful in the present invention can be any compatible diol, polyol, or polyglycol. Suitable exemplified diols Contains ethylene glycol, propylene glycol, 3-propanediol, 1,2-butanediol, diethylene glycol, dipropylene glycol, hexanediol, glycerin, low molecular weight polyethylene glycol and very low molecular weight polypropylene glycol. Furthermore, 87453 -13- 200412852 Glycol ethers exhibiting water solubility such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monobutyl ether, monoisobutyl Both ethers and dipropylene glycol monomethyl ether are within the scope of the present invention. Surfactants such as block copolymers of ethylene oxide and propylene oxide can be used. The composition of the present invention contains an amine source, which can be any compatible Amines. Suitable amines may include alkylamines such as monomethylamine, dimethylamine, trimethylamine , Diethylamine, triethylamine, propylamine, di-n-propanolamine, n-butylamine, n-dibutylamine, n-tributylamine, isobutylamine, diisobutylamine Methylamine, second butylamine, mono-n-butylamine, n-pentylamine, dipentylamine, tripentylamine, hexylamine, 2-ethylbutylamine, n-heptylamine, 2-Ethylhexylamine, cyclohexylamine. Alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, diethylene glycolamine, 2_ Amine_2_methyl-1-propanol, 2_amino_2_methyl_ΐ53 · propanol, 2_amino_2_ethyl-n propanol, mono (hydroxymethyl) aminomethane . Suitable amidines may include amidines. The ratio of N-phosphine methylglycine herbicide to phenylene ether herbicide can vary widely. For example, the ratio of N-phosphine methylglycine herbicide to phenylene ether herbicide can range from a 1: 1 molar ratio to about 10:05 molar. —In a specific example, the ratio of the phosphonomethylglycine herbicide to the benzene-herbicide is from about 2: mol ratio to about 4: 0.5 mol ratio. The composition preferably includes a carrier. Any suitable carrier can be used including water, aqueous solution, N-methylpyrrolidone, methanol, ethanol, isopropanol, acetone, butyl I cellulose, 2-ethylhexanol, cyclohexanone, tobacco And other water-immiscible ethers, esters and ketones, and combinations thereof. 87453 -14- 200412852 In general, Xi & Carfosin salt compositions contain one or more surfactants to increase the active ingredient < biological effect. Surfactants are not necessarily required to form the herbicidal composition in the solution state of the present invention. However, the presence of surfactants in aqueous compositions has many beneficial benefits. ⑴Surface active sprays change the size distribution of spray drops to increase the number of small-sized drops, which seems less likely to bounce from the surface of plants; (2 ) Surface active shots can improve the adhesion of spray drops to reduce the composition of n (3) surfactant from the plant surface, which can improve the permeability of the plant surface. Advantageously, the carrier and / or salt-forming cation of the present invention may be selected to increase the biological activity of the active ingredient; thus eliminating the need for a surfactant. However, if desired, one or more surfactants may be added to the composition in. Suitable surfactants include surfactants, emulsifiers, and wetting agents. A wide range of surfactants are available and can be easily selected by those skilled in the art, Handbook of Industrial Surfactants, 2nd Edition, Gower 997), which is incorporated herein by reference. There are no restrictions on the types or chemical classes of surfactants that can be used. Non-ionic, cationic and amphoteric types, or a combination of more than one of these types can be used in a particular state. Among the nonionic surfactants, examples include polyoxyethylene alkyl, alkyne, alkynyl, or alkaryl ethers such as polyoxyethylene primary or secondary alcohols, alkylphenols or acetylene alcohols, and oxyethyl ethyl alcohol. Or decyl esters such as ethoxylated fatty acids; sorbitan k-based esters, whether ethoxylated or not; glyceryl alkyl esters; sucrose esters; and alkyl polysaccharides. Exemplary anionic surfactant categories include fatty acids, sulfates, sulfonates, and phosphate mono- and diesters of alcohols, alkylphenols, polyoxyethylene alcohols, and polyoxyethylene alkylphenols, and polyoxylates Vinyl alcohol and polyoxyethylene alkyl 87453 -15-200412852 A lot of acid salts. These can be used in their acid state but are more typically used as salts such as # 9, _ or ammonium salts. Cationic surfactant classes include polyoxyethylene tertiary alkylamines or alkenylamines such as ethoxylated fatty acid amines, quaternary ammonium surfactants, and polyoxyethylene alkylamines. Representative specific examples of this cationic surfactant include polyoxyethylamine (5) cocoamine, polyoxyethylene (15) tallowamine, distearyldimethylammonium chloride, and N-dodecyl chloride Pyridine and polyoxypropyl chloride (8) ethoxytrimethylammonium. Many cationic ammonium surfactants of various structures are known in the art and can be used in combination with Carbosam and in the compositions desired herein. The composition of the present invention may also contain other active ingredients such as a variety of phosphinomethylglycine herbicides and / or phenyl ether herbicides; fertilizers such as ammonium nitrate, alkaline water and superphosphates; phytotoxic agents and plant growth regulators; And pesticides. These additional ingredients can be used sequentially or in combination with the above composition. For example, the plant may be sprayed with the composition of the present invention before and after treatment with other active ingredients. Other optional ingredients can be mixed with the composition of the present invention to accelerate the full application and / or effectiveness of the active ingredients. According to this, the optional ingredients that can be added include defoaming agents (including silica-based antifoaming agents); thickeners (such as fuming silica "antimicrobial muc agents, · buffering agents; dyes, · Xiangke, Stabilizers; and antifreeze agents. Examples of antifreeze agents include, but are not limited to, diols such as propylene glycol and ethylene glycol, N-methylpyrrolidone, cyclohexanone, and alcohols such as ethanol and methanol. The solution of the present invention may be Liquid concentrates and dilute solutions. Generally, concentrated solutions are commercially available and can be mixed with water by the end user to produce a transparent solution. The concentrated solution can also be opaque so that the active ingredients do not self-dissolve from the solution 87453 -16-200412852. It is not an emulsion. In a specific example, the composition includes about 2 wt% to about 20 wt% of one or more 1 ^ -phosphonophosphoglycine herbicides; from about 1 wt% to about 30 wt % —One or more of the present ether herbicides, from about 10 wt% to about 50 wt% of one or more sweeteners ★ · from about 10 wt% to about 50 wt% of one or more amines; and the rest are carriers, Such as N_methylpyrrolidone and / or water. In another specific example, the phosphine methylglycine in the solution is removed The concentration of the agent is from about 1.0 lb / gal to about 1.5 lb / gal. When prepared according to the present invention, the growth of unfavorable plants can be inhibited by contacting the plant with a herbicidally effective amount of the composition of the present invention. The herbicidal composition is applied to land Plants can be applied by conventional methods such as mechanical sprayers and manual sprayers and dusters. The composition can also be sprayed from an airplane because it is also effective at low doses. The application of herbicidal compositions to aquatic plants is generally by Spray the composition on the aquatic plant where it is desired to control the aquatic plant. Applying a herbicidally effective amount of the composition of the present invention to the target plant will respond to the plant's needs and, for example, the plant species and its stage of development, the amount of rain and the specific xiphosate used Different factors such as salt. In controlling foliar treatment of terrestrial plants, the active ingredient is preferably applied in an amount of about 0 to about or more pounds per British enemy or better 0.2 to about 5 or more per British enemy For the purpose of controlling the application of budding aquatic plants, the active ingredient is typically applied to the plant at a level of from 0.2 to about 5 or more pounds per acre. The composition of the invention may also be Many crops are used as harvesting aids. So 'for example, the crop can be sprayed with the composition of the present invention to reduce the agglomeration of unfavorable substances and make the harvesting of the crop easier. This crop is, for example, peanuts, soybeans and root crops such as potatoes, Beets, red beets, etc. 87453 -17- 200412852 The composition of the present invention can be used for sowing seeds in the planting area without ploughing or mechanically preparing seedbeds. The crop seeds can be seeded or sown before or after applying the composition of the present invention To kill unfavorable plants, but the composition is applied before the crops sprout. Because the sprayed plants wither and die, its role is to provide a moisturizing layer for the roots and seeds in them to germinate or to maintain the soil's warmth and moisture. The composition provides a wide spectrum of weed control grasses and is also extremely useful as a general herbicide and to control unfavorable plants in orchards, tree plains and various crops. For example, it has been found that spraying the composition of the present invention directly on unfavorable plants while substantially avoiding the spray from contacting the leaves of the trees, the unfavorable plants can be controlled without significant damage to the trees. In this direct spray, the spray can fall on the wood part of the fruit tree or a bat tree without any noticeable effect. Therefore, the direct spray control method can be used for economic crops such as rubber, coffee, fragrant, tea, etc. and can be used in orchards such as lemon trees, apple trees, pears, peaches, olives and vineyards and raspberry crops. And nursery crops to control unfavorable plants and materials such as cotton, soybean, and Ganlin crops. This direct spray may or may not be used with a protective device to prevent the spray from coming into contact with the foliage of this crop plant. The composition can be easily used. Techniques known in the field of organic synthetic chemistry can be used. The composition can be mixed by a) at least one ^, methylglycine or homophosphonic acid alanine methyl herbicide or its salt. Or an acid; b) at least one benzoic acid herbicide or a salt or purpose thereof; a small amount of a diol; d) at least one amine source; and e) at least one carrier to prepare a solution. Experiments 87453 -18- 200412852 The following experiments are provided to provide a more complete disclosure and description of the compounds, compositions, articles, devices and / or methods applied to those skilled in the art, and are intended only to illustrate the present invention It is not intended to limit the scope of the invention. Various efforts have been made to ensure the accuracy of the values (such as quantity, temperature, etc.), but some errors and deviations need to be considered. Unless otherwise indicated, percentages are percentages by weight of a given ingredient and the total weight of the composition, temperature is ° C or ambient temperature, and pressure is at or near atmospheric. Example 1 A mixture of isopropylamine salt, axifen sodium, and water was produced for carbosulfam to determine the solubility and stability of the mixture. The results are shown in Table 1. Table 1: Active ingredients of a mixture of isopropylamine salt of gacitrazine and sodium acetifene (molar ratio) Physical observation of total activity / Stability of component concentration (g / l) Carboxamide isopropylamine salt 540 transparent Solution (IPA Carbosac) (100%) Sodium Axifen (Axifen Sodium) (100%) 530 Clear solution IPA Carbosam + Sodium Axifen (3: 1) 432 White precipitated IPA Carbos Plug + Axifene Sodium (3 ·· 1) 240 White precipitated IPA Carfosin + Axifene Sodium (3: 1) 120 White precipitated IPA Carfosin + Axifene Sodium (3: 1) 50 White precipitated IPA Carfosin + sodium axifene (3: 1) 43 Clear solution Example 2 A mixture of isopropylamine salt, sodium axifene and water of carfosin was generated to determine the interaction of the mixture. The mixture was filtered through a 0.45 micron membrane and the amount of sodium azexifene in the filtered solution was measured from 87453-19 to 200412852. The results are shown in Table 2. Table 2: Mixture of isopropylamine salt of afosin and axifene sodium Mixture 1 Mixture 2 Mixture 3 Carofion: Axifen Molar ratio 2: 1 1: 1 1: 2 Axifen steel (Wt ° / o) 5.00 5.00 5.00 Carfosin sodium (wt%) 4.67 2.33 1.16 Axifen steel in weight loss solution (wt%) 5.16 5.14 5.07 Observation of transparent haze in physical solution Transparent haze in physical filtration solution -Haze-Solution Colloidal Colloid Example 3 A mixture of isopropylamine salt of Carbosam, sodium acetifene, co-solvent and water was produced to observe the solution. The component amounts are shown in Table 3a and the specific co-solvents and the resulting solutions are shown in Table 3b. Table 3a: Mixture of the ingredients in Example 3 (wt%) Sodium Axifen TGA1 (44% A1) 16.3 IPA Carbofuran (45.72% A1) 43.3 Co-solvent (see Table 3b) 4.5 Carrier (water) 45.1 Total 100.0 87453 -20- 200412852 Table 3b: Co-solvent and solution evaluation Co-solvent chemical classification Physical observation Ethylene glycol polyol initial solution 'Crystallized propylene glycol initial solution within 24 hours, Crystallized hexanediol initial solution within 24 hours, Phase within 24 hours Separation of Pluracol E-400 Polyethylene glycol with 2-phase gel at the bottom of the container Pluracol E-300 2-phase gel with the bottom of the container Iconol TDA-3 2-based gel with the bottom of the ethoxylate container Tetronic 90R4 embedded Segment copolymer surfactants 2-phase gel Tetronic 150R1 at the bottom of the container 2-phase gel Tetronic 701 at the bottom of the container 2-phase gel Tetronic 704 at the bottom of the container Tetronic 704 2-phase gel at the bottom of the container 2 -Phase gel Pluronic L62 2-stage gel surfactant at the bottom of the container 2-phase gel Pluronic L92 at the bottom of the container 2-phase gel APG 2067 2-phase gel at the bottom of the glycosaminoglycan container Tween 20 The sorbitan surfactant has a 2-phase gel at the bottom of the container. Tween 80 A 2-phase gel at the bottom of the container. Example 4 Isopropylamine salt that produces carbosulfone, sodium acetifene, ethylene glycol, amine source, and A mixture of water to observe the solution. The component amounts are shown in Table 4a and the specific amine source and the resulting solution are shown in Table 4b. 87453 -21- 200412852 Table 4a: The composition of the mixture in Example 4 (wt%) Sodium Axifen TGA1 (44% A1) 11.21 IPA Carbosam (76% A1) 17.93 Amine source (see Table 4b) 20.0 Ethylene Alcohol 40.0 Carrier (water) 10.86 Total 100.0 Table 4b: Amine source and solution evaluation Amine source Physical observation Isopropylamine crystal Monoisopropanolamine transparent solution Diisopropanolamine transparent solution Triisopropanolamine transparent solution Diethylene glycol Ethanolamine two-phase separation Ethylethanolamine transparent solution Ethyldiethanolamine transparent solution Diethanolamine transparent solution Triethanolamine transparent solution Diethylene glycolamine Two-phase separation Example 5 Production of a mixture of carbohydrate, axifen, co-solvent system, and water To observe the solubility of AXIFEN. The obtained solubility is shown in Table 5. 87453 -22- 200412852 Sodium solubility cosolvent Carbothiazine Sodium / Axifenamide solubility system concentration at 20 ° C (mixture% ~ / \\ 〇 (acid-based) Afi alcohol / water ratio 0.0 0.5 1.0 2.0 Isopropanolamine 0% > 44.0% * > 29.2% * > 23.0% * > 17.8% * and ethylene glycol 6% 0.0% 0.0% 1.4% 9.7% 12% 0.0% 0.0% 0.0% 9.7% 18% 0.0% 0.0% 0.0% 0.0% Diisopropanol 0% > 44.0% * > 29.2% * > 23.4% * > 17.8% * Amine and ethylene glycol 6% 0.0% 0.1% 9.2% 9.8% alcohol 12% 0.0% 0.0% 0.24% 9.8% 18% 0.0% 0.0% 0.0% 0.9% The maximum value is limited by the TGA1 concentration. Example 6 A mixture of carbosulfan, axifen, a co-solvent system, and water was produced. Observe the effect of storage on the surface liquid. The solution was produced and stored for one month, and the results are shown in Tables 6a and 6b. Hui 6a ·· Physical test results of various storage conditions Composition Axifen: Jialinsai ratio 1: 2 1: 3 1: 4 1: 6 1: 8 Sodium Axifen (40.5%) 13.46 8.97 6.73 4.49 3.36 Diisopropanolamine (99%) 10.67 10.67 10.67 10.67 10.67 Calphosate (0.76%) 14.34 14.34 14.34 14.34 14.34 Water 26.53 31.02 33.26 35.50 36.62 B Diol 35.00 35.00 35.00 35.00 35.00 Total 100.00 100.00 100.00 100.00 100.00 87453 -23-200412852 Physical storage conditions 1 month after physical observation Freeze / thaw 5 cycles solution solution solution solution solution 5 ° C solution solution solution solution solution 25 ° C solution Solution solution solution solution 50 ° C solution solution solution solution solution solution = axifen-containing solution samples remain transparent Table 6b: Physical test results of various storage conditions Composition Axifen: Carbosac ratio 1: 2 1: 3 1: 4 Sodium Axifen (40.5%) 13.46 8.97 6.73 Diisopropanolamine (99%) 10.67 10.67 10.67 Calphosate (0.76%) 14.34 14.34 14.34 Water 26.53 31.02 33.26 Glycol 35.00 35.00 35.00 Total 100.00 100.00 100.00 Physical Storage conditions 1 month after physical observation Freeze / thaw 5 cycles of solution solution solution 5 ° C solution solution solution 25 ° C solution solution solution 50 ° C solution solution solution Example 7 Carbofuran, flusulfuron, axifen And water mixture to determine the interaction of the mixture. The results are shown in Table 7. 87453 -24- 200412852 Mixture of sulfasulfuron, acifluorfen, and axifen. Mixture of acisulfuron (wt%) Axifen mixture (wt%) Carbosam 16.5 16.5 Axifen sodium 0.0 4.1 Fluoxamine_ 4.1 0.0 Water 79.4 79.4 Total 100.0 100.0 Physical observation Transparent solution Transparent solution Example 8 Carbosulfan-trimethylsulfide, sodium acefene, sulfasulfuron, amine, monoalcohol, and water were produced to determine the mutuality of the mixtures effect. The results are shown in the table of ingredients. Fensulfazone formulations Axifen (wt%) (wt%) Carbosulfam-trimethylsulfide 16.5 16.5 16.5 Sodium axifen --------- 0.0 4 · 1_ Fluramine oxalic acid ----- 4.1 Diisopropanolamine -------- 0 · 0 j ^ O Ethylene glycol 0.0 40.0 0.0 Water 79.4 29.4-. 79.4 Total 100.0 100.0 100.0 Physical observation crystal Crystallization of transparent solution 16.5 4.1 0.0 10.0 40.0 29.4 100.0 The entire disclosure of the bulletin such as “less than 11¾” is hereby incorporated herein by reference 87453 -25- 200412852. Those skilled in the art will understand without departing from the scope and spirit of benzene invention Various improvements and changes can be made. For the purposes of this publication, the descriptions and examples disclosed by this document are to be regarded as examples only, as defined by the patent application park of this application. Other specific examples will become apparent to those skilled in the art and operations. The exact style and spirit of the specification can be expressed by the following

87453 • 26 ·87453 • 26 ·

Claims (1)

200412852 拾、申請專利範園: h —種除草組合物,包括: a) N-膦甲基甘胺酸或均膦酸丙胺酸甲基酯除草劑或其 鹽或酸; b) 二苯醚除草劑或其鹽或酯; c) 乙二醇; d) 胺源;及 e) 載劑; 其中該組合物為溶液。 2·如申請專利範圍第1項之組合物,其中該N-膦甲基甘胺酸 或均膦酸丙胺酸甲基酯除草劑對二苯醚除草劑之莫耳比 自約1:1至約10:1。 3·如申請專利範圍第1項之組合物,其中該N-膦甲基甘胺酸 或均膦酸丙胺酸甲基酯除草劑對二苯醚除草劑之莫耳比 自約2:1至約4:1。 4·如申請專利範圍第1項之組合物,其中該N-膦甲基甘胺酸 為嘉鱗塞(glyphosate)之異丙基胺鹽。 5·如申請專利範圍第1項之組合物,其中該均膦酸丙胺酸甲 基酉旨為固殺草(glufosinate)之铵鹽。 6·如申請專利範圍第1項之組合物,其中該二苯醚除草劑為 亞喜芬(acifluorfen)。 7·如申請專利範圍第1項之組合物,其中該N-膦甲基甘胺酸 或均膦酸丙胺酸甲基酯除草劑存在量為總溶液之約2 wt%至約 1〇 wt%。 87453 ^00412852 •如申請專利範圍第1項之組合物,其中該二苯駿除草劑存 在量為總溶液之約1 wt%至约30 wt%。 •如申請專利範圍第1項之組合物,其中該載劑為水。 10.如申請專利範園第1項之組合物,其中該膦甲基甘胺酸 或均膦酸丙胺酸甲基酯除草劑濃度自約1 〇磅/加奋至約 15磅/加备。 U. —種抑制不欲植物生長之方法,包括使該植物與除草有 效量之如申請專利範圍第1項之除草組合物接觸。 12·如申請專利範園第11項之方法,其中該接觸係藉對植物 嘴霧該除草組合物而進行。 13·如申請專利範園第^項之方法,其中該义膦甲基甘胺酸 除草劑為嘉磷塞之異丙基胺鹽。 14·如申請專利範圍第n項之方法,其中該均膦酸丙胺酸甲 基酉旨為固殺卓之按鹽。 15.如申請專利範圍第〖丨項之方法,其中該二苯醚除草劑為 亞喜芬。 16·如申請專利範圍第11項之方法,其中該^膦甲基甘胺酸 或均膦酸丙胺酸甲基酯除草劑存在量為總溶液之約2 wt%至約 10 wt%。 17.如申請專利範圍第11項之方法,其中該二苯醚除草劑存 在量為總溶液之約1 wt%至約30 wt%。 18· —種除草組合物,包括混合如申請專利範圍第丨項之成分 a)、b)、c)、d)及e)而形成溶液所得之產物。 19. 一種製造除草組合物之方法,包括混合: 87453 200412852 a) 膦甲基甘胺酸或均膦酸丙胺酸甲基酯除草劑或其 鹽或酸; b) 二苯醚除草劑或其鹽或酯; c) 乙二醇; d) 胺源;及 e) 載劑; 而形成溶液。 〇’如申請專利範圍第19項之方法,其中該膦甲基甘胺酸 或均膦酸丙胺酸甲基酯除草劑濃度自約1〇磅/加崙至約 15磅/加崙。 21·如申請專利範圍第19項之方法,其中該N-膦甲基甘胺酸 除草劑為嘉磷塞之異丙基胺鹽。 22·如申請專利範圍第19項之方法,其中該均膦酸丙胺酸甲 基酯為固殺草之銨鹽。 23.如申請專利範圍第19項之方法,其中該苯醚除草劑為亞 喜芬。 87453 200412852 柴、指定代表圖: (一) 本案指定代表圖為:第( )圖。 (二) 本代表圖之元件代表符號簡單說明: 捌、本案若有化學式時,請揭示最能顯示發明特徵的化學式: 〇 丨丨〆^ Z—CH9—NH—CH2 P R2 (I) NH2 o I II Z-CHCH2CH2P-CH3 (III) I Ri 87453200412852 Garden for patent application: h — a kind of herbicidal composition, including: a) N-phosphine methylglycine or homophosphonic acid alanine methyl ester herbicide or its salt or acid; b) diphenyl ether herbicide An agent or a salt or ester thereof; c) ethylene glycol; d) an amine source; and e) a carrier; wherein the composition is a solution. 2. The composition according to item 1 of the patent application range, wherein the molar ratio of the N-phosphine methylglycine or homophosphonic acid alanine methyl ester herbicide to diphenyl ether herbicide is from about 1: 1 to About 10: 1. 3. The composition according to item 1 of the patent application range, wherein the molar ratio of the N-phosphine methylglycine or homophosphonic acid alanine methyl ester herbicide to diphenyl ether herbicide is from about 2: 1 to About 4: 1. 4. The composition according to item 1 of the application, wherein the N-phosphonomethylglycine is an isopropylamine salt of glycphosate. 5. The composition according to item 1 of the scope of patent application, wherein the methyl phosphonate alanine is intended to be an ammonium salt of glufosinate. 6. The composition according to item 1 of the application, wherein the diphenyl ether herbicide is acifluorfen. 7. The composition according to item 1 of the patent application scope, wherein the N-phosphine methylglycine or homophosphonic acid alanine methyl ester herbicide is present in an amount of about 2 wt% to about 10 wt% of the total solution . 87453 ^ 00412852 • The composition according to item 1 of the patent application range, wherein the diphenyl-jun herbicide is present in an amount of about 1 wt% to about 30 wt% of the total solution. • The composition of claim 1 in which the carrier is water. 10. The composition of claim 1 in the patent application, wherein the concentration of the phosphine methylglycine or homophosphonic acid alanine methyl ester herbicide is from about 10 lbs / plus to about 15 lbs / plus. U. A method for inhibiting the growth of an undesired plant, comprising contacting the plant with an herbicidally effective amount of a herbicidal composition such as the one in the scope of patent application. 12. The method according to item 11 of the patent application park, wherein the contacting is performed by misting the herbicidal composition with a plant mouth. 13. The method according to item ^ of the patent application park, wherein the isophosphine methylglycine herbicide is isopropylamine salt of Carfosin. 14. The method according to item n of the scope of patent application, wherein the methylphosphonium aluminophosphonate is intended to be a solid salt of chlorpyrrolate. 15. The method according to the scope of application for a patent, wherein the diphenyl ether herbicide is Ascifene. 16. The method according to item 11 of the application, wherein the phosphonomethylglycine or homophosphonic acid alanine methyl ester herbicide is present in an amount of about 2 wt% to about 10 wt% of the total solution. 17. The method according to claim 11 in which the diphenyl ether herbicide is present in an amount of about 1 wt% to about 30 wt% of the total solution. 18. · A herbicidal composition comprising a product obtained by mixing components a), b), c), d) and e) such as those in the scope of application for a patent to form a solution. 19. A method for manufacturing a herbicidal composition comprising mixing: 87453 200412852 a) a phosphinomethylglycine or a homophosphonic acid alanine methyl ester herbicide or a salt or acid thereof; b) a diphenyl ether herbicide or a salt thereof Or an ester; c) ethylene glycol; d) an amine source; and e) a carrier; and a solution is formed. O 'The method of claim 19, wherein the concentration of the phosphinomethylglycine or homophosphonate alanine herbicide is from about 10 pounds per gallon to about 15 pounds per gallon. 21. The method according to claim 19, wherein the N-phosphine methylglycine herbicide is isopropylamine salt of Carfosin. 22. The method according to claim 19, wherein the methyl aluminophosphonate is an ammonium salt of imazapyr. 23. The method according to claim 19, wherein the phenyl ether herbicide is axifene. 87453 200412852 Chai, designated representative map: (1) The designated representative map in this case is: (). (II) Brief description of the element representative symbols of this representative diagram: 捌 If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: 〇 丨 丨 〆 ^ Z—CH9—NH—CH2 P R2 (I) NH2 o I II Z-CHCH2CH2P-CH3 (III) I Ri 87453
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