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TW201924527A - Liquid weeding composition - Google Patents

Liquid weeding composition Download PDF

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Publication number
TW201924527A
TW201924527A TW107140594A TW107140594A TW201924527A TW 201924527 A TW201924527 A TW 201924527A TW 107140594 A TW107140594 A TW 107140594A TW 107140594 A TW107140594 A TW 107140594A TW 201924527 A TW201924527 A TW 201924527A
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Taiwan
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herbicidal composition
liquid herbicidal
pyridine
composition according
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TW107140594A
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Chinese (zh)
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TWI702000B (en
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柳基鉉
全三才
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南韓商Ｌｇ化學股份有限公司
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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
    • A01N25/12—Powders or granules
    • A01N25/14—Powders or granules wettable
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof

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

Abstract

The present invention relates to an herbicidal liquid composition including a pyridine sulfonylurea compound, as an active ingredient, represented by Formula 1 below, a surfactant, and a buffer, the surfactant including a sulfosuccinate-based compound: wherein n represents an integer of 1 to 3, R is a hydrogen atom or a C1 to C4 alkyl group, R' is a hydrogen atom, a C1 to C4 alkyl group, a C1 to C3 haloalkyl group, a halogen group, or a C1 to C2 alkoxy group, and X and Y are each independently a C1 to C2 alkyl group, a C1 to C2 alkoxy group, a C1 to C2 haloalkoxy group, or a halogen group.

Description

液體除草組成物Liquid herbicidal composition

本發明關於液體除草液體組成物，其包括展現極佳的除草活性之活性除草成分。The present invention relates to a liquid herbicidal liquid composition comprising an active herbicidal ingredient exhibiting excellent herbicidal activity.

在作物栽培中，重要的是藉由控制抑制作物生長之雜草以保護作物。為了降低由於生長在栽培區域中的雜草之損害，諸如作物生長或產率的損失，已發展出能夠有效控制雜草且對作物安全的活性除草物質。迄今已發展的許多活性除草物質經登記用於特定作物及用於雜草控制。用於控制生長在特定作物之栽培區域中的雜草之此等除草活性物質較佳的是具有高的除草活性及寬廣的除草光譜，且對環境和作物是安全的。
同時，已發展包括此等活性除草物質之除草組成物，且已將之用於調配物中諸如可濕性粉劑、可乳化濃縮物、水分散性粒劑、粒劑、水懸劑(suspension concentrate)及類似者。然而，在通常以水稀釋成預定濃度以製備可噴霧溶液之可濕性粉劑、可乳化濃縮物及水分散性粒劑的例子中，為了使彼等均勻地噴霧在目標稻田或田地的整個表面上而有高成本及耗費時間的問題。儘管可濕性粉劑、可乳化濃縮物及水分散性粒劑的問題可藉由使用可直接使用而無需以水稀釋的粒劑應付，但是此等粒劑包括以除草劑總量為基礎計而相對低含量的活性除草物質、必然應包括用於形成除草劑之輔助劑、以複雜的方法製造(包括粉碎、混合、研磨、造粒、乾燥、分級及類似者)且具有由於噴霧所致問題，諸如出現污斑。
為了應付此等問題，已發展出水懸劑調配物、相對簡單且不損害生態環境及容許簡單且有效噴霧之製造方法。然而，在液體調配物(諸如水懸劑)的例子中，當在高溫下經長時間貯存時，則除草組成物的穩定性降低，這是因為展現極佳的除草活性之特定的活性成分係由於熱及水解而分解。
因此，對改進作為水懸劑調配物之包括展現極佳的除草活性之活性成分的除草組成物之穩定性的研究仍有迫切的需求。
[相關的技術文件]
[專利文件]
韓國專利第10-0399366號In crop cultivation, it is important to protect crops by controlling weeds that inhibit crop growth. In order to reduce damage due to weeds growing in cultivated areas, such as loss of crop growth or yield, active herbicidal substances that can effectively control weeds and are safe for crops have been developed. Many active herbicidal substances that have been developed to date are registered for specific crops and for weed control. These herbicidal active substances for controlling weeds growing in a cultivated area of a specific crop preferably have high herbicidal activity and a broad herbicidal spectrum, and are safe for the environment and crops.
At the same time, herbicidal compositions including these active herbicidal substances have been developed and used in formulations such as wettable powders, emulsifiable concentrates, water-dispersible granules, granules, suspension concentrates ) And the like. However, in the example of a wettable powder, an emulsifiable concentrate, and a water-dispersible granule that are usually diluted with water to a predetermined concentration to prepare a sprayable solution, in order to uniformly spray them over the entire surface of the target paddy field or field There are problems of high cost and time consuming. Although the problems of wettable powders, emulsifiable concentrates, and water-dispersible granules can be addressed by using granules that can be used directly without dilution with water, these granules include Relatively low levels of active herbicidal substances must necessarily include adjuvants for the formation of herbicides, be manufactured by complex methods (including comminution, mixing, grinding, granulation, drying, classification and the like) and have problems due to spraying , Such as the appearance of stains.
In order to cope with these problems, manufacturing methods of aqueous suspension formulations that are relatively simple and do not harm the ecological environment and allow simple and effective spraying have been developed. However, in the case of a liquid formulation such as an aqueous suspension, the stability of the herbicidal composition is reduced when stored at a high temperature for a long time, because the specific active ingredient system exhibiting excellent herbicidal activity Decomposes due to heat and hydrolysis.
Therefore, there is still an urgent need for research to improve the stability of a herbicidal composition including an active ingredient exhibiting excellent herbicidal activity as an aqueous suspension formulation.
[Related technical documents]
[Patent Document]
Korean Patent No. 10-0399366

[技術問題]
因此，本發明係鑑於上述問題而提出，且本發明的一個目的係提供包括展現極佳的除草活性之活性成分的液體除草組成物，且更特別地提供具有極佳的穩定性及因此能夠在高溫下經長時間貯存(儘管其為液體調配物)的液體除草組成物。

[技術解決辦法]
本發明的一個態樣係提供液體除草組成物，其包括作為活性成分之以下列式1代表的吡啶磺醯脲化合物、界面活性劑及緩衝劑，界面活性劑包括基於磺基琥珀酸鹽(sulfosuccinate-based)之化合物，

其中n代表1至3的整數，R為氫原子或C1至C4烷基，R’為氫原子、C1至C4烷基、C1至C3鹵烷基、鹵基或C1至C2烷氧基，且X和Y各自獨立為C1至C2烷基、C1至C2烷氧基、C1至C2鹵烷氧基或鹵基。

[有利的效果]
依照本發明，可提供具有改進的穩定性及因此能夠經長時間貯存的液體除草組成物，這是因為防止了活性除草成分的水解，即使在液體調配物中。[technical problem]
Accordingly, the present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a liquid herbicidal composition including an active ingredient exhibiting excellent herbicidal activity, and more particularly, to provide an herbicidal composition having excellent stability and thus capable of A liquid herbicidal composition that has been stored for a long time at high temperatures (although it is a liquid formulation).

[Technical solution]
One aspect of the present invention provides a liquid herbicidal composition comprising, as an active ingredient, a pyridinium sulfonamide compound represented by the following formula 1, a surfactant, and a buffering agent. The surfactant includes a sulfosuccinate-based -based) compounds,

Where n represents an integer from 1 to 3, R is a hydrogen atom or a C1 to C4 alkyl group, R ′ is a hydrogen atom, a C1 to C4 alkyl group, a C1 to C3 haloalkyl group, a halo group, or a C1 to C2 alkoxy group, and X and Y are each independently C1 to C2 alkyl, C1 to C2 alkoxy, C1 to C2 haloalkoxy or halo.

[Beneficial effect]
According to the present invention, a liquid herbicidal composition having improved stability and thus capable of being stored for a long time can be provided because hydrolysis of the active herbicidal ingredient is prevented, even in liquid formulations.

[本發明之模式]
現將更詳細說明本發明以助於理解本發明。在說明書及接續的申請專利範圍中所使用的術語或文字不應受限於常見或字典的含義，而具有對應於本發明之具體實例的技術態樣之含義及觀念，以便於最適當地表達本發明之具體實例。
本發明之液體除草組成物包括作為活性成分之以下列式1代表的吡啶磺醯脲化合物、界面活性劑及緩衝劑，界面活性劑包括基於磺基琥珀酸鹽之化合物，

其中n代表1至3的整數，R為氫原子或C1至C4烷基，R’為氫原子、C1至C4烷基、C1至C3鹵烷基、鹵基或C1至C2烷氧基，且X和Y各自獨立為C1至C2烷基、C1至C2烷氧基、C1至C2鹵烷氧基或鹵基。
更佳地，在式1中，n可為1或2的整數，R可為氫原子或甲基，R’可為氫原子、鹵基或甲基，且X和Y可各自為甲氧基。
甚至更佳地，在式1中，n可為1或2的整數，R可為甲基，R’可為氫原子、Cl、Br或甲基，且X和Y可各自為甲氧基。
作為活性成分之以式1代表的吡啶磺醯脲化合物可為例如至少一種選自由下列所組成之群組的化合物：N-[(4,6-二甲氧基嘧啶-2-基)胺基羰基]-2-(2-氟-1-甲氧基乙醯氧基-正丙基)吡啶-3-磺醯胺、N-[(4,6-二甲氧基嘧啶-2-基)胺基羰基]-2-(2-氟-1-羥基乙醯氧基-正丙基)吡啶-3-磺醯胺、N-[(4,6-二甲氧基嘧啶-2-基)胺基羰基]-2-(2-氟-1-(3-羥基丙醯)氧基-正丙基)吡啶-3-磺醯胺、N-[(4,6-二甲氧基嘧啶-2-基)胺基羰基]-2-(2-氟-1-(3-甲氧基丙醯)氧基-正丙基)吡啶-3-磺醯胺、N-[(4,6-二甲氧基嘧啶-2-基)胺基羰基]-4-甲基-2-(2-氟-1-甲氧基乙醯氧基-正丙基)吡啶-3-磺醯胺、N-[(4,6-二甲氧基嘧啶-2-基)胺基羰基]-4-氯-2-(2-氟-1-甲氧基乙醯氧基-正丙基)吡啶-3-磺醯胺和N-[(4,6-二甲氧基嘧啶-2-基)胺基羰基]-4-溴-2-(2-氟-1-甲氧基乙醯氧基-正丙基)吡啶-3-磺醯胺。
更佳地，作為活性成分之以式1代表的吡啶磺醯脲化合物可為以下列式A代表的化合物(提出之ISO名稱：氟吡磺隆(flucetosulfuron))：

以式1代表的吡啶磺醯脲化合物具有極佳的除草活性，但是由於磺醯脲基團在液體調配物中水解而難以確保其穩定性。特別地，由於水解的分解率係隨著以式1代表的吡啶磺醯脲化合物之含量降低而進一步增加，因而難以確保在化合物在液體調配物中的穩定性。
因此，本發明之作為液體調配物的除草組成物包括作為界面活性劑的基於磺基琥珀酸鹽之化合物連同作為活性除草成分之以式1代表的吡啶磺醯脲化合物，因而使除草組成物改進在液體調配物中的穩定性。因為界面活性劑之磺基琥珀酸基團保護吡啶磺醯脲化合物之磺醯脲基團免於水解，所以可確保除草組成物的穩定性，即使在液體調配物中。
更特別地，界面活性劑可包括以下列式2代表的基於磺基琥珀酸鹽之化合物：

其中M為至少一種選自由下列所組成之群組者：Na、NH4 和K，且R1 和R2 各自獨立為C1至C20烷基、環烷基或芳基。
更佳地，在式2中，M可為Na，且R1 和R2 可各自獨立為C4至C10烷基或環烷基。
以式2化表的界面活性劑可為例如至少一種選自由下列所組成之群組的化合物：磺基琥珀酸二辛酯鈉、磺基琥珀酸二異丁酯鈉和二環己烷磺基琥珀酸鈉(sodium dicyclohexane sulfosuccinate)，更佳為磺基琥珀酸二辛酯鈉或磺基琥珀酸二異丁酯鈉。
根據本發明之具體實例的液體除草組成物可包括1至50重量%之作為活性成分之以式1代表的吡啶磺醯脲化合物。吡啶磺醯脲化合物的內含量可更佳為1.5至25重量%，甚至更佳為3至10重量%。當活性成分的內含量少於1重量%時，則在液體除草組成物中的活性成分含量太低，因而可降低除草活性。當活性成分的內含量大於50重量%時，則與活性成分含量增加的相比未顯著地改進除草效果，其可導致非必要增加的製造成本。
根據本發明之具體實例的液體除草組成物可包括1至7重量%之作為界面活性劑的基於磺基琥珀酸鹽之化合物。基於磺基琥珀酸鹽之化合物的內含量可更佳為1至5重量%，甚至更佳為3至5重量%。當作為界面活性劑的基於磺基琥珀酸鹽之化合物的內含量少於1重量%時，則活性成分之磺醯脲基團可能在液體調配物中未受到保護且可能水解，其可導致穩定性降低。當基於磺基琥珀酸鹽之化合物的內含量大於7重量%時，則與界面活性劑含量的增加相比未顯著地改進穩定性改進效果，且使黏度增加，其可導致生產力降低。
根據本發明之具體實例的液體除草組成物另外包括緩衝劑。緩衝劑用於調節液體除草組成物之pH。液體除草組成物之pH可較佳為6至7。當pH係在6至7的範圍內時，則可進一步降低液體除草組成物的分解率且可進一步改進穩定性。
根據本發明之具體實例的液體除草組成物可另外包括防凍摻合物。防凍摻合物的內含量可為0.01至10重量%，更佳為2至8重量%，甚至更佳為2至4重量%。當防凍摻合物的內含量係在該等範圍內時，則可展現極佳的防凍效果且可進一步降低液體除草組成物的分解率。
防凍摻合物可包括基於二醇之化合物或基於醇之化合物。特別地，基於二醇之化合物可為丙二醇(P.G)、乙二醇、二乙二醇、二丙二醇、三丙二醇或類似者，及基於醇之化合物可為甘油、異丙醇或類似者。更佳地，防凍摻合物可包括丙二醇。
根據本發明之具體實例的液體除草組成物可另外包括增稠劑。增稠劑的內含量可為0.05至1.2重量%，更佳為0.05至0.6重量%，甚至更佳為0.05至0.15重量%。當增稠劑的內含量係在該等範圍內時，則可改進增稠效果且可進一步降低液體除草組成物的分解率。
增稠劑未受到特別的限制，只要是通常用於相關的技術領域者。特別地可使用三仙膠、皂土、矽礬石黏土、微晶高嶺石、阿拉伯膠、瓜爾膠、纖維素化合物、藻酸鈉、澱粉或其混合物。更佳地可使用三仙膠、微晶高嶺石或其混合物。
依照本發明之具體實例，除了上述組份以外，若必要時，液體除草組成物可另外包括消泡劑、防腐劑、穩定劑、顏料等。
依照本發明之具體實例，液體除草組成物包括作為活性成分之以式1代表的吡啶磺醯脲化合物；及界面活性劑，且可另外包括添加劑，諸如防凍摻合物、增稠劑、消泡劑、防腐劑和穩定劑。除了添加劑體積以外的剩餘體積可以緩衝劑填充。換言之，以100重量%之液體除草組成物計，緩衝劑的含量可為除了組份含量以外的剩餘含量。
依照本發明之具體實例，液體除草組成物之調配物未受到特別的限制，只要其為液體調配物。液體除草組成物可特別為以液體或水懸劑(SC)調配物存在的液體調配物，更佳為SC調配物。SC調配物在此可為水分散性懸浮液調配物。
儘管根據本發明之具體實例的液體除草組成物為液體調配物，但是包括作為界面活性劑的基於磺基琥珀酸鹽之化合物，使得吡啶磺醯脲化合物之磺醯脲基團可受到保護而免於水解。因此，液體除草組成物展現極佳的穩定性，即使於液體調配物中，且可方便長時間貯存。
本發明之特定的具體實例將於下文說明。然而，應理解具體實例的提供並非限制本發明之範圍且在所附申請專利範圍內的所有替代物及修飾皆包括在本發明中。因此，下列特定的具體實例係以例證為目的而完整說明，且提供方法及態樣以便於容易理解。
僅以例證為目的提供下列的實施例，對那些一般熟習此項技術者說明如何達成及評估所提供的化合物、組成物及方法。因此，不意欲以下列的實施例限制本發明者視為本發明之範圍。有許多可利用的條件變化及組合，使反應條件、組份濃度、所欲溶劑、溶劑混合物、溫度、壓力、其他的反應參數及產物特性最優化，諸如純度和產率。該等被認為是包括在本發明之範圍內。所有可能的變化之任何組合皆包括在本發明中，除非在本文另有其他的指示或另與上下文有明確的抵觸。

實施例 1
將水添加至K2 HPO4 及KH2 PO4 中以製備總共1公升溶液，藉此製備0.1 M磷酸鹽緩衝劑。接著將3.0重量%之CR-DOS70P (磺基琥珀酸二(2-乙基己基)酯，鈉鹽，Cas編號577-11-7)、1.0重量%之NK-SU500 (蔗糖月桂酸酯，Cas編號25339-99-5)及作為消泡劑的0.2重量%之SAG-622 (由Momentive製造)添加至65.8重量%之緩衝劑中，隨後充分混合。在均勻混合的狀態下，將10.0重量%之甲氧化乙酸1-(3-{[(4,6-二甲氧基-嘧啶-2-基)胺甲醯基]胺磺醯基}-2-吡啶基)-2-氟丙基酯(氟吡磺隆，FTS)添加至混合物中，隨後使用攪拌器充分混合。將玻璃珠添加至所得混合物中以進行粉碎。進行此粉碎，直到平均粒徑達到1至2微米為止。結果製得濕部分。
接著將0.1重量%之X.G (三仙膠，Cas編號11138-66-2)及0.2重量%之M.V [5-氯-2-甲基-4-異噻唑啉-3-酮(Cas編號26172-55-4)及2-甲基-4-異噻唑啉-3-酮(Cas編號2682-20-4)]添加至3.0重量%之P.G (丙二醇，Cas編號57-55-6)中，隨後充分混合且同時攪拌。接著將16.7重量%之0.1M磷酸鹽緩衝劑添加至其中，隨後充分混合且同時攪拌。結果製得增稠部分。
接著將30重量%之增稠部分添加至70重量%之濕部分中，隨後充分混合且同時攪拌。結果製得具有水懸劑調配物之除草組成物。

實施例 2
具有水懸劑調配物之除草組成物係以與實施例1相同的方式製備，除了使用3重量%之磺基琥珀酸二異丁酯鈉(CR-DIBS)代替3重量%之磺基琥珀酸二辛酯鈉(DOS70P)以外。

實施例 3
具有水懸劑調配物之除草組成物係以與實施例1相同的方式製備，除了使用3重量%之二環己烷磺基琥珀酸鈉(CR-DCHS)代替3重量%之DOS70P以外。

比較例 1
具有水懸劑調配物之除草組成物係以與實施例1相同的方式製備，除了使用3重量%之Altox 4915 (由Croda製造)代替3重量%之DOS70P以外。

比較例 2
具有水懸劑調配物之除草組成物係以與實施例1相同的方式製備，除了使用3重量%之萘磺酸甲醛液濃縮物(NK-D425)代替3重量%之DOS70P以外。

比較例 3
具有水懸劑調配物之除草組成物係以與實施例1相同的方式製備，除了使用3重量%之磺酸木質素(NK-SLS)代替3重量%之DOS70P以外。
實驗實施例：評估液體除草組成物之貯存穩定性
為了評估實施例1至3及比較例1至3的液體除草組成物之貯存穩定性，將約100克各樣品填充至以聚乙烯(PE)製成的塑膠瓶中，隨後密封。接著將每一瓶子貯存在維持於54(±2)℃之烘箱中4週，且接著使用HPLC (由Waters製造)測量活性成分之面積值以評估分解率。將結果總結於以下表1中。
HPLC分析條件係如下：
管柱：100毫米×4.6毫米內徑「Capcell Pak」C18管柱，3微米粒子
移動相：乙腈/水(0.02M乙酸銨+ 0.1M乙酸) = 32/68
流速：1.0毫升/分鐘
管柱溫度：30℃
注入體積：10微升
檢測器波長：254奈米
操作時間：20分鐘
[Mode of the invention]
The present invention will now be explained in more detail to help understand the present invention. The terms or words used in the description and subsequent patent applications should not be limited to common or dictionary meanings, but should have meanings and concepts corresponding to the technical aspects of the specific examples of the present invention in order to best express this Specific examples of the invention.
The liquid herbicidal composition of the present invention includes, as an active ingredient, a pyridosulfuronium compound represented by the following Formula 1, a surfactant, and a buffering agent, and the surfactant includes a sulfosuccinate-based compound,

Where n represents an integer from 1 to 3, R is a hydrogen atom or a C1 to C4 alkyl group, R ′ is a hydrogen atom, a C1 to C4 alkyl group, a C1 to C3 haloalkyl group, a halo group, or a C1 to C2 alkoxy group, and X and Y are each independently C1 to C2 alkyl, C1 to C2 alkoxy, C1 to C2 haloalkoxy or halo.
More preferably, in Formula 1, n may be an integer of 1 or 2, R may be a hydrogen atom or a methyl group, R ′ may be a hydrogen atom, a halogen group, or a methyl group, and X and Y may each be a methoxy group. .
Even more preferably, in Formula 1, n may be an integer of 1 or 2, R may be a methyl group, R ′ may be a hydrogen atom, Cl, Br, or a methyl group, and X and Y may each be a methoxy group.
The pyridinium sulfonylurea compound represented by Formula 1 as an active ingredient may be, for example, at least one compound selected from the group consisting of N-[(4,6-dimethoxypyrimidin-2-yl) amino Carbonyl] -2- (2-fluoro-1-methoxyethoxyl-n-propyl) pyridine-3-sulfonamide, N-[(4,6-dimethoxypyrimidin-2-yl) Aminocarbonyl] -2- (2-fluoro-1-hydroxyethylfluorenyloxy-n-propyl) pyridine-3-sulfonamide, N-[(4,6-dimethoxypyrimidin-2-yl) Aminocarbonyl] -2- (2-fluoro-1- (3-hydroxypropanyl) oxy-n-propyl) pyridine-3-sulfonamide, N-[(4,6-dimethoxypyrimidine- 2-yl) aminocarbonyl] -2- (2-fluoro-1- (3-methoxypropylhydrazine) oxy-n-propyl) pyridine-3-sulfonamide, N-[(4,6- Dimethoxypyrimidin-2-yl) aminocarbonyl] -4-methyl-2- (2-fluoro-1-methoxyethenyloxy-n-propyl) pyridine-3-sulfonamide, N -[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -4-chloro-2- (2-fluoro-1-methoxyethenyloxy-n-propyl) pyridine-3 -Sulfamethoxamine and N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -4-bromo-2- (2-fluoro-1-methoxyethenyloxy-n Propyl) pyridine-3-sulfonamide.
More preferably, the pyridosulfuronium compound represented by Formula 1 as an active ingredient may be a compound represented by the following Formula A (proposed ISO name: flucetosulfuron):

The pyridinium sulfonylurea compound represented by Formula 1 has excellent herbicidal activity, but it is difficult to ensure its stability because the sulfonylurea group is hydrolyzed in a liquid formulation. In particular, since the decomposition rate of hydrolysis is further increased as the content of the pyridosulfuronium compound represented by Formula 1 decreases, it is difficult to ensure the stability of the compound in a liquid formulation.
Therefore, the herbicidal composition as a liquid formulation of the present invention includes a sulfosuccinate-based compound as a surfactant together with a pyridinium sulfonamide compound represented by Formula 1 as an active herbicidal ingredient, thereby improving the herbicidal composition Stability in liquid formulations. Because the sulfosuccinic acid group of the surfactant protects the sulfonylurea group of the pyridinesulfonylurea compound from hydrolysis, the stability of the herbicidal composition can be ensured, even in liquid formulations.
More specifically, the surfactant may include a sulfosuccinate-based compound represented by the following Formula 2:

Wherein M is at least one selected from the group consisting of Na, NH 4 and K, and R 1 and R 2 are each independently a C1 to C20 alkyl group, a cycloalkyl group or an aryl group.
More preferably, in Formula 2, M may be Na, and R 1 and R 2 may each independently be a C4 to C10 alkyl group or a cycloalkyl group.
The surfactant represented by Formula 2 may be, for example, at least one compound selected from the group consisting of: sodium dioctyl sulfosuccinate, sodium diisobutyl sulfosuccinate, and dicyclohexanesulfo Sodium dicyclohexane sulfosuccinate is more preferably sodium dioctyl sulfosuccinate or sodium diisobutyl sulfosuccinate.
The liquid herbicidal composition according to a specific example of the present invention may include 1 to 50% by weight of a pyridosulfuronium compound represented by Formula 1 as an active ingredient. The internal content of the pyridosulfuronium compound may be more preferably 1.5 to 25% by weight, and even more preferably 3 to 10% by weight. When the internal content of the active ingredient is less than 1% by weight, the content of the active ingredient in the liquid herbicidal composition is too low, thereby reducing the herbicidal activity. When the internal content of the active ingredient is more than 50% by weight, the herbicidal effect is not significantly improved as compared with an increase in the content of the active ingredient, which may cause an unnecessary increase in manufacturing costs.
The liquid herbicidal composition according to a specific example of the present invention may include 1 to 7% by weight of a sulfosuccinate-based compound as a surfactant. The internal content of the sulfosuccinate-based compound may be more preferably 1 to 5 wt%, even more preferably 3 to 5 wt%. When the internal content of the sulfosuccinate-based compound as a surfactant is less than 1% by weight, the sulfonylurea group of the active ingredient may not be protected in the liquid formulation and may be hydrolyzed, which may cause Reduced stability. When the internal content of the sulfosuccinate-based compound is more than 7% by weight, the stability improvement effect is not significantly improved compared with the increase in the content of the surfactant, and the viscosity is increased, which may result in reduced productivity.
The liquid herbicidal composition according to a specific example of the present invention further includes a buffering agent. Buffers are used to adjust the pH of the liquid herbicidal composition. The pH of the liquid herbicidal composition may be preferably 6 to 7. When the pH is in the range of 6 to 7, the decomposition rate of the liquid herbicidal composition can be further reduced and the stability can be further improved.
The liquid herbicidal composition according to a specific example of the present invention may further include an antifreeze blend. The antifreeze blend may have an internal content of 0.01 to 10% by weight, more preferably 2 to 8% by weight, and even more preferably 2 to 4% by weight. When the internal content of the antifreeze blend is within these ranges, an excellent antifreeze effect can be exhibited and the decomposition rate of the liquid herbicidal composition can be further reduced.
Antifreeze blends can include glycol-based compounds or alcohol-based compounds. In particular, the diol-based compound may be propylene glycol (PG), ethylene glycol, diethylene glycol, dipropylene glycol, tripropylene glycol, or the like, and the alcohol-based compound may be glycerin, isopropyl alcohol, or the like. More preferably, the antifreeze blend may include propylene glycol.
The liquid herbicidal composition according to a specific example of the present invention may further include a thickener. The internal content of the thickener may be 0.05 to 1.2% by weight, more preferably 0.05 to 0.6% by weight, and even more preferably 0.05 to 0.15% by weight. When the internal content of the thickener is within these ranges, the thickening effect can be improved and the decomposition rate of the liquid herbicidal composition can be further reduced.
The thickener is not particularly limited as long as it is generally used in the relevant technical field. In particular, three cents gum, bentonite, diaspore clay, microcrystalline kaolinite, acacia, guar gum, cellulose compounds, sodium alginate, starch or mixtures thereof can be used. More preferably, sagenite, microcrystalline kaolinite or mixtures thereof can be used.
According to a specific example of the present invention, in addition to the above components, the liquid herbicidal composition may further include a defoaming agent, a preservative, a stabilizer, a pigment, and the like, if necessary.
According to a specific example of the present invention, the liquid herbicidal composition includes, as an active ingredient, a pyridosulfuronium compound represented by Formula 1; and a surfactant, and may further include additives such as an antifreeze blend, a thickener, and an antifoam Agents, preservatives and stabilizers. The remaining volume in addition to the additive volume may be filled with a buffer. In other words, based on 100% by weight of the liquid herbicidal composition, the content of the buffering agent may be the remaining content other than the component content.
According to a specific example of the present invention, the formulation of the liquid herbicidal composition is not particularly limited as long as it is a liquid formulation. The liquid herbicidal composition may be, in particular, a liquid formulation in the form of a liquid or an aqueous suspension (SC) formulation, and more preferably an SC formulation. The SC formulation can be a water-dispersible suspension formulation here.
Although the liquid herbicidal composition according to a specific example of the present invention is a liquid formulation, the sulfosuccinate-based compound is included as a surfactant so that the sulfonylurea group of the pyridinesulfonylurea compound can be protected from In hydrolysis. Therefore, the liquid herbicidal composition exhibits excellent stability, even in liquid formulations, and can be conveniently stored for a long time.
Specific specific examples of the present invention will be described below. However, it should be understood that specific examples are not provided to limit the scope of the present invention and that all alternatives and modifications within the scope of the attached patent application are included in the present invention. Therefore, the following specific specific examples are fully explained for the purpose of illustration, and methods and aspects are provided for easy understanding.
The following examples are provided for the purpose of illustration only, and to those of ordinary skill in the art, how to achieve and evaluate the provided compounds, compositions, and methods. Therefore, the following examples are not intended to limit the scope of the present inventors' view of the present invention. There are many variations and combinations of conditions available to optimize reaction conditions, component concentrations, desired solvents, solvent mixtures, temperature, pressure, other reaction parameters and product characteristics, such as purity and yield. These are considered to be included within the scope of the present invention. Any combination of all possible variations is included in the present invention unless otherwise indicated herein or otherwise clearly contradicted by context.

Example 1
Water was added to K 2 HPO 4 and KH 2 PO 4 to prepare a total of 1 liter solution, thereby preparing a 0.1 M phosphate buffer. Next, 3.0% by weight of CR-DOS70P (bis (2-ethylhexyl) sulfosuccinate, sodium salt, Cas No. 577-11-7), 1.0% by weight of NK-SU500 (sucrose laurate, Cas No. 25339-99-5) and 0.2% by weight of SAG-622 (manufactured by Momentive) as an antifoaming agent were added to 65.8% by weight of a buffer, followed by thorough mixing. In a uniformly mixed state, 10.0% by weight of methoxyacetic acid 1- (3-{[(4,6-dimethoxy-pyrimidin-2-yl) aminomethylamidino] aminesulfonyl} -2 -Pyridyl) -2-fluoropropyl ester (floxasulfuron, FTS) was added to the mixture, followed by thorough mixing using a stirrer. Glass beads were added to the obtained mixture to perform pulverization. This pulverization is performed until the average particle diameter reaches 1 to 2 microns. As a result, a wet portion was prepared.
Next, 0.1% by weight of XG (Sanxian gum, Cas No. 11138-66-2) and 0.2% by weight of MV [5-Chloro-2-methyl-4-isothiazolin-3-one (Cas No. 26172- 55-4) and 2-methyl-4-isothiazolin-3-one (Cas No. 2682-20-4)] were added to 3.0% by weight of PG (propylene glycol, Cas No. 57-55-6), and then Mix well while stirring. Then, 16.7% by weight of 0.1 M phosphate buffer was added thereto, followed by thorough mixing while stirring. As a result, a thickened portion was obtained.
30% by weight of the thickened portion was then added to the 70% by weight of the wet portion, followed by thorough mixing while stirring. As a result, a herbicidal composition having an aqueous suspension formulation was prepared.

Example 2
The herbicidal composition with the aqueous suspension formulation was prepared in the same manner as in Example 1, except that 3% by weight of sodium diisobutyl sulfosuccinate (CR-DIBS) was used instead of 3% by weight of sulfosuccinic acid. Other than dioctyl sodium (DOS70P).

Example 3
The herbicidal composition with the aqueous suspension formulation was prepared in the same manner as in Example 1, except that 3% by weight of sodium dicyclohexanesulfosuccinate (CR-DCHS) was used instead of 3% by weight of DOS70P.

Comparative Example 1
The herbicidal composition with the aqueous suspension formulation was prepared in the same manner as in Example 1, except that 3% by weight of Altox 4915 (manufactured by Croda) was used instead of 3% by weight of DOS70P.

Comparative Example 2
The herbicidal composition with the aqueous suspension formulation was prepared in the same manner as in Example 1, except that 3% by weight of naphthalenesulfonic acid formaldehyde liquid concentrate (NK-D425) was used instead of 3% by weight of DOS70P.

Comparative Example 3
The herbicidal composition with the aqueous suspension formulation was prepared in the same manner as in Example 1, except that 3% by weight of sulfonic lignin (NK-SLS) was used instead of 3% by weight of DOS70P.
Experimental Example: Evaluation of the storage stability of the liquid herbicidal composition In order to evaluate the storage stability of the liquid herbicidal composition of Examples 1 to 3 and Comparative Examples 1 to 3, about 100 g of each sample was filled with polyethylene (PE) The finished plastic bottle is then sealed. Each bottle was then stored in an oven maintained at 54 (± 2) ° C for 4 weeks, and then the area value of the active ingredient was measured using HPLC (manufactured by Waters) to evaluate the decomposition rate. The results are summarized in Table 1 below.
The HPLC analysis conditions are as follows:
Column: 100mm × 4.6mm inner diameter “Capcell Pak” C18 column, 3 micron particle mobile phase: acetonitrile / water (0.02M ammonium acetate + 0.1M acetic acid) = 32/68
Flow rate: 1.0 ml / mincolumn temperature: 30 ° C
Injection volume: 10 microliters Detector wavelength: 254 nm Operating time: 20 minutes

Claims (9)

一種液體除草組成物，其包含： 作為活性成分之以下列式1代表的吡啶磺醯脲化合物、界面活性劑及緩衝劑，該界面活性劑包含基於磺基琥珀酸鹽之化合物， 其中n代表1至3的整數， R為氫原子或C1至C4烷基， R’為氫原子、C1至C4烷基、C1至C3鹵烷基、鹵基或C1至C2烷氧基，且 X和Y各自獨立為C1至C2烷基、C1至C2烷氧基、C1至C2鹵烷氧基或鹵基。A liquid herbicidal composition comprising, as an active ingredient, a pyridinium sulfonylurea compound represented by the following Formula 1, a surfactant, and a buffer, the surfactant comprising a sulfosuccinate-based compound, Where n represents an integer from 1 to 3, R is a hydrogen atom or a C1 to C4 alkyl group, R ′ is a hydrogen atom, a C1 to C4 alkyl group, a C1 to C3 haloalkyl group, a halo group, or a C1 to C2 alkoxy group, and X and Y are each independently C1 to C2 alkyl, C1 to C2 alkoxy, C1 to C2 haloalkoxy or halo. 根據申請專利範圍第1項之液體除草組成物，其中，該界面活性劑包含以下列式2代表的基於磺基琥珀酸鹽之化合物： 其中M為至少一種選自由下列所組成之群組者：Na、NH4 和K，且R1 和R2 各自獨立為C1至C20烷基、環烷基或芳基。The liquid herbicidal composition according to the first patent application range, wherein the surfactant comprises a sulfosuccinate-based compound represented by the following formula 2: Wherein M is at least one selected from the group consisting of Na, NH 4 and K, and R 1 and R 2 are each independently a C1 to C20 alkyl group, a cycloalkyl group or an aryl group. 根據申請專利範圍第2項之液體除草組成物，其中，在式2中，M為Na，且R1 和R2 各自獨立為C4至C10烷基或環烷基。The liquid herbicidal composition according to item 2 of the scope of patent application, wherein, in Formula 2, M is Na, and R 1 and R 2 are each independently a C4 to C10 alkyl group or a cycloalkyl group. 根據申請專利範圍第1項之液體除草組成物，其中，該界面活性劑包含至少一種選自由下列所組成之群組的化合物：磺基琥珀酸二辛酯鈉、磺基琥珀酸二異丁酯鈉及二環己烷磺基琥珀酸鈉。The liquid herbicidal composition according to item 1 of the application, wherein the surfactant comprises at least one compound selected from the group consisting of: sodium dioctyl sulfosuccinate, diisobutyl sulfosuccinate Sodium and sodium dicyclohexanesulfosuccinate. 根據申請專利範圍第1項之液體除草組成物，其中，該基於磺基琥珀酸鹽之化合物的內含量為1至7重量%。The liquid herbicidal composition according to item 1 of the patent application scope, wherein the sulfosuccinate-based compound has an internal content of 1 to 7% by weight. 根據申請專利範圍第1項之液體除草組成物，其中，在式1中，n為1或2的整數， R為氫原子或甲基， R’為氫原子、鹵基或甲基，且 X和Y各自為甲氧基。The liquid herbicidal composition according to item 1 of the scope of patent application, wherein, in Formula 1, n is an integer of 1 or 2, R is a hydrogen atom or a methyl group, R 'is a hydrogen atom, a halogen group, or a methyl group, and X and Y are each methoxy. 根據申請專利範圍第1項之液體除草組成物，其中，作為活性成分之該吡啶磺醯脲化合物為至少一種選自由下列所組成之群組的化合物：N-[(4,6-二甲氧基嘧啶-2-基)胺基羰基]-2-(2-氟-1-甲氧基乙醯氧基-正丙基)吡啶-3-磺醯胺、N-[(4,6-二甲氧基嘧啶-2-基)胺基羰基]-2-(2-氟-1-羥基乙醯氧基-正丙基)吡啶-3-磺醯胺、N-[(4,6-二甲氧基嘧啶-2-基)胺基羰基]-2-(2-氟-1-(3-羥基丙醯)氧基-正丙基)吡啶-3-磺醯胺、N-[(4,6-二甲氧基嘧啶-2-基)胺基羰基]-2-(2-氟-1-(3-甲氧基丙醯)氧基-正丙基)吡啶-3-磺醯胺、N-[(4,6-二甲氧基嘧啶-2-基)胺基羰基]-4-甲基-2-(2-氟-1-甲氧基乙醯氧基-正丙基)吡啶-3-磺醯胺、N-[(4,6-二甲氧基嘧啶-2-基)胺基羰基]-4-氯-2-(2-氟-1-甲氧基乙醯氧基-正丙基)吡啶-3-磺醯胺和N-[(4,6-二甲氧基嘧啶-2-基)胺基羰基]-4-溴-2-(2-氟-1-甲氧基乙醯氧基-正丙基)吡啶-3-磺醯胺。The liquid herbicidal composition according to item 1 of the scope of patent application, wherein the pyridosulfuronium compound as an active ingredient is at least one compound selected from the group consisting of N-[(4,6-dimethoxy Pyrimidin-2-yl) aminocarbonyl] -2- (2-fluoro-1-methoxyethenyloxy-n-propyl) pyridine-3-sulfonamide, N-[(4,6-di Methoxypyrimidin-2-yl) aminocarbonyl] -2- (2-fluoro-1-hydroxyacetamyloxy-n-propyl) pyridine-3-sulfonamide, N-[(4,6-di Methoxypyrimidin-2-yl) aminocarbonyl] -2- (2-fluoro-1- (3-hydroxypropanyl) oxy-n-propyl) pyridine-3-sulfonamide, N-[(4 , 6-dimethoxypyrimidin-2-yl) aminocarbonyl] -2- (2-fluoro-1- (3-methoxypropylamidine) oxy-n-propyl) pyridine-3-sulfonamide , N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -4-methyl-2- (2-fluoro-1-methoxyethenyloxy-n-propyl) Pyridine-3-sulfonamide, N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -4-chloro-2- (2-fluoro-1-methoxyethanyloxy -N-propyl) pyridine-3-sulfonamide and N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -4-bromo-2- (2-fluoro-1- Methoxyacetamido-n-propyl) pyridine-3-sulfonamide. 根據申請專利範圍第1項之液體除草組成物，其中，作為活性成分之該吡啶磺醯脲化合物的內含量為1至50重量%。The liquid herbicidal composition according to item 1 of the scope of patent application, wherein the internal content of the pyridosulfuronium compound as an active ingredient is 1 to 50% by weight. 根據申請專利範圍第1項之液體除草組成物，其中，該液體除草組成物為水懸劑(SC)調配物。The liquid herbicidal composition according to item 1 of the patent application scope, wherein the liquid herbicidal composition is an aqueous suspension (SC) formulation.
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