在作物種植情形下，重要的是藉由控制會抑制作物生長之雜草來保護作物。為了減少種植區域內的雜草生長所引起之損害比如作物生長或產量的損失，能夠有效地控制雜草並對作物是安全的活性除草物質已經被開發。迄今為止所開發之許多活性除草物質已經以特異作物登記並用於雜草控制。用於控制在特異作物的種植區域內之雜草生長的這樣之除草活性物質優選為具有高除草活性與廣泛除草廣效性且優選為對環境與作物安全。
同時，包括這樣的活性除草物質之除草組成物已經被開發並用於調配物，比如可濕性粉劑、可乳化濃縮物、水分散性粒劑、粒劑、懸浮濃縮物等。然而，在一般用水稀釋成預定濃度以製備可噴霧溶液的可濕性粉劑、可乳化濃縮物、與水分散性粒劑情況下，對均勻地噴灑在目標稻田或田野之整個表面上有昂貴且費時的問題。儘管可濕性粉劑、可乳化濃縮物、與水分散性粒劑之問題可以用能夠直接被使用而不用水稀釋的粒劑來解決，然而這樣之粒劑包括以除草劑總量為基準計相對低含量的活性除草物質，必須包括用於形成除草劑之助劑，係藉由包括粉碎、混合、研磨、粒化、乾燥、分級等的複合程序來製得，並有比如由於噴霧導致斑出現之問題。為了解決這樣的問題，已經開發懸浮濃縮物調配物，其之製造程序相對簡單且環保並允許簡單與高效率噴灑。同時，在利用這樣的各種除草劑調配物時，重要的是即使在長期儲存時，也能保障這些除草組成物之穩定性。
下列化學式a所示之化合物[提議的ISO名稱：氟吡磺隆(flucetosulfuron)]，其係屬於磺醯脲類之活性除草物質，已經在韓國專利號10-0399366(韓國專利申請號
10-2000-0059990)中被提議為活性除草物質：
已知氟吡磺隆在土壤或葉片處理時對米、小麥、大麥(適當劑量：10至40 g a.i./ha)、與草(適當劑量：50至200 g a.i./ha)是安全的並對各種雜草類型比如闊葉雜草、禾本科雜草、莎草科雜草、一年生雜草、與多年生雜草發揮極佳之除草效果。
然而，在保障包括這樣的磺醯脲類之活性除草物質的除草組成物之穩定性方面仍有一個問題。特別地，由於當在高溫下儲存時懸浮濃縮物(SC)調配物的穩定性因為水解而進一步惡化，所以很難長期儲存該SC調配物。
[ 相關技術文件 ]
[ 專利文件 ]
韓國專利號10-0399366In the case of crop cultivation, it is important to protect the crop by controlling weeds that inhibit the growth of the crop. In order to reduce damage caused by weed growth in the planted area, such as crop growth or loss of yield, active herbicidal substances that can effectively control weeds and are safe for crops have been developed. Many active herbicides developed to date have been registered as specific crops and used for weed control. Such a herbicidally active substance for controlling the growth of weeds in a planting area of a specific crop is preferably one having high herbicidal activity and broad herbicidal efficacy, and is preferably safe to the environment and crops.
Meanwhile, herbicidal compositions including such 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 case of wettable powders, emulsifiable concentrates, and water-dispersible granules which are generally diluted with water to a predetermined concentration to prepare a sprayable solution, it is expensive and uniformly sprayed on the entire surface of the target paddy field or field and Time-consuming issue. Although the problems of wettable powders, emulsifiable concentrates, and water-dispersible granules can be solved with granules that can be used directly without dilution with water, such granules include relative amounts based on the total amount of herbicides. Low levels of active herbicidal substances must include auxiliary agents for the formation of herbicides, which are prepared by a compound process including comminution, mixing, grinding, granulation, drying, classification, etc., and for example, spots caused by spraying Problem. To solve such problems, suspension concentrate formulations have been developed, the manufacturing process of which is relatively simple and environmentally friendly and allows for simple and efficient spraying. At the same time, when using such various herbicide formulations, it is important to ensure the stability of these herbicide compositions even during long-term storage.
The compound represented by the following chemical formula a [proposed ISO name: flucetosulfuron], which is an active herbicidal substance belonging to the sulfonylurea class, has been registered in Korean Patent No. 10-0399366 (Korean Patent Application No.
10-2000-0059990) is proposed as an active herbicidal substance:
Flumesulfuron is known to be safe in rice, wheat, barley (appropriate dose: 10 to 40 g ai / ha), and grass (appropriate dose: 50 to 200 g ai / ha) in soil or leaf treatment. Various weed types such as broadleaf weeds, gramineous weeds, sedge family weeds, annual weeds, and perennial weeds have excellent weed control effects.
However, there is still a problem in ensuring the stability of a herbicidal composition including such an active herbicidal material of sulfonylurea. In particular, since the stability of the suspension concentrate (SC) formulation is further deteriorated by hydrolysis when stored at high temperatures, it is difficult to store the SC formulation for a long period of time.
[ Related technical documents ]
[ Patent Document ]
Korean Patent No. 10-0399366
[ 技術問題 ]
因此，本發明係鑒於上述問題完成，並且本發明之一個目的是提供包括屬於磺醯脲類之活性除草物質的除草組成物，該除草組成物具有極佳穩定性連同極佳除草活性，從而能夠長期儲存。
[ 技術方案 ]
本發明之一個態樣提供除草組成物，其包括作為活性成分的下式1所示之吡啶磺醯脲化合物，該吡啶磺醯脲化合物是包括赤型(erythro form)與蘇型的異構物混合物，該異構物混合物包括92重量%或更多之赤型：
其中n代表1至3的整數，R是氫原子或C1至C4烷基，R'是氫原子、C1至C4烷基、C1至C3鹵烷基、鹵素基、或C1至C2烷氧基，及X與Y各獨立地是C1至C2烷基、C1至C2烷氧基、C1至C2鹵烷氧基、或鹵素基。
[ 有利功效 ]
根據本發明，能提供除草組成物，其即使在高溫下長期儲存時也具有極佳除草活性與低分解速率，特別地，甚至在懸浮濃縮物(SC)調配物中也具有極佳穩定性。
[ 本發明之模式 ]
現在，將更詳細描述本發明以助於了解本發明。在本說明書與隨附申請專利範圍中所用之用語或字詞不應受限於通用意義或字典意義，並且具有對應於本發明的實施方式之技術態樣的意義與概念，以便最適當地表達本發明之實施方式。
本發明之除草組成物包括作為活性成分的下式1所示之吡啶磺醯脲化合物，該吡啶磺醯脲化合物是包括赤型與蘇型的異構物混合物，該異構物混合物包括92重量%或更多之赤型：
其中n代表1至3的整數，R是氫原子或C1至C4烷基，R'是氫原子、C1至C4烷基、C1至C3鹵烷基、鹵素基、或C1至C2烷氧基，及X與Y各獨立地是C1至C2烷基、C1至C2烷氧基、C1至C2鹵烷氧基、或鹵素基。
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、鹵素基、或甲基，及X與Y可各為甲氧基。
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，及X與Y可各為甲氧基。
式1所示之吡啶磺醯脲化合物可為例如選自由下列所組成之組群中的至少一者：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、及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，式1所示之吡啶磺醯脲化合物可為下式2所示之化合物[提議的ISO名稱：氟吡磺隆(flucetosulfuron)]：
由於式1所示之化合物包括二個不對稱碳，該化合物可能以赤型異構物或蘇型異構物形式存在。
本發明之除草組成物包括為異構物混合物(包括赤型與蘇型)之式1所示的化合物。在這裡，包括以該異構物混合物總量為基準計92重量%或更多之量的赤型。更佳地，可包括以該異構物混合物總量為基準計95重量%或更多之量的赤型。甚至更佳地，可包括以該異構物混合物總量為基準計95重量%至99重量%之量的赤型。
由於包括以該異構物混合物(包括赤型與蘇型)總量為基準計92重量%或更多之量的赤型，所以展現出極佳除草活性，且即使在高溫下長期儲存時由於低分解速率而保障穩定性。
當只包括式1所示之化合物的赤型時，生產效率大減。當只包括式1所示之化合物的蘇型時，除草活性減少，而分解速率大增，其導致穩定性降低。此外，當式1所示之化合物是為異構物混合物(包括赤型與蘇型)形式存在，但在該異構物混合物中的赤型含量少於92重量%時，除草活性減少，而分解速率增加。特別地，在液態調配物情況下，由於水解使其穩定性進一步減少，據此很難在高溫下長期儲存。
在本發明中，包括式1所示之化合物的異構物混合物之除草組成物可能以通用除草組成物調配物形式使用。包括該異構物混合物的除草組成物可能另外包括載體、界面活性劑、或添加劑(一般用於調配物領域者，根據需要)，並可能以各種調配物形式利用。該載體與添加劑中之每一者可能是固體或液體，特別是用於調配物領域的有用成分，例如天然或合成無機物質、溶劑、分散劑、潤濕劑、黏著劑、增稠劑、黏合劑等。
例如，該除草組成物可被製備成至少一種選自由下列所組成之組群中的調配物：懸浮濃縮物、擴散油、可濕性粉劑、水分散性粒劑、分散性粉劑、散布劑、丸劑、粒劑、及錠劑。更佳地，該除草組成物可為懸浮濃縮物。當該除草組成物是懸浮濃縮物時，該除草組成物可能另外包括緩衝劑、界面活性劑、與抗凍摻合物。在懸浮濃縮物情況下，其製造程序相對簡單，對生態環境友善，且對噴灑之而言簡單且高效率，但其穩定性由於水解所引起之分解而減少。然而，由於在本發明的除草組成物之異構物混合物(包括赤型與蘇型)中包括92重量%或更多的量之赤型，所以穩定性大增。因此，由於這樣的懸浮濃縮物調配物水解所引起之分解減少且可以在高溫下長期儲存。
該除草組成物可被製備成各種調配物，例如利用根據已知方法混合與/或粉碎有效成分與溶劑、固體載體、界面活性劑或其他添加劑。
下列物質可作為溶劑：芳烴類，例如二甲苯混合物或經取代萘；醇類與二醇類，比如乙醇、乙二醇、乙二醇一甲醚、或乙二醇一乙醚及其醚類與酯類；酮類，比如環己酮；強極性溶劑，比如N-甲基-2-吡咯啶酮、二甲亞碸、與二甲基甲醯胺；及環氧化或未環氧化植物油，比如環氧化椰子油與大豆油；或水。這樣的溶劑可作為用於液態調配物之溶劑或用於粒狀調配物的共溶劑。
作為一般用於散布劑與粒狀調配物之固體載體的例子，有經粉碎之天然礦物，比如滑石、高嶺土、蒙脫石、葉蠟石、膨土、與碳酸鈣、吸收劑載體，比如沸石、與砂。此外，可使用各種預粉碎的無機材料或有機材料。
上述界面活性劑可能選自非離子、陽離子與/或陰離子界面活性劑，其展現出令人滿意之分散、潤濕、與潤滑特性，取決於待調配的式1所示之化合物的性質。
就投予包括式1所示之化合物的異構物混合物之除草組成物的更佳方法而論，有用液態調配物潤濕植物棲地的方法或把固態形式(例如粒狀調配物形式)之活性成分加到土壤(土壤處理)中以透過土壤或水透過根與莖到達植物。或者，可藉由直接投予植物的葉(葉片應用)來展現出組成物之除草活性。投予的頻率與速率可根據植物、氣候、與土壤環境之生物特性而不同。
以下，將說明本發明之具體實施方式。然而，應當理解該實施方式並非提供來限制本發明的範圍且在隨附申請專利範圍之範圍中的所有替代件與修改件皆包括在本發明中。因此，為說明起見將仔細地說明下列具體實施方式，並且為容易了解起見將提供方法與態樣。
只為說明起見而提供下列實施例來向該領域之具有普通技藝者說明所提供的化合物、組成物、與方法如何製造與評估。因此，下列實施例無意限制發明者認為是本發明之範圍。有許多可用於使下列優化的條件之變型與組合：反應條件、成分濃度、所欲溶劑、溶劑混合物、溫度、壓力、其他反應參數、與產物性質比如純度與產率。這些被認為包括在本發明的範圍中。所有可能之變型的任何組合包括在本發明之範圍中，除非在本文中另外指出或除非與上下文明顯地相矛盾。 [ Technical issue ]
Therefore, the present invention has been made in view of the above problems, and it is an object of the present invention to provide a herbicidal composition including an active herbicidal substance belonging to the sulfonylurea class. The herbicidal composition has excellent stability and excellent herbicidal activity, thereby enabling Long-term storage.
[ Technical solution ]
According to one aspect of the present invention, there is provided a herbicidal composition comprising, as an active ingredient, a pyridosulfuronium compound represented by the following formula 1, which is an isomer including an erythro form and a threonine type A mixture comprising 92% by weight or more of the red form:
Where n represents an integer from 1 to 3, R is a hydrogen atom or a C1 to C4 alkyl group, and 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.
[ Beneficial effect ]
According to the present invention, it is possible to provide a herbicidal composition which has excellent herbicidal activity and low decomposition rate even when stored at high temperature for a long time, and particularly has excellent stability even in a suspension concentrate (SC) formulation.
[ Mode of the invention ]
Now, the present invention will be described in more detail to help understand the present invention. The terms or words used in the specification and the scope of the accompanying patent application should not be limited to general meanings or dictionary meanings, and have meanings and concepts corresponding to the technical aspects of the embodiments of the present invention in order to best express the present invention. Embodiments of the invention.
The herbicidal composition of the present invention includes, as an active ingredient, a pyridosulfuronium compound represented by the following formula 1. The pyridosulfuronium compound is a mixture of isomers of red and threo forms, and the isomer mixture includes 92 weight % Or more red type:
Where n represents an integer from 1 to 3, R is a hydrogen atom or a C1 to C4 alkyl group, and 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.
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. base.
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 may be, for example, at least one selected from the group consisting of N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl]- 2- (2-fluoro-1-methoxyethoxyl-n-propyl) pyridine-3-sulfonamide, N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl ] -2- (2-fluoro-1-hydroxyethoxyl-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-dimethoxypyrimidin-2-yl ) Aminocarbonyl] -2- (2-fluoro-1- (3-methoxypropylhydrazone) oxy-n-propyl) pyridine-3-sulfonamide, N-[(4,6-dimethoxy Pyrimidin-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-sulfofluorene Amine and N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -4-bromo-2- (2-fluoro-1-methoxyethenyloxy-n-propyl ) Pyridine-3-sulfonamide.
More preferably, the pyridinium sulfonylurea compound represented by Formula 1 may be a compound represented by the following Formula 2 [proposed ISO name: flucetosulfuron]:
Since the compound represented by Formula 1 includes two asymmetric carbons, the compound may exist as an erythro isomer or a threo isomer.
The herbicidal composition of the present invention includes a compound represented by Formula 1 which is a mixture of isomers (including red and threo forms). Here, a red form in an amount of 92% by weight or more based on the total amount of the isomer mixture is included. More preferably, a red form may be included in an amount of 95% by weight or more based on the total amount of the isomer mixture. Even more preferably, a red form may be included in an amount of 95% to 99% by weight based on the total amount of the isomer mixture.
Since the red form is included in an amount of 92% by weight or more based on the total amount of the isomer mixture (including the red form and the threo form), it exhibits excellent herbicidal activity, and even when stored at high temperature for a long time due to Low decomposition rate to ensure stability.
When only the red form of the compound represented by Formula 1 is included, the production efficiency is greatly reduced. When the threo form of only the compound represented by Formula 1 is included, the herbicidal activity is reduced and the decomposition rate is greatly increased, which results in a decrease in stability. In addition, when the compound represented by Formula 1 exists as a mixture of isomers (including erythroform and threotype), but the erythroform content in the isomer mixture is less than 92% by weight, the herbicidal activity decreases, and The decomposition rate increases. In particular, in the case of liquid formulations, the stability is further reduced due to hydrolysis, which makes it difficult to store at high temperatures for a long time.
In the present invention, a herbicidal composition including an isomer mixture of a compound represented by Formula 1 may be used in the form of a universal herbicidal composition formulation. The herbicidal composition including the isomer mixture may additionally include a carrier, a surfactant, or an additive (generally used in the field of formulations, as needed), and may be used in various formulations. Each of the carriers and additives may be solid or liquid, especially useful ingredients in the formulation field, such as natural or synthetic inorganic substances, solvents, dispersants, wetting agents, adhesives, thickeners, adhesives Agent.
For example, the herbicidal composition can be prepared as at least one formulation selected from the group consisting of: suspension concentrates, diffusion oils, wettable powders, water-dispersible granules, dispersible powders, dispersants, Pills, granules, and lozenges. More preferably, the herbicidal composition may be a suspension concentrate. When the herbicidal composition is a suspension concentrate, the herbicidal composition may additionally include a buffering agent, a surfactant, and an antifreeze blend. In the case of suspension concentrates, the manufacturing process is relatively simple, ecologically friendly, and simple and efficient for spraying, but its stability is reduced due to decomposition caused by hydrolysis. However, since the isomer form of the herbicidal composition of the present invention (including the red form and threo form) includes the red form in an amount of 92% by weight or more, the stability is greatly increased. As a result, decomposition due to the hydrolysis of such suspension concentrate formulations is reduced and can be stored for long periods at high temperatures.
The herbicidal composition can be prepared into various formulations, for example, by mixing and / or pulverizing an active ingredient with a solvent, a solid carrier, a surfactant, or other additives according to a known method.
The following can be used as solvents: aromatic hydrocarbons, such as xylene mixtures or substituted naphthalenes; alcohols and glycols, such as ethanol, ethylene glycol, ethylene glycol monomethyl ether, or ethylene glycol monoethyl ether and their ethers and Esters; ketones, such as cyclohexanone; strong polar solvents, such as N-methyl-2-pyrrolidone, dimethylarsine, and dimethylformamide; and epoxidized or unepoxidized vegetable oils, such as Epoxidized coconut oil and soybean oil; or water. Such solvents can be used as solvents for liquid formulations or as co-solvents for granular formulations.
As examples of solid carriers commonly used in dispersants and granular formulations, there are comminuted natural minerals such as talc, kaolin, montmorillonite, pyrophyllite, bentonite, and calcium carbonate, absorbent carriers such as zeolite , And sand. In addition, various pre-pulverized inorganic or organic materials can be used.
The surfactant may be selected from non-ionic, cationic and / or anionic surfactants, which exhibit satisfactory dispersing, wetting, and lubricating properties, depending on the properties of the compound represented by Formula 1 to be formulated.
In terms of a more preferable method of administering a herbicidal composition including an isomer mixture of a compound represented by Formula 1, a method of wetting a plant habitat with a liquid formulation or a method of solid state (e.g., a granular formulation) The active ingredient is added to the soil (soil treatment) to reach the plant through the soil or water through the roots and stems. Alternatively, the herbicidal activity of the composition can be exhibited by directly administering to the leaves of a plant (leaf application). The frequency and rate of administration may vary depending on the biological characteristics of the plant, climate, and soil environment.
Hereinafter, specific embodiments of the present invention will be described. However, it should be understood that this embodiment is not provided to limit the scope of the present invention and all alternatives and modifications within the scope of the accompanying patent application are included in the present invention. Therefore, the following specific embodiments will be carefully explained for the sake of explanation, and methods and aspects will be provided for easy understanding.
The following examples are provided for the purpose of illustration only to illustrate to those of ordinary skill in the art how the provided compounds, compositions, and methods are made and evaluated. Therefore, the following examples are not intended to limit the scope which the inventors consider to be the present invention. There are many variations and combinations that can be used to optimize the following conditions: reaction conditions, ingredient concentrations, desired solvents, solvent mixtures, temperature, pressure, other reaction parameters, and product properties such as purity and yield. These are considered to be included in the scope of the present invention. Any combination of all possible variations is included within the scope of the invention, unless otherwise indicated herein or unless clearly contradicted by context.
實施例 1
將水加到K2
HPO4
與KH2
PO4
以製備總共1 L之溶液，藉此製備0.1 M磷酸鹽緩衝劑。其次，把3.0重量份的CR-DOS70P(二(2-乙基己基)磺琥珀酸鹽，鈉鹽，Cas No. 577-11-7)、1.0重量份之NK-SU500 (蔗糖十二烷酸酯，Cas No. 25339-99-5)、與0.2重量份的作為消泡劑之SAG-622(由Momentive製造)加到65.8重量份的緩衝劑，接著充分混合。在均勻混合狀態下，將10.0重量份的包括96重量%之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-氟丙基甲氧基乙酸酯(氟吡磺隆(flucetosulfuron)
，FTS)的赤型與4重量%之其蘇型之異構物混合物加到該混合物，接著用攪拌器充分混合。把玻璃珠加到所得混合物以進行粉碎。進行此粉碎直到平均粒徑達到1至2 µm。從而，製備好濕部分。
其次，將0.1重量份之X.G(三仙膠，Cas No. 11138-66-2)與0.2重量份的M.V [5-氯-2-甲基-4-異噻唑啉-3-酮(Cas No. 26172-55-4)與2-甲基-4-異噻唑啉-3-酮(Cas No. 2682-20-4)]加到3.0重量份之P.G(丙二醇，Cas No. 57-55-6)，接著在攪拌下充分混合。其次，加入16.7重量份的0.1 M磷酸鹽緩衝劑，接著在攪拌下充分混合。從而，製備好稠化部分。
其次，把30重量份之稠化部分加到70重量份的濕部分，接著在攪拌下充分混合。從而，製備好具有懸浮濃縮物調配物之除草組成物。
實施例 2
以同於實施例1中之方式製備具有懸浮濃縮物調配物的除草組成物，但是使用包括92重量%之FTS的赤型與8重量%之其蘇型之異構物混合物。
實施例 3
在20重量份之Celite 281 (煅燒矽藻土，Cas No. 91053-39-3)上吸附15重量份的CR-PE62 (聚乙二醇聚丙二醇共聚物，Cas No. 9003-11-6)，然後混合10重量份之包括96重量%的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-氟丙基甲氧基乙酸酯(氟吡磺隆，FTS)之赤型與4重量%之其蘇型的異構物混合物、2重量份之NK-EFW(2-萘磺酸，具甲醛的聚合物，鈉鹽，Cas No. 36290-04-7)、3重量份之NK-D425 (2-萘磺酸，具甲醛的聚合物，鈉鹽，Cas No. 36290-04-7)、1重量份之CR-SDS(十二烷基硫酸鈉，Cas No. 151-21-3)、與10重量份的CR-UF100F(脲-甲醛樹脂(CAS no.9011-05-6))。其次，混合作為剩餘部分之滑石以使得組成物總量為100重量份，接著使用空氣噴射磨機粉碎。將10至12重量份的水加到經粉碎之混合物，接著捏和，使用造粒機造粒，然後在約80℃下熱風乾燥。從而，製備好具有水分散性粒劑調配物的除草組成物。
比較例 1
以同於實施例1中之方式製備具有懸浮濃縮物調配物的除草組成物，但是使用包括88重量%之FTS的赤型與12重量%之其蘇型之異構物混合物。
比較例 2
以同於實施例1中之方式製備具有懸浮濃縮物調配物的除草組成物，但是使用包括85重量%之FTS的赤型與15重量%之其蘇型之異構物混合物。
比較例 3
以同於實施例3中之方式製備具有水分散性粒劑調配物的除草組成物，但是使用包括88重量%之FTS的赤型與12重量%之其蘇型之異構物混合物。
[ 實驗例：除草組成物之儲存穩定性的評估 ]
為評估實施例1至3與比較例1至3之除草組成物的儲存穩定性，在用聚乙烯(PE)製成之塑膠瓶中填充約100 g的液體樣本各者，及在銀箔包封填充粒狀樣本，接著密封。其次，將包封各者在保持於54(±2)℃的烘箱中儲存4週，然後使用HPLC(由Waters製造)測量活性成分之面積值以評估分解速率。結果概述在下表1中。
HPLC分析條件如下：
管柱：100 mm×4.6 mm內徑“Capcell Pak” C18管柱，3 µm粒子
移動相：乙腈/水(0.02 M乙酸銨+0.1 M乙酸) = 32/68
流率：1.0 mL/分。
管柱溫度：30℃
注射體積：10 µl
檢測器波長：254 nm
操作時間：20分。
Example 1
Water was added to K 2 HPO 4 and KH 2 PO 4 to prepare a total of 1 L of a solution, thereby preparing a 0.1 M phosphate buffer. Next, 3.0 parts by weight of CR-DOS70P (bis (2-ethylhexyl) sulfosuccinate, sodium salt, Cas No. 577-11-7), 1.0 parts by weight of NK-SU500 (sucrose dodecanoic acid) Ester, Cas No. 25339-99-5), and 0.2 parts by weight of SAG-622 (manufactured by Momentive) as a defoamer were added to 65.8 parts by weight of a buffering agent, followed by thorough mixing. In a uniformly mixed state, 10.0 parts by weight including 96% by weight of 1- (3-{[((4,6-dimethoxy-pyrimidin-2-yl) aminomethylamidino] aminesulfonyl}- 2-pyridyl) -2-fluoropropylmethoxyacetate (flucetosulfuron)
A mixture of the red form of FTS) and an isomer of 4 wt% of its threo form was added to the mixture, followed by thorough mixing with a stirrer. Glass beads were added to the obtained mixture to perform pulverization. This pulverization is performed until the average particle size reaches 1 to 2 µm. Thus, a wet portion is prepared.
Next, 0.1 parts by weight of XG (Sanxian gum, Cas No. 11138-66-2) and 0.2 parts 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)] are added to 3.0 parts by weight of PG (propylene glycol, Cas No. 57-55- 6), then mix well with stirring. Next, 16.7 parts by weight of a 0.1 M phosphate buffer was added, followed by thorough mixing with stirring. Thus, a thickened portion is prepared.
Next, 30 parts by weight of the thickened portion was added to 70 parts by weight of the wet portion, followed by thorough mixing with stirring. Thus, a herbicidal composition having a suspension concentrate formulation is prepared.
Example 2
A herbicidal composition having a suspension concentrate formulation was prepared in the same manner as in Example 1, but using a mixture of isomers including a red form of 92% by weight of FTS and an 8% by weight of its threo form.
Example 3
Adsorbed 15 parts by weight of CR-PE62 (polyethylene glycol polypropylene glycol copolymer, Cas No. 9003-11-6) on 20 parts by weight of Celite 281 (calcined diatomaceous earth, Cas No. 91053-39-3) And then mixed with 10 parts by weight including 96% by weight of 1- (3-{[((4,6-dimethoxy-pyrimidin-2-yl) aminomethylamidino] aminesulfonyl} -2-pyridyl ) 2-Fluoropropylmethoxyacetate (fluprazuron, FTS) mixture of erythro form and 4% by weight of its threo form, 2 parts by weight of NK-EFW (2-naphthalenesulfonate Acid, polymer with formaldehyde, sodium salt, Cas No. 36290-04-7), 3 parts by weight of NK-D425 (2-naphthalenesulfonic acid, polymer with formaldehyde, sodium salt, Cas No. 36290-04 -7), 1 part by weight of CR-SDS (sodium dodecyl sulfate, Cas No. 151-21-3), and 10 parts by weight of CR-UF100F (urea-formaldehyde resin (CAS no. 9011-05- 6)). Next, the remaining talc was mixed so that the total amount of the composition was 100 parts by weight, followed by pulverization using an air jet mill. 10 to 12 parts by weight of water is added to the pulverized mixture, followed by kneading, granulation using a granulator, and then hot air drying at about 80 ° C. Thus, a herbicidal composition having a water-dispersible granule formulation is prepared.
Comparative Example 1
A herbicidal composition having a suspension concentrate formulation was prepared in the same manner as in Example 1, but using a mixture of isomers including a red form of 88% by weight of FTS and a 12% by weight of its threo form.
Comparative Example 2
A herbicidal composition having a suspension concentrate formulation was prepared in the same manner as in Example 1, but using a mixture of isomers including a red form of 85% by weight of FTS and a 15% by weight of its threo form.
Comparative Example 3
A herbicidal composition having a water-dispersible granule formulation was prepared in the same manner as in Example 3, but using an isomer mixture of a red form including 88% by weight of FTS and 12% by weight of its threo form.
[ Experimental example: Evaluation of storage stability of herbicidal composition ]
In order to evaluate the storage stability of the herbicidal compositions of Examples 1 to 3 and Comparative Examples 1 to 3, each of approximately 100 g of a liquid sample was filled in a plastic bottle made of polyethylene (PE), and encapsulated in silver foil Fill the granular sample and seal. Next, each package was 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: 100 mm × 4.6 mm ID “Capcell Pak” C18 column, 3 µm particle mobile phase: acetonitrile / water (0.02 M ammonium acetate + 0.1 M acetic acid) = 32/68
Flow rate: 1.0 mL / min.
Column temperature: 30 ℃
Injection volume: 10 µl
Detector wavelength: 254 nm
Operating time: 20 minutes.