在作物栽培技術中，重要的是藉由控制抑制作物生長之雜草以保護作物。為了降低由作物生長區域中產生的雜草所引起之損害，諸如降低作物生長或產率，已發展出能夠有效控制且對作物安全的除草活性材料。迄今已發展的許多除草活性材料經登記用於特定作物及用於控制雜草。較佳的是用於控制在生長此等作物之區域中產生的雜草之除草活性材料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，包括除草活性材料之除草組成物已發展成可濕性粉劑、可乳化濃縮物、水分散性粒劑、粒劑或懸浮濃縮物之調配物且用作為除草劑。然而，可濕性粉劑、可乳化濃縮物或水分散性粒劑調配物通常係藉由以水稀釋成預定濃度而製備成可噴霧液體，但是使其均勻地噴霧在稻田或田地的整個表面上卻有過高的成本及時間的問題，因為其應以大量施予。粒劑調配物可直接使用及因此可解決可濕性粉劑、可乳化濃縮物及水分散性粒劑調配物的問題。然而，粒劑調配物具有以除草劑總量為基礎計而相對低含量的除草活性材料、必需包括製備除草劑之輔助劑、具有複雜的製備方法，包括粉碎、混合、捏合、造粒、乾燥、分級等，且產生噴霧染污斑。為了克服該等調配物的問題，所以發展出具有相對簡單的製備方法、具有環保性且簡單及有效地噴霧之懸浮液濃縮調配物。同時，當除草組成物被用作為各種調配物中所製備之除草劑時，則重要的是確保除草組成物的穩定性，即使當長時間貯存時。
下式之化合物(提出之ISO名稱：氟吡磺隆(flucetosulfuron))為基於磺醯脲之除草活性材料且已先前於韓國專利第10-0399366號(韓國專利申請案第10-2000-0059990號)中說明為除草活性材料。
[式a]
氟吡磺隆在土壤或葉面處理時對作物(諸如稻米、小麥、大麥)(適當的使用量：10至40克活性成分/公頃)及禾草(適當的使用量：50至200克活性成分/公頃)是安全的，且已知對各種類型之雜草展現極佳的除草效應，諸如闊葉型雜草、禾草雜草、莎草雜草、一年生雜草和多年生雜草。
然而，仍有確保包括此等基於磺醯脲之除草活性材料的除草組成物之穩定性的問題。特別難以長時間貯存懸浮液濃縮(SC)調配物，因為當在高溫下貯存時，穩定性係由於水解而進一步降低。
[先前文獻]
[專利文獻]
韓國專利第10-0399366號In crop cultivation technology, it is important to protect crops by controlling weeds that inhibit crop growth. In order to reduce damage caused by weeds generated in crop growing areas, such as reducing crop growth or yield, herbicidally active materials that can be effectively controlled and safe to crops have been developed. Many herbicidal active materials that have been developed to date are registered for specific crops and for controlling weeds. It is preferable that the herbicidal active material for controlling weeds generated in the area where these crops are grown has high herbicidal activity and a broad herbicidal spectrum, and is safe for the environment and crops.
At the same time, herbicidal compositions including herbicidally active materials have been developed into formulations of wettable powders, emulsifiable concentrates, water-dispersible granules, granules or suspension concentrates and have been used as herbicides. However, wettable powders, emulsifiable concentrates, or water-dispersible granule formulations are usually prepared as a sprayable liquid by diluting it with water to a predetermined concentration, but spraying it uniformly over the entire surface of a paddy field or field However, there is a problem of excessive cost and time, because it should be given in large quantities. Granule formulations can be used directly and therefore the problems of wettable powders, emulsifiable concentrates and water-dispersible granule formulations can be solved. However, granule formulations have a relatively low content of herbicidal active materials based on the total amount of herbicides, must include auxiliary agents for the preparation of herbicides, and have complex preparation methods, including crushing, mixing, kneading, granulating, drying , Classification, etc., and produce spray stains. In order to overcome the problems of such formulations, suspension concentrate formulations with relatively simple preparation methods, environmental protection, simple and effective spraying have been developed. Meanwhile, when the herbicidal composition is used as a herbicide prepared in various formulations, it is important to ensure the stability of the herbicidal composition even when stored for a long time.
The compound of the following formula (the proposed ISO name: flucetosulfuron) is a sulforamide-based herbicidally active material and has been previously disclosed in Korean Patent No. 10-0399366 (Korean Patent Application No. 10-2000-0059990 ) Is described as a herbicidally active material.
[Formula a]
Flumesulfuron-methyl is active on crops (such as rice, wheat, barley) (appropriate amount: 10 to 40 g active ingredient / ha) and grass (appropriate amount: 50 to 200 g) Composition / ha) is safe and is known to exhibit excellent herbicidal effects on various types of weeds, such as broad-leaved weeds, grass weeds, sedge weeds, annual weeds, and perennial weeds.
However, there is still a problem of ensuring the stability of a herbicidal composition including such a sulfonylurea-based herbicidal active material. It is particularly difficult to store suspension concentrate (SC) formulations for long periods of time, as stability is further reduced due to hydrolysis when stored at high temperatures.
[Previous Literature]
[Patent Literature]
Korean Patent No. 10-0399366
[技術問題]
為了解決習知的問題，本發明旨在提供具有極佳的除草活性、具有高穩定性(即使當製備成液體調配物時)及易於高溫下經長時間貯存之液體除草組成物。
[技術手段]
本發明提供液體除草組成物，其包含：
活性成分，其包含以下列式1代表的吡啶磺醯脲化合物；及
具有5.80至6.25之pH的緩衝劑：
[式1]
在式1中，
n為1至3的整數，
R為氫或具有1至4個碳原子的烷基，
R’為氫、具有1至4個碳原子的烷基、具有1至3個碳原子的鹵烷基、鹵基或具有1至2個碳原子的烷氧基，且
X和Y各自獨立為具有1至2個碳原子的烷基、具有1至2個碳原子的烷氧基、具有1至2個碳原子的鹵烷氧基或鹵基。
[有利效果]
根據本發明，可提供作為除草劑之液體除草組成物，其具有極佳的除草活性、低的分解率及極佳的穩定性(即使當製備成液體調配物、特別為懸浮液濃縮(SC)調配物時亦然)及易於高溫下經長時間貯存。
[本發明之模式]
本發明將於下文詳細說明。
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，而應解釋為對應於本發明之具體實例的技術態樣之含義及觀念，其以本發明者可適當地定義術語而最適當地表達他/她的發明之原理為基礎。
根據本發明之例示性具體實例的液體除草組成物可包括活性成分及緩衝劑，其中活性成分可包含以下列式1代表的吡啶磺醯脲化合物，且緩衝劑可具有5.80至6.25之pH。
[式1]
在式1中，n為1至3的整數，R為氫或具有1至4個碳原子的烷基，R’為氫、具有1至4個碳原子的烷基、具有1至3個碳原子的鹵烷基、鹵基或具有1至2個碳原子的烷氧基，且X和Y各自獨立為具有1至2個碳原子的烷基、具有1至2個碳原子的烷氧基、具有1至2個碳原子的鹵烷氧基或鹵基。
更佳地，在代表吡啶磺醯脲化合物的式1中，n為1或2的整數，R為氫或甲基，R’為氫、鹵基或甲基，且X和Y各自獨立為甲氧基，且甚至更佳地，n為1或2的整數，R為甲基，R’為氫、氯(Cl)、溴(Br)或甲基，且X和Y各自獨立為甲氧基。
根據本發明之例示性具體實例的式1之吡啶磺醯脲化合物可為一或多種選自下列之化合物：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，以式1代表的吡啶磺醯脲化合物可為下列式2之化合物(提出之ISO名稱：氟吡磺隆)。
[式2]
在根據本發明之例示性具體實例的液體除草組成物中，活性成分的內含量可以相對於100重量份的液體除草組成物而為1至50重量份，較佳為1至25重量份，且更佳為3至15重量份。當液體除草組成物包括少於1重量份的活性成分時，則由於除草組成物中的活性成分含量非常少，即使僅分解少量的活性成分，但相對的分解率(%)快速增加，導致降低的除草效應，且當包括超過50重量份的活性成分時，則可能引起產物具有降低的物理及/或化學特性的問題，例如增加的黏度。
同時，在液體調配物的例子中，由於包括以式1代表的吡啶磺醯脲化合物之活性成分的水解而有穩定性降低的問題。然而，根據本發明之例示性具體實例的液體除草組成物係藉由適當地控制緩衝液之pH以顯著地降低分解率而確保穩定性，即使以液體調配物。
根據本發明之例示性具體實例的液體除草組成物可具有5.80至6.25之pH，較佳為6.00至6.20之pH，且更佳為6.10至6.20之pH，且pH可以緩衝劑控制。亦即，本發明之液體除草組成物可包括具有5.80至6.25，較佳為6.00至6.20，且更佳為6.10至6.20之pH的緩衝劑。在本發明中，液體除草組成物之pH可由於液體除草組成物的水解而為影響分解率的因素之一，且若pH係在5.80至6.25之範圍內，即時以長期高溫貯存液體除草組成物，分解率仍為低的，且因此明顯地改進穩定性。
緩衝劑較佳為基於磷酸鹽之緩衝劑、碳酸與碳酸氫鈉之混合溶液(H2
CO3
/NaHCO3
之混合溶液)或Bis-Tris溶液，且尤其包括磷酸氫二鉀(K2
HPO4
)、磷酸二氫鉀(KH2
PO4
)、磷酸氫二鈉(Na2
HPO4
)、磷酸二氫鈉(NaH2
PO4
)、碳酸與碳酸氫鈉之混合溶液(H2
CO3
/NaHCO3
之混合溶液)及Bis-Tris溶液中之一或多者，且更尤其包括磷酸氫二鉀、磷酸二氫鉀、磷酸氫二鈉、磷酸二氫鈉或其混合物。
另外，當緩衝劑為混合溶液時，則可控制緩衝劑之混合比，使得整體緩衝劑具有5.80至6.25之pH。
本文所使用之術語「Bis-Tris溶液」為含有Bis-Tris之溶液，該Bis-Tris為那些一般熟習此項技術領域者熟知的化合物，且IUPAC名稱為2-[雙(2-羥乙基)胺基]-2-(羥甲基)丙-1,3-二醇及CAS編號為6976-37-0。
而且，緩衝劑可為具有0.03至0.2M，較佳為0.05至0.1M之濃度的溶液。當緩衝劑滿足上述的數字範圍時，則進一步降低液體除草組成物的分解率及改進穩定性。另外，如本發明，當濃度為0.2M或更低時，則由於極佳的黏度而易於製備除草組成物。
根據本發明之例示性具體實例的液體除草組成物可進一步包括界面活性劑，其促進活性成分的可濕性及分散性且有助於維持組成物經長時間的懸浮穩定性。
另外，界面活性劑的內含量可以相對於100重量份的液體除草組成物而為1至20重量份，尤其為1至10重量份。
界面活性劑的類型可為陰離子界面活性劑及非離子界面活性劑(特別為非離子界面活性劑)中的聚合性界面活性劑。特定言之，陰離子界面活性劑可為基於磺基琥珀酸二辛酯鈉鹽、基於磺基琥珀酸二辛酯鈣鹽或基於α-烯烴磺酸鹽之界面活性劑，及非離子界面活性劑可為以包括環氧乙烷單元之環氧乙烷接枝共聚物、氧乙烯與氧丙烯之共聚物、聚氧乙烯三苯乙烯基苯醚、基於羧酸酯之聚合物或蔗糖月桂酸酯為基礎之界面活性劑。
根據本發明之例示性具體實例的液體除草組成物可進一步包括防凍劑，其內含量可以相對於100重量份的總液體除草組成物而為0.01至10重量份，尤其為1.0至6.0重量份，且更尤其為2.0至4.0重量份，且甚至更尤其為2.0至3.0重量份，因為其具有防凍效應及大大地改進分解率。
另外，防凍劑可包括基於二醇之化合物及基於醇之化合物，且基於二醇之化合物尤其可包括丙二醇(P.G.)、乙二醇、二乙二醇、二丙二醇及三丙二醇，及基於醇之化合物可包括甘油及異丙醇，且較佳為丙二醇。
在本發明中，當上述類型之防凍劑的內含量係在上述的數字範圍內時，則其具有極佳的防凍效應及降低液體除草組成物的分解率之效應。另外，當防凍劑的含量比超過上述的數字範圍時，則可增加液體除草組成物的分解率且因此可降低穩定性。當防凍劑的內含量少於上述的數字範圍時，則其含量無意義且不可能實現充分的防凍效應。
根據本發明之例示性具體實例的液體除草組成物可包括增稠劑，且增稠劑的內含量較佳地以相對於100重量份的總液體除草組成物而為0.001至1.2重量份或更少，尤其為0.05至1.0重量份，且更尤其為0.05至0.15重量份。
另外，增稠劑可為通常可用於相關技術中的任何增稠劑而沒有限制，且尤其可包括三仙膠、皂土、矽礬石黏土、微晶高嶺石、阿拉伯膠、瓜爾膠、基於纖維素之化合物、藻酸鈉、澱粉或其混合物，且較佳為三仙膠、微晶高嶺石或其混合物。
根據本發明之例示性具體實例，當增稠劑的內含量係在上述的數字範圍內時，則改進增稠效應且降低液體除草組成物的分解率。
根據本發明之例示性具體實例，在液體除草組成物中，除了上述組份以外，若必要時可進一步包括消泡劑、保存劑、穩定劑、顏料等。
而且，根據本發明之例示性具體實例，液體除草組成物可由緩衝劑所組成，該緩衝劑為除了作為活性成分之以式1代表的化合物、界面活性劑、防凍劑、增稠劑及添加劑(諸如消泡劑、保存劑、穩定劑等)的含量以外的剩餘物。換言之，緩衝劑的含量可為除了相對於100重量%之液體除草組成物的其他組份含量以外的量。
另外，根據本發明之例示性具體實例，可使用任何液體調配物作為液體除草組成物之調配物而沒有限制，且尤其為液體溶液或懸浮液濃縮(SC)調配物，且更尤其為懸浮液濃縮調配物。懸浮液濃縮調配物在此可為水分散型懸浮液調配物。
當包括上述活性成分之除草組成物製備成懸浮液濃縮調配物時，則由於水解的高分解率而難以長期貯存除草組成物。因此，在本發明中，具有改進之穩定性及易於經長時間貯存之液體除草組成物可藉由控制液體除草組成物之pH來製備。
根據本發明之例示性具體實例的液體除草組成物包括控制pH之緩衝劑，儘管組成物為液體，但是由於液體除草組成物的受控制之pH範圍，使得吡啶磺醯脲化合物之磺醯脲基團免於水解而顯著地降低由於水解的分解率，由此確保液體調配物的穩定性及促進長期貯存。因此，本發明可解決具有液體調配物之習知的除草組成物之低穩定性的問題，該組成物含有因大部分的活性成分水解所造成的少量活性成分，因為組成物係由於水解而具有非常高的分解率。[technical problem]
In order to solve the conventional problems, the present invention aims to provide a liquid herbicidal composition having excellent herbicidal activity, high stability (even when prepared as a liquid formulation), and easy storage at high temperature for a long time.
[Technical means]
The present invention provides a liquid herbicidal composition comprising:
An active ingredient comprising a pyridosulfuronium compound represented by the following formula 1; and a buffering agent having a pH of 5.80 to 6.25:
[Formula 1]
In Equation 1,
n is an integer from 1 to 3,
R is hydrogen or an alkyl group having 1 to 4 carbon atoms,
R 'is hydrogen, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, a halo group, or an alkoxy group having 1 to 2 carbon atoms, and
X and Y are each independently an alkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, a haloalkoxy group or a halo group having 1 to 2 carbon atoms.
[Beneficial effect]
According to the present invention, a liquid herbicidal composition can be provided as a herbicide, which has excellent herbicidal activity, low decomposition rate, and excellent stability (even when prepared as a liquid formulation, especially for suspension concentration (SC) The same is true when formulating) and easy to store at high temperature for a long time.
[Mode of the invention]
The present invention will be described in detail below.
The terms or words used in the specification and subsequent patent applications should not be limited to common or dictionary meanings, but should be interpreted as meanings and concepts corresponding to the technical aspects of specific examples of the present invention. The person can define the term appropriately and most appropriately express the principle of his / her invention.
The liquid herbicidal composition according to an exemplary embodiment of the present invention may include an active ingredient and a buffering agent, wherein the active ingredient may include a pyridosulfuronium compound represented by the following Formula 1, and the buffering agent may have a pH of 5.80 to 6.25.
[Formula 1]
In Formula 1, n is an integer of 1 to 3, R is hydrogen or an alkyl group having 1 to 4 carbon atoms, R ′ is hydrogen, an alkyl group having 1 to 4 carbon atoms, and 1 to 3 carbons Atomic haloalkyl, halo or alkoxy having 1 to 2 carbon atoms, and X and Y are each independently alkyl having 1 to 2 carbon atoms, alkoxy having 1 to 2 carbon atoms Haloalkoxy or halo having 1 to 2 carbon atoms.
More preferably, in Formula 1 representing a pyridinium sulfonylurea compound, n is an integer of 1 or 2, R is hydrogen or methyl, R ′ is hydrogen, halo, or methyl, and X and Y are each independently Oxygen, and even more preferably, n is an integer of 1 or 2, R is methyl, R 'is hydrogen, chlorine (Cl), bromine (Br), or methyl, and X and Y are each independently methoxy .
The pyridinium sulfonylurea compound of Formula 1 according to an exemplary embodiment of the present invention may be one or more compounds 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) amino Carbonyl] -2- (2-fluoro-1-hydroxyethytoxy-n-propyl) pyridine-3-sulfonamide, N-[(4,6-dimethoxypyrimidin-2-yl) amino Carbonyl] -2- (2-fluoro-1- (3-hydroxypropanyl) oxy-n-propyl) pyridine-3-sulfonamide, N-[(4,6-dimethoxypyrimidine-2- (Amino) aminocarbonyl] -2- (2-fluoro-1- (3-methoxypropylhydrazine) oxy-n-propyl) pyridine-3-sulfonamide, N-[(4,6-dimethyl Oxypyrimidin-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-methoxyacetamido-n-propyl) pyridine-3-sulfonate Amido 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 may be a compound of Formula 2 below (proposed ISO name: flursulfuron-methyl).
[Formula 2]
In the liquid herbicidal composition according to the illustrative specific example of the present invention, the internal content of the active ingredient may be 1 to 50 parts by weight, preferably 1 to 25 parts by weight relative to 100 parts by weight of the liquid herbicidal composition, and More preferably, it is 3 to 15 parts by weight. When the liquid herbicidal composition includes less than 1 part by weight of the active ingredient, since the content of the active ingredient in the herbicidal composition is very small, even if only a small amount of the active ingredient is decomposed, the relative decomposition rate (%) increases rapidly, resulting in a decrease Herbicidal effects, and when including more than 50 parts by weight of active ingredients, it may cause problems with products having reduced physical and / or chemical properties, such as increased viscosity.
Meanwhile, in the example of the liquid formulation, there is a problem that the stability is reduced due to the hydrolysis of the active ingredient including the pyridosulfuronium compound represented by Formula 1. However, the liquid herbicidal composition according to the illustrative embodiment of the present invention ensures stability by appropriately controlling the pH of the buffer solution to significantly reduce the decomposition rate, even with liquid formulations.
The liquid herbicidal composition according to an exemplary embodiment of the present invention may have a pH of 5.80 to 6.25, preferably a pH of 6.00 to 6.20, and more preferably a pH of 6.10 to 6.20, and the pH may be controlled by a buffer. That is, the liquid herbicidal composition of the present invention may include a buffering agent having a pH of 5.80 to 6.25, preferably 6.00 to 6.20, and more preferably 6.10 to 6.20. In the present invention, the pH of the liquid herbicidal composition can be one of the factors affecting the decomposition rate due to the hydrolysis of the liquid herbicidal composition, and if the pH is in the range of 5.80 to 6.25, the liquid herbicidal composition is stored at high temperature for a long time immediately. The decomposition rate is still low, and therefore the stability is significantly improved.
The buffering agent is preferably a phosphate-based buffering agent, a mixed solution of carbonic acid and sodium bicarbonate (a mixed solution of H 2 CO 3 / NaHCO 3 ) or a Bis-Tris solution, and especially includes dipotassium hydrogen phosphate (K 2 HPO 4 ), Potassium dihydrogen phosphate (KH 2 PO 4 ), disodium hydrogen phosphate (Na 2 HPO 4 ), sodium dihydrogen phosphate (NaH 2 PO 4 ), mixed solution of carbonic acid and sodium bicarbonate (H 2 CO 3 / NaHCO 3 ) and one or more of Bis-Tris solutions, and more particularly include dipotassium hydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, or a mixture thereof.
In addition, when the buffer is a mixed solution, the mixing ratio of the buffer can be controlled so that the overall buffer has a pH of 5.80 to 6.25.
As used herein, the term "Bis-Tris solution" refers to a solution containing Bis-Tris, which is a compound well known to those skilled in the art, and the IUPAC name is 2- [bis (2-hydroxyethyl) ) Amino] -2- (hydroxymethyl) propane-1,3-diol and CAS number 6976-37-0.
Moreover, the buffering agent may be a solution having a concentration of 0.03 to 0.2M, preferably 0.05 to 0.1M. When the buffering agent satisfies the above-mentioned numerical range, the decomposition rate of the liquid herbicidal composition is further reduced and the stability is improved. In addition, according to the present invention, when the concentration is 0.2M or less, it is easy to prepare a herbicidal composition due to excellent viscosity.
The liquid herbicidal composition according to the illustrative embodiment of the present invention may further include a surfactant, which promotes the wettability and dispersibility of the active ingredient and helps maintain the suspension stability of the composition over a long period of time.
In addition, the internal content of the surfactant may be 1 to 20 parts by weight, and particularly 1 to 10 parts by weight relative to 100 parts by weight of the liquid herbicidal composition.
The type of the surfactant may be an anionic surfactant and a polymerizable surfactant in a nonionic surfactant (particularly, a nonionic surfactant). Specifically, the anionic surfactant may be a surfactant based on sodium dioctyl sulfosuccinate, a calcium salt based on dioctyl sulfosuccinate, or an α-olefin sulfonate, and a nonionic surfactant It may be an ethylene oxide graft copolymer including ethylene oxide units, a copolymer of oxyethylene and oxypropylene, a polyoxyethylene tristyryl phenyl ether, a carboxylic acid ester-based polymer, or a sucrose laurate Based surfactants.
The liquid herbicidal composition according to the illustrative specific example of the present invention may further include an antifreeze, and the content thereof may be 0.01 to 10 parts by weight, particularly 1.0 to 6.0 parts by weight relative to 100 parts by weight of the total liquid herbicidal composition. And more particularly 2.0 to 4.0 parts by weight, and even more particularly 2.0 to 3.0 parts by weight, because it has an antifreeze effect and greatly improves the decomposition rate.
In addition, the antifreeze may include diol-based compounds and alcohol-based compounds, and the diol-based compounds may particularly include propylene glycol (PG), ethylene glycol, diethylene glycol, dipropylene glycol, and tripropylene glycol, and alcohol-based compounds. The compound may include glycerol and isopropanol, and is preferably propylene glycol.
In the present invention, when the internal content of the above type of antifreeze is within the above-mentioned numerical range, it has an excellent antifreeze effect and an effect of reducing the decomposition rate of the liquid herbicidal composition. In addition, when the content ratio of the antifreeze exceeds the above-mentioned numerical range, the decomposition rate of the liquid herbicidal composition can be increased and thus the stability can be reduced. When the internal content of the antifreeze is less than the above-mentioned numerical range, its content is meaningless and it is impossible to achieve a sufficient antifreeze effect.
The liquid herbicidal composition according to an illustrative embodiment of the present invention may include a thickener, and the internal content of the thickener is preferably 0.001 to 1.2 parts by weight or more relative to 100 parts by weight of the total liquid herbicidal composition. Less, especially 0.05 to 1.0 parts by weight, and more particularly 0.05 to 0.15 parts by weight.
In addition, the thickener may be any thickener that can be generally used in the related art without limitation, and may particularly include Sanxian gum, bentonite, silicate, clay, kaolinite, acacia, guar, Cellulose-based compounds, sodium alginate, starch, or mixtures thereof, and preferably xanthan gum, microcrystalline kaolinite, or mixtures thereof.
According to an exemplary embodiment of the present invention, when the internal content of the thickener is within the above-mentioned numerical range, the thickening effect is improved and the decomposition rate of the liquid herbicidal composition is reduced.
According to the illustrative specific example of the present invention, in the liquid herbicidal composition, in addition to the above components, if necessary, a defoamer, a preservative, a stabilizer, a pigment, and the like may be further included.
Further, according to an exemplary embodiment of the present invention, the liquid herbicidal composition may be composed of a buffering agent, which is a compound represented by Formula 1 as an active ingredient, a surfactant, an antifreezing agent, a thickener, and an additive ( Such as defoamers, preservatives, stabilizers, etc.). In other words, the content of the buffering agent may be an amount other than the content of other components relative to 100% by weight of the liquid herbicidal composition.
In addition, according to an illustrative specific example of the present invention, any liquid formulation may be used as a formulation of a liquid herbicidal composition without limitation, and is particularly a liquid solution or suspension concentrate (SC) formulation, and more particularly a suspension Concentrate the formulation. Suspension concentrate formulations can be water-dispersible suspension formulations.
When the herbicidal composition including the above active ingredients is prepared as a suspension concentrated formulation, it is difficult to store the herbicidal composition for a long time due to the high decomposition rate of hydrolysis. Therefore, in the present invention, a liquid herbicidal composition having improved stability and easy storage over a long period of time can be prepared by controlling the pH of the liquid herbicidal composition.
The liquid herbicidal composition according to the illustrative embodiment of the present invention includes a pH-controlling buffer. Although the composition is a liquid, due to the controlled pH range of the liquid herbicidal composition, the sulfonylurea group of the pyridosulfuronium compound The mass is free from hydrolysis and significantly reduces the decomposition rate due to hydrolysis, thereby ensuring the stability of the liquid formulation and promoting long-term storage. Therefore, the present invention can solve the problem of low stability of a conventional herbicidal composition having a liquid formulation, which contains a small amount of an active ingredient due to the hydrolysis of most of the active ingredients, because the composition has Very high resolution.
實施例
在下文，為幫助理解本發明，提出例示性實施例。然而，應理解實施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。
實施例1
製備方法大致分成兩個程序，諸如濕部分程序及增稠部分程序，且在室溫下進行。
製備0.1M 磷酸鹽緩衝劑(pH 6.15)：將水添加至K2
HPO4
及KH2
PO4
中以製備1公升溶液。然後將3.0重量份的CR-DOS70P磺基琥珀酸(二(2-乙基己基)酯鈉鹽，Cas編號577-11-7)、1.0重量份的NK-SU500 (蔗糖月桂酸酯，Cas編號25339-99-5)及作為消泡劑之0.2重量份的SAG-622 (Momentive)添加至65.8重量份的緩衝劑中且充分混合。在均化狀態下，將10.0重量份的乙酸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-氟丙基甲氧酯(氟吡磺隆，FTS)添加至混合物中，隨後使用攪拌器充分混合。在此使用玻璃珠研磨混合物，直到平均粒徑成為1至2微米為止，由此獲得濕部分。
然後將0.1重量份的X.G (三仙膠，Cas編號11138-66-2)0.2重量份的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重量份的P.G (丙二醇，Cas編號57-55-6)中且充分攪拌。接著將16.7重量份的0.1M磷酸鹽緩衝劑(pH 6.15)(其中將K2
HPO4
與KH2
PO4
在水中混合)添加至其中，隨後充分攪拌。
將20重量份的增稠部分添加至80重量份的濕部分中且充分攪拌，得到具有懸浮液濃縮調配物之除草組成物。
實施例2
具有懸浮液濃縮調配物之除草組成物係以與實施例1相同的方式製備，除了濕部分緩衝劑及增稠部分緩衝劑之pH改變成5.8以外。
實施例3
具有懸浮液濃縮調配物之除草組成物係以與實施例1相同的方式製備，除了添加2重量份的丙二醇及對增稠部分添加17.7重量份的磷酸鹽緩衝劑以外。
實施例4
具有懸浮液濃縮調配物之除草組成物係以與實施例1相同的方式製備，除了添加4重量份的丙二醇對增稠部分添加15.7重量份的磷酸鹽緩衝劑以外。
比較例1
具有懸浮液濃縮調配物之除草組成物係以與實施例1相同的方式製備，除了濕部分緩衝劑及增稠部分緩衝劑之pH改變成5.5以外。
比較例2
具有懸浮液濃縮調配物之除草組成物係以與實施例1相同的方式製備，除了濕部分緩衝劑及增稠部分緩衝劑之pH改變成6.3以外。
比較例3
具有懸浮液濃縮調配物之除草組成物係以與實施例1相同的方式製備，除了濕部分緩衝劑及增稠部分緩衝劑之pH改變成6.8以外。
比較例4
具有懸浮液濃縮調配物之除草組成物係以與實施例1相同的方式製備，除了濕部分緩衝劑及增稠部分緩衝劑之pH改變成7.4以外。
實驗例：評估液體除草組成物之貯存穩定性
為了評估實施例及比較例的液體除草組成物之貯存穩定性，將約100毫升各樣品填充至聚乙烯瓶中且接著密封，隨後貯存在維持於54(±2)℃之烘箱中4週。接著以HPLC (由Waters製造)測量活性成分之面積值以評估分解率，且將結果顯示於以下表1中。
HPLC分析條件係如下：
管柱：100毫米 X 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
檢測波長：254奈米
操作時間：20分鐘
[表1]
如表1中所示，可確認在實施例1至4中的根據本發明之例示性具體實例的液體除草組成物(其包括作為活性成分的吡啶磺醯脲化合物及具有5.80至6.25之pH的緩衝劑)具有比其中緩衝劑之pH範圍超出本發明之範圍的比較例1至4中的那些液體除草組成物更低的分解率，且因此彼等具有高的穩定性，即使在高溫經長時間的貯存期間亦然。
當實施例中的緩衝劑溶液之pH相同時，亦可觀察出含有2.0至3.0重量份的防凍劑之實施例1和3的分解率甚至更低。
雖然本發明已參考具體的細節(諸如特定的組份等)及有限的實施例和圖形予以說明，但是彼等的提供僅為了有助於全面理解本發明。然而，不應該理解為本發明不受限於該等實施例，且因此那些一般熟習此項技術領域者可自上述說明進行各種修飾及變更。
因此，本發明之範圍不應受限於上文所述之實施例，且意欲使所有的修飾及等效物以及後列的申請專利範圍皆在本發明之範圍內。EXAMPLES In the following, to help understand the present invention, illustrative examples are presented. However, it should be understood that the embodiments are not provided to limit the scope of the present invention, and all alternatives and modifications within the scope of the attached patent application are included in the present invention.
Example 1
The preparation method is roughly divided into two procedures, such as a wet portion procedure and a thickening portion procedure, and is performed at room temperature.
Preparation of 0.1 M phosphate buffer (pH 6.15): Water was added to K 2 HPO 4 and KH 2 PO 4 to prepare a 1 liter solution. Then 3.0 parts by weight of CR-DOS70P sulfosuccinic acid (bis (2-ethylhexyl) ester sodium salt, Cas number 577-11-7), 1.0 parts by weight of NK-SU500 (sucrose laurate, Cas number 25339-99-5) and 0.2 parts by weight of SAG-622 (Momentive) as a defoamer are added to 65.8 parts by weight of the buffer and mixed well. In a homogenized state, 10.0 parts by weight of 1- (3-{[((4,6-dimethoxy-pyrimidin-2-yl) aminomethylamidino] aminesulfonyl} -2-pyridyl) ) -2-Fluoropropylmethoxylate (floxasulfuron, FTS) was added to the mixture, followed by thorough mixing using a stirrer. Here, the mixture was ground using glass beads until the average particle diameter became 1 to 2 micrometers, thereby obtaining a wet portion.
Then 0.1 parts by weight of XG (Sanxian gum, Cas number 11138-66-2) and 0.2 parts by weight of MV [5-chloro-2-methyl-4-isothiazolin-3-one (Cas number 26172-55 -4) and 2-methyl-4-isothiazolin-3-one (Cas No. 2682-20-4)] were added to 3.0 parts by weight of PG (propylene glycol, Cas No. 57-55-6) and stirred well . Next, 16.7 parts by weight of a 0.1 M phosphate buffer (pH 6.15) (where K 2 HPO 4 and KH 2 PO 4 were mixed in water) was added thereto, followed by sufficient stirring.
20 parts by weight of the thickened portion was added to 80 parts by weight of the wet portion and stirred sufficiently to obtain a herbicidal composition having a suspension concentrated formulation.
Example 2
The herbicidal composition with the suspension concentration formulation was prepared in the same manner as in Example 1, except that the pH of the wet portion buffer and the thickened portion buffer was changed to 5.8.
Example 3
The herbicidal composition having the suspension concentrated formulation was prepared in the same manner as in Example 1, except that 2 parts by weight of propylene glycol was added and 17.7 parts by weight of a phosphate buffer was added to the thickened portion.
Example 4
The herbicidal composition with the suspension concentrated formulation was prepared in the same manner as in Example 1, except that 4 parts by weight of propylene glycol was added to the thickened portion and 15.7 parts by weight of a phosphate buffer was added.
Comparative Example 1
The herbicidal composition with the suspension concentrated formulation was prepared in the same manner as in Example 1, except that the pH of the wet portion buffer and the thickened portion buffer was changed to 5.5.
Comparative Example 2
The herbicidal composition with the suspension concentrated formulation was prepared in the same manner as in Example 1, except that the pH of the wet portion buffer and the thickened portion buffer was changed to 6.3.
Comparative Example 3
The herbicidal composition with the suspension concentrated formulation was prepared in the same manner as in Example 1, except that the pH of the wet portion buffer and the thickened portion buffer was changed to 6.8.
Comparative Example 4
The herbicidal composition with the suspension concentration formulation was prepared in the same manner as in Example 1, except that the pH of the wet part buffer and the thick part buffer was changed to 7.4.
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 the examples and comparative examples, about 100 ml of each sample was filled into a polyethylene bottle and then sealed, and then stored at In an oven at 54 (± 2) ° C for 4 weeks. The area value of the active ingredient was then measured by HPLC (manufactured by Waters) to evaluate the decomposition rate, and the results are shown in Table 1 below.
The HPLC analysis conditions are as follows:
Column: 100mm X 4.6mm ID "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 μl Detection wavelength: 254 nm Operating time: 20 minutes
[Table 1]
As shown in Table 1, it was confirmed that the liquid herbicidal composition according to the illustrative specific example of the present invention in Examples 1 to 4 (which includes the pyridosulfuronium compound as an active ingredient and a compound having a pH of 5.80 to 6.25 Buffers) have lower decomposition rates than those of the liquid herbicidal compositions in Comparative Examples 1 to 4 in which the pH range of the buffers exceeds the range of the present invention, and therefore they have high stability even at high temperatures The same goes for the storage period of time.
When the pHs of the buffer solutions in the examples were the same, the decomposition rates of Examples 1 and 3 containing 2.0 to 3.0 parts by weight of the antifreeze were also observed to be even lower.
Although the invention has been described with reference to specific details (such as specific components, etc.) and limited embodiments and figures, they are provided only to assist in a comprehensive understanding of the invention. However, it should not be construed that the present invention is not limited to these embodiments, and therefore those skilled in the art can make various modifications and changes from the above description.
Therefore, the scope of the present invention should not be limited to the embodiments described above, and it is intended that all modifications and equivalents and the scope of the following patent applications are within the scope of the present invention.