TWI702000B - Liquid herbicidal composition - Google Patents

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: [Formula 1]

Description

Liquid herbicidal composition

The present invention relates to a liquid herbicidal liquid composition, which includes active herbicidal ingredients exhibiting excellent herbicidal activity.

In crop cultivation, it is important to protect crops by controlling weeds that inhibit crop growth. In order to reduce the damage due to weeds growing in the cultivation area, such as loss of crop growth or yield, active herbicides that can effectively control weeds and are safe to crops have been developed. Many active herbicides that have been developed so far have been registered for specific crops and for weed control. These herbicidal active substances for controlling weeds growing in the cultivation 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 have been 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 that are usually diluted with water to a predetermined concentration to prepare sprayable solutions, in order to spray them uniformly on the entire surface of the target rice field or field There are high cost and time-consuming problems. Although the problems of wettable powders, emulsifiable concentrates, and water-dispersible granules can be dealt with by using granules that can be used directly without diluting with water, these granules are included on the basis of the total amount of herbicides. Relatively low content of active herbicides must include auxiliary agents used to form herbicides, manufactured by complex methods (including crushing, mixing, grinding, granulating, drying, classification and the like) and having problems due to spraying , Such as stains. In order to cope with these problems, an aqueous suspension formulation has been developed that is relatively simple and does not harm the ecological environment and allows simple and effective spray manufacturing methods. However, in the case of liquid formulations (such as aqueous suspensions), when stored at high temperatures for a long time, the stability of the herbicidal composition decreases, because the specific active ingredient system exhibits excellent herbicidal activity Decomposes due to heat and hydrolysis. Therefore, there is still an urgent need for research on improving the stability of herbicidal compositions that include active ingredients exhibiting excellent herbicidal activity as aqueous suspension formulations. [Related technical documents] [Patent Document] Korean Patent No. 10-0399366

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] Therefore, the present invention is 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 a liquid herbicidal composition with excellent stability And therefore a liquid herbicidal composition that can be stored for a long time at a high temperature (although it is a liquid formulation). [Technical Solution] One aspect of the present invention provides a liquid herbicidal composition, which includes a pyridine sulfonylurea compound represented by the following formula 1 as an active ingredient, a surfactant, and a buffer. The surfactant includes a sulfo-based Sulfosuccinate-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 a C1 to C2 alkyl group, a C1 to C2 alkoxy group, a C1 to C2 haloalkoxy group, or a halo group. [Advantageous Effects] According to the present invention, it is possible to provide a liquid herbicidal composition having improved stability and therefore capable of being stored for a long time, because the hydrolysis of the active herbicidal ingredient is prevented, even in a liquid formulation.

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：

[Modes of the present invention] The present invention will now be explained in more detail to help understand the present invention. The terms or words used in the specification and subsequent patent applications should not be limited to common or dictionary meanings, but have meanings and concepts corresponding to the technical aspects of the specific examples of the present invention, so as to most appropriately express the text. Specific examples of inventions. The liquid herbicidal composition of the present invention includes a pyridine sulfonylurea compound represented by the following formula 1 as active ingredients, a surfactant, and a buffer. 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 a C1 to C2 alkyl group, a C1 to C2 alkoxy group, a C1 to C2 haloalkoxy group, or a halo 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 . 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 pyridine 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 group Carbonyl]-2-(2-fluoro-1-methoxyacetoxy-n-propyl)pyridine-3-sulfonamide, N-[(4,6-dimethoxypyrimidin-2-yl) Aminocarbonyl]-2-(2-fluoro-1-hydroxyacetoxy-n-propyl)pyridine-3-sulfonamide, N-[(4,6-dimethoxypyrimidin-2-yl) Aminocarbonyl]-2-(2-fluoro-1-(3-hydroxypropionyl)oxy-n-propyl)pyridine-3-sulfonamide, N-[(4,6-dimethoxypyrimidine- 2-yl)aminocarbonyl)-2-(2-fluoro-1-(3-methoxypropionyl)oxy-n-propyl)pyridine-3-sulfonamide, N-[(4,6- Dimethoxypyrimidin-2-yl)aminocarbonyl)-4-methyl-2-(2-fluoro-1-methoxyacetoxy-n-propyl)pyridine-3-sulfonamide, N -[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-4-chloro-2-(2-fluoro-1-methoxyacetoxy-n-propyl)pyridine-3 -Sulfonamide and N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-4-bromo-2-(2-fluoro-1-methoxyacetoxy-n Propyl)pyridine-3-sulfonamide. More preferably, the pyridine sulfonylurea compound represented by formula 1 as the active ingredient may be a compound represented by the following formula A (proposed ISO name: flucetosulfuron):

The pyridine sulfonylurea compound represented by Formula 1 has excellent herbicidal activity, but it is difficult to ensure its stability due to the hydrolysis of the sulfonylurea group in the liquid formulation. In particular, since the decomposition rate of hydrolysis is further increased as the content of the pyridinesulfonylurea compound represented by Formula 1 decreases, it is difficult to ensure the stability of the compound in the liquid formulation. Therefore, the herbicidal composition as a liquid formulation of the present invention includes a sulfosuccinate-based compound as a surfactant and a pyridine sulfonylurea 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 pyridine sulfonylurea compound from hydrolysis, the stability of the herbicidal composition can be ensured, even in a liquid formulation. 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 in the table of formula 2 may be, for example, at least one compound selected from the group consisting of dioctyl sodium sulfosuccinate, sodium diisobutyl sulfosuccinate, and bicyclic sulfosuccinate Sodium dicyclohexane sulfosuccinate, more preferably dioctyl sodium sulfosuccinate or sodium diisobutyl sulfosuccinate.

The liquid herbicidal composition according to the specific example of the present invention may include 1 to 50% by weight of the pyridinesulfonylurea compound represented by Formula 1 as an active ingredient. The internal content of the pyridine sulfonylurea compound may be more preferably 1.5 to 25% by weight, 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 greater than 50% by weight, the herbicidal effect is not significantly improved compared with the increased active ingredient content, which may cause unnecessary increase in manufacturing costs.

The liquid herbicidal composition according to specific examples of the present invention may include 1 to 7 Weight% of sulfosuccinate-based compound as a surfactant. The internal content of the sulfosuccinate-based compound may be more preferably 1 to 5% by weight, even more preferably 3 to 5% by weight. 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 be unprotected in the liquid formulation and may be hydrolyzed, which may cause Stability is reduced. When the internal content of the sulfosuccinate-based compound is greater than 7% by weight, the stability improvement effect is not significantly improved compared to the increase in the content of the surfactant, and the viscosity is increased, which may lead to a decrease in productivity.

The liquid herbicidal composition according to the specific example of the present invention additionally includes a buffer. The buffer is used to adjust the pH of the liquid herbicidal composition. The pH of the liquid herbicidal composition may preferably be 6-7. 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 the specific example of the present invention may additionally include an antifreeze blend. The internal content of the antifreeze blend may be 0.01 to 10% by weight, more preferably 2 to 8% by weight, even more preferably 2 to 4% by weight. When the inner 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.

The antifreeze blend may include glycol-based compounds or alcohol-based compounds. In particular, the glycol-based compound may be propylene glycol (P.G), ethylene glycol, diethylene glycol, dipropylene glycol, tripropylene glycol, or the like, and the alcohol-based compound may be glycerol, isopropanol, or the like. More preferably, the antifreeze blend may include propylene glycol.

The liquid herbicidal composition according to the specific example of the present invention may additionally include a thickening agent. The internal content of the thickener may be 0.05 to 1.2% by weight, more preferably 0.05 to 0.6% by weight, 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, trixian gum, bentonite, alumite clay, microcrystalline kaolinite, gum arabic, guar gum, cellulose compounds, sodium alginate, starch or mixtures thereof can be used. More preferably, sanxian gum, microcrystalline kaolinite or a mixture thereof can be used. According to specific examples of the present invention, in addition to the above-mentioned components, the liquid herbicidal composition may additionally include defoamers, preservatives, stabilizers, pigments, etc., if necessary. According to a specific example of the present invention, the liquid herbicidal composition includes a pyridinesulfonylurea compound represented by Formula 1 as an active ingredient; and a surfactant, and may additionally include additives such as antifreeze blends, thickeners, and defoamers Agents, preservatives and stabilizers. The remaining volume other than the additive volume can be filled with buffer. In other words, based on 100% by weight of the liquid herbicidal composition, the content of the buffer may be the remaining content except for the component content. According to the 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 particularly be a liquid formulation in the form of a liquid or an aqueous suspension (SC) formulation, more preferably an SC formulation. The SC formulation here can be a water-dispersible suspension formulation. Although the liquid herbicidal composition according to the specific example of the present invention is a liquid formulation, it includes a sulfosuccinate-based compound as a surfactant so that the sulfonylurea group of the pyridine sulfonylurea compound can be protected from于hydrolysis. Therefore, the liquid herbicidal composition exhibits excellent stability, even in liquid formulations, and can be conveniently stored for a long time. Specific examples of the present invention will be described below. However, it should be understood that the provision of specific examples does not limit the scope of the present invention and all alternatives and modifications within the scope of the appended patent application are included in the present invention. Therefore, the following specific specific examples are completely described for the purpose of illustration, and provide methods and aspects for easy understanding. The following examples are provided for the purpose of illustration only to explain how to achieve and evaluate the provided compounds, compositions and methods for those who are generally familiar with the technology. Therefore, the following examples are not intended to limit the scope of the present invention deemed by the inventors. There are many available condition changes and combinations 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 in the scope of the present invention. Any combination of all possible changes are included in the present invention, unless there are other instructions in this document or a clear conflict with the context. Example 1 Water was added to K ₂ HPO ₄ and KH ₂ PO ₄ to prepare a total of 1 liter of solution, thereby preparing a 0.1 M phosphate buffer. Then 3.0% by weight of CR-DOS70P (bis(2-ethylhexyl) sulfosuccinate, sodium salt, Cas number 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 a defoamer were added to 65.8% by weight of buffer, and then mixed thoroughly. In a uniformly mixed state, 10.0% by weight of methoxyacetic acid 1-(3-{[(4,6-dimethoxy-pyrimidin-2-yl)aminomethanyl]sulfonamide}-2 -Pyridyl)-2-fluoropropyl ester (flupisulfuron, FTS) was added to the mixture, and then mixed thoroughly using a stirrer. Glass beads are added to the resulting mixture for pulverization. This pulverization is carried out until the average particle size reaches 1 to 2 microns. As a result, a wet part was produced.

Then 0.1% by weight of XG (Sanxian gum, Cas number 11138-66-2) and 0.2% 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% by weight of PG (Propylene Glycol, Cas No. 57-55-6), and then Mix well and stir at the same time. Then, 16.7% by weight of 0.1M phosphate buffer was added to it, followed by thorough mixing and simultaneous stirring. The result is a thickened part.

Then 30% by weight of the thickening part is added to the 70% by weight of the wet part, followed by thorough mixing and simultaneous stirring. As a result, a herbicidal composition with 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 Sodium dioctyl ester (DOS70P) with outer.

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 dicyclohexyl sodium sulfosuccinate (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 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 acid 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 compositions of Examples 1 to 3 and Comparative Examples 1 to 3, about 100 grams of each sample was filled into a plastic bottle made of polyethylene (PE), and then sealed. Then each bottle 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: 100mm×4.6mm inner diameter "Capcell Pak" C18 column, 3 micron particles Mobile phase: acetonitrile/water (0.02M ammonium acetate + 0.1M 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

Claims (7)

A liquid herbicidal composition comprising: a pyridine sulfonylurea compound represented by the following formula 1 as an active ingredient, 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 a C1 to C2 alkyl group, a C1 to C2 alkoxy group, a C1 to C2 haloalkoxy group or a halogen group, wherein the liquid herbicidal composition is a suspension concentrate (SC) dispersed in water The formulation, wherein the internal content of the sulfosuccinate-based compound is 1 to 7% by weight. The liquid herbicidal composition according to item 1 of the scope of patent application, 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. 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. The liquid herbicidal composition according to item 1 of the scope of patent application, wherein the surfactant comprises at least one compound selected from the group consisting of: dioctyl sodium sulfosuccinate, diisobutyl sulfosuccinate Sodium and sodium dicyclohexyl sulfosuccinate. 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 a methoxy group. The liquid herbicidal composition according to item 1 of the scope of patent application, wherein the pyridine sulfonylurea compound as the 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-methoxyacetoxy-n-propyl)pyridine-3-sulfonamide, N-[(4,6-di Methoxypyrimidin-2-yl)aminocarbonyl)-2-(2-fluoro-1-hydroxyacetoxy-n-propyl)pyridine-3-sulfonamide, N-{(4,6-di Methoxypyrimidin-2-yl)aminocarbonyl]-2-(2-fluoro-1-(3-hydroxypropionyl)oxy-n-propyl)pyridine-3-sulfonamide, N-[(4 ,6-Dimethoxypyrimidin-2-yl)aminocarbonyl)-2-(2-fluoro-1-(3-methoxypropionyl)oxy-n-propyl)pyridine-3-sulfonamide , N-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-4-methyl-2-(2-fluoro-1-methoxyacetoxy-n-propyl) Pyridine-3-sulfonamide, N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-4-chloro-2-(2-fluoro-1-methoxyacetoxy -N-propyl)pyridine-3-sulfonamide and N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-4-bromo-2-(2-fluoro-1- Methoxyacetoxy-n-propyl)pyridine-3-sulfonamide. The liquid herbicidal composition according to item 1 of the scope of patent application, wherein the internal content of the pyridine sulfonylurea compound as the active ingredient is 1 to 50% by weight.