Title of the invention: Liquid herbicide composition
Technology field
[One]
Cross-citation with relevant application(s)
[2]
This application claims the benefit of priority based on Korean Patent Application No. 10-2017-0153279 filed on November 16, 2017, and all content disclosed in the literature of the Korean patent application is incorporated as part of this specification.
[3]
Technology field
[4]
The present invention relates to a liquid herbicide composition, and more particularly, to a liquid herbicide composition comprising a herbicidal active ingredient showing excellent herbicidal activity.
[5]
Background
[6]
In crop cultivation technology, it is important to protect crops by controlling weeds that hinder crop growth. In order to reduce damage such as sluggish growth of crops due to weeds in crop fields or reduction in yield, safe herbicide active substances have been developed for crops. A number of herbicidal active substances developed to date have been registered for specific crops and used for weed control. The herbicidal active material for use in controlling weeds occurring in the cultivation of such a specific crop has high herbicidal activity and has a broad herbicidal spectrum, but it is desirable that it is safe for the environment and crops.
[7]
[8]
On the other hand, as described above, the herbicidal composition containing the herbicidal active substance is formulated as a wettable powder, an emulsifiable concentrate, a water-dispersible granule, a granule, and a suspension concentrate. It has been developed and used as a herbicide. However, in the case of hydrating agents, emulsions, and granular hydrating agents, it is generally diluted with water to a predetermined concentration and manufactured as a spraying solution. have. In the case of granules, they can be used directly as they are, so the problems of hydrating agents, emulsions and granular hydrating agents could be solved, but the content of herbicidal active substances is relatively small based on the total herbicide, and an auxiliary agent for forming a herbicide must be included. , Crushing, mixing, sharpening, assembling, drying, classification, etc. The manufacturing process is complicated, and there is a problem that spray stains, etc. occur. In order to overcome the problems of the above formulations, the manufacturing process is relatively simple, environmentally friendly, and a liquid hydration formulation (Suspension concentrate) that can be simplified and efficient during spraying has been developed. On the other hand, when used as a herbicide of various formulations, it is an important task to secure the stability of the herbicide composition even when stored for a long time.
[9]
[10]
The compound of the following formula (a) [ISO proposal name: flucetosulfuron] is a herbicidal active material belonging to the sulfonylurea family and has herbicidal activity in Korean Patent No. 10-0399366 (Application No. 10-2000-0059990) It has already been described as a substance.
[11]
[Formula a]
[12]

[13]
The flucetosulfuron is safe for these crops when treating soil or foliage with respect to rice, wheat, barley (appropriate dosage: 10-40 g ai/ha) and grass (appropriate dosage: 50-200 g ai/ha), It is a material known to have excellent herbicidal effect on a wide range of herbaceous species such as broad-leaved weeds, flower weeds, weeds and weeds, annual and perennial weeds.
[14]
[15]
However, the stability of the herbicide composition containing the herbicidal active material belonging to the sulfonylurea system as described above is still a problem. In particular, in the case of a suspension concentrate (SC) formulation, there is a problem in that it is difficult to store for a long time because the stability is further reduced by hydrolysis under high temperature storage conditions.
[16]
Detailed description of the invention
Technical challenges
[17]
An object of the present invention is to solve the problems of the prior art, it is an object of the present invention to provide a liquid herbicide composition that has excellent herbicidal activity and is excellent in stability even in a liquid formulation, so that it is easy to store for a long time at high temperature.
[18]
Task resolution
[19]
The present invention is an active ingredient comprising a pyridine sulfonyl urea compound represented by the following formula (1); And it provides a liquid herbicide composition comprising a buffer solution (buffer) having a pH of 5.80 to 6.25.
[20]
[Formula 1]
[21]

[22]
In Chemical Formula 1,
[23]
n is an integer of 1 to 3,
[24]
R is hydrogen or an alkyl group having 1 to 4 carbon atoms,
[25]
R'is hydrogen, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, a halogen group or an alkoxy group having 1 to 2 carbon atoms,
[26]
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 having 1 to 2 carbon atoms, or a halogen group.
[27]
Effects of the Invention
[28]
According to the present invention, in the herbicidal composition, the herbicidal activity is excellent, the decomposition rate is low and the stability is excellent even in the liquid form, especially in the formulation of a liquid hydrating agent (Suspension concentrate, SC), so that it is a liquid herbicide composition that is easy to store for a long time at high temperature as a herbicide. Can provide
[29]
Mode for carrying out the invention
[30]
Hereinafter, the present invention will be described in detail.
[31]
The terms or words used in the present specification and claims should not be interpreted as being limited to ordinary or lexical meanings, and the inventor can appropriately define the concept of terms to describe his or her invention in the best way. Based on the principle that it should be interpreted as a meaning and concept consistent with the technical idea of ​​the present invention.
[32]
[33]
Liquid herbicide composition according to an embodiment of the present invention is an active ingredient containing a pyridine sulfonyl urea compound represented by the following formula (1); And it may include a buffer (buffer) pH is 5.80 to 6.25.
[34]
[Formula 1]
[35]

[36]
In Formula 1, n is an integer of 1 to 3, R is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R'is hydrogen, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, a halogen group or a carbon number 1 to 2 alkoxy groups, 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 having 1 to 2 carbon atoms, or a halogen group.
[37]
More preferably, the pyridine sulfonylurea compound represented by Formula 1 is in Formula 1, n is an integer of 1 or 2, R is hydrogen or a methyl group, R'is hydrogen, a halogen group or a methyl group, and X And Y may each independently be a methoxy group, more preferably n is an integer of 1 or 2, R is a methyl group, R'is hydrogen, chlorine (Cl), bromine (Br), or methyl group, X and Y may each independently be a methoxy group.
[38]
[39]
The pyridinesulfonylurea compound of Formula 1 according to an embodiment of the present invention is, for example, N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(2- Fluoro-1-methoxyacetoxy-n-propyl)pyridin-3-sulfonamide, N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(2-fluoro Ro-1-hydroxyacetoxy-n-propyl)pyridin-3-sulfonamide, N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(2-fluoro -1-(3-hydroxypropion)oxy-n-propyl)pyridin-3-sulfonamide, N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(2 -Fluoro-1-(3-methoxypropion)oxy-n-propyl)pyridin-3-sulfonamide, N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-4 -Methyl-2-(2-fluoro-1-methoxyacetoxy-n-propyl)pyridin-3-sulfonamide, N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl ]-4-chloro-2-(2-fluoro-1-methoxyacetoxy-n-propyl)pyridin-3-sulfonamide and N-[(4,6-dimethoxypyrimidin-2-yl) It may be one or more compounds selected from aminocarbonyl]-4-bromo-2-(2-fluoro-1-methoxyacetoxy-n-propyl)pyridin-3-sulfonamide.
[40]
More preferably, the pyridine sulfonylurea compound represented by Formula 1 may be a compound of Formula 2 [ISO proposal name: flucetosulfuron].
[41]
[Formula 2]
[42]

[43]
[44]
In the liquid herbicide composition according to an embodiment of the present invention, the active ingredient is 1 part by weight to 50 parts by weight, preferably 1 part by weight to 25 parts by weight, and even more preferably 3 parts by weight based on 100 parts by weight of the liquid herbicide composition. It may include parts by weight to 15 parts by weight. When the active ingredient of the liquid herbicide composition is contained in less than 1 part by weight, the content of the active ingredient present in the herbicide composition is too small, so even if only a small amount of the active ingredient is decomposed, the decomposition rate (%) increases rapidly and the herbicidal effect decreases. May occur, and when the active ingredient is contained in excess of 50 parts by weight, there may be a problem in that the physical properties of the product such as an increase in viscosity are decreased.
[45]
On the other hand, in the case of a liquid formulation, there is a problem in that stability is deteriorated due to hydrolysis of an active ingredient containing a pyridine sulfonylurea compound represented by Chemical Formula 1 above. However, in the liquid herbicide composition according to an embodiment of the present invention, by appropriately adjusting the pH of the buffer solution, the decomposition rate was significantly lowered even in the liquid formulation to ensure stability.
[46]
[47]
The liquid herbicide composition according to an 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 even more preferably a pH of 6.10 to 6.20, wherein the pH is a buffer solution (buffer ) Can be adjusted. That is, the liquid herbicide composition of the present invention may include a buffer solution having a pH of 5.80 to 6.25, preferably 6.00 to 6.20, and even more preferably 6.10 to 6.20. In the present invention, the pH of the liquid herbicide composition is one of the factors affecting the decomposition rate due to hydrolysis of the liquid herbicide composition, and if it meets the numerical range of the pH 5.80 to 6.25, the decomposition rate is low even during long-term storage of the liquid herbicide composition at high temperature. There is an effect of remarkably improving stability.
[48]
The buffer may be preferably a phosphate-based buffer, a mixture of carbonic acid and sodium hydrogen carbonate (H 2 CO 3 /NaHCO 3 mixture), or a Bis-Tris solution, specifically, 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 ), a mixture of carbonic acid and sodium hydrogen carbonate (H 2 CO 3 /NaHCO 3 mixed solution) and Bis-Tris solution, and more specifically, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, or It may be a mixture of these.
[49]
In addition, when mixing the buffer solutions, the mixing ratio of each buffer solution may be adjusted to a ratio in which the pH of the total buffer solution is 5.80 to 6.25.
[50]
In the present specification, "Bis-Tris solution" is a solution containing Bis-Tris, and Bis-Tris 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 its CAS number is 6976-37-0.
[51]
Furthermore, the buffer solution may be a solution having a concentration of 0.03 M to 0.2 M, preferably 0.05 M to 0.1 M. When the buffer solution satisfies the above numerical range, the decomposition rate of the liquid herbicide composition is further lowered, and stability is improved. In addition, when the concentration is 0.2M or less as in the present invention, there is an advantage in that it is easy to prepare a herbicide composition because of excellent viscosity properties.
[52]
[53]
The liquid herbicide composition according to an embodiment of the present invention may further include a surfactant, and the surfactant facilitates the wettability and dispersibility of the active ingredient, and may help to maintain the suspension stability of the composition for a long time. .
[54]
In addition, the surfactant may include 1 to 20 parts by weight, specifically 1 to 10 parts by weight, based on 100 parts by weight of the total liquid herbicide composition.
[55]
As the type of surfactant, an anionic surfactant, a nonionic surfactant, especially a polymeric surfactant may be used among nonionic surfactants. Specifically, sodium salt dioctyl sulfosuccinate as an anionic surfactant Oxylane graft copolymer containing ethylene oxide units as a nonionic surfactant, including Dioctyl sulfosuccinate Sodium salt, Dioctyl sulfosuccinate Calcuim salt, or alpha olefin sulfonate surfactant. Copolymers, copolymers of oxyethylene and oxypropylene, polyoxyethylene tristyryl phenyl ether or carboxylate-based polymers, sucrose laurate surfactants can be used.
[56]
[57]
The liquid herbicide composition according to an embodiment of the present invention may further include a cryoprotectant, and the cryoprotectant is 0.01 parts by weight to 10 parts by weight, specifically 1.0 parts by weight to 6.0 based on 100 parts by weight of the total liquid herbicide composition. It may include parts by weight, more specifically 2.0 parts by weight to 4.0 parts by weight, and more specifically 2.0 parts by weight to 3.0 parts by weight in terms of greatly improving the decomposition rate while having a freezing preventing effect.
[58]
In addition, the cryoprotectant may include an alcohol-based compound, and specifically, may include a glycol-based compound such as propylene glycol (PG), ethylene glycol, diethylene glycol, dipropylene glycol, tripropylene glycol, etc. As an alcohol-based compound other than the glycol-based compound, glycerin, isopropanol, or a mixture thereof may be included, and propylene glycol may be more preferably included in terms of improving stability while securing an excellent antifreeze effect.
[59]
In the present invention, when the above-described type of anti-freeze agent is included in the above numerical range, the anti-freezing effect is excellent, as well as the effect of lowering the decomposition rate of the liquid herbicide composition. In other words, when the content ratio of the cryoprotectant exceeds the above numerical range, the decomposition rate of the liquid herbicide composition is increased, which may cause a problem of poor stability. If it is contained within the above numerical range, the content is insignificant, and a problem in that sufficient antifreeze effect may not be realized may occur.
[60]
[61]
The liquid herbicide composition according to an embodiment of the present invention may include a thickener, and the thickener is 0.001 parts by weight to 1.2 parts by weight or less, specifically 0.05 parts by weight to 1.0 parts by weight, based on 100 parts by weight of the total liquid herbicide composition. Part, more specifically, may include 0.05 parts by weight to 0.15 parts by weight.
[62]
In addition, the thickener may be used without limitation, a thickener that can be generally used in the related art, and specifically, xanthan gum, bentonite, smectite clay, montmorillonite, gum arabic, guar gum, cellulose-based compounds, Sodium alginate, starch, or mixtures thereof, preferably xanthan gum, montmorillonite, or mixtures thereof.
[63]
According to an embodiment of the present invention, when the thickener is included in the above numerical range, the increasing effect is improved and the decomposition rate of the liquid herbicide composition is reduced.
[64]
[65]
According to an embodiment of the present invention, in addition to the above components, the liquid herbicide composition may further include an antifoaming agent, an antiseptic agent, a stabilizer, a colorant, and the like as necessary.
[66]
[67]
In addition, according to an embodiment of the present invention, the liquid herbicide composition is the active ingredient, except for the content of additives such as a compound represented by Formula 1, a surfactant, an antifreeze agent, a thickener, and an antifoam, preservative, and stabilizer. All of the content may be made of a buffer. In other words, the content of the buffer solution may be the rest of 100% by weight of the liquid herbicide composition excluding the content of other components.
[68]
[69]
In addition, according to an embodiment of the present invention, the formulation of the liquid herbicide composition is not limited to any formulation as long as it is a liquid formulation, but specifically, may be a solution formulation or a suspension concentrate (SC) formulation present in a liquid form. , More specifically, it may be a liquid wettable formulation. Here, the liquid wettable formulation may mean an aqueous suspension formulation.
[70]
When the herbicide composition containing the above-described active ingredient is prepared in a liquid wettable formulation, there is a problem that it is not easy to store for a long time even when the herbicide composition is prepared due to high decomposition rate due to hydrolysis.In the present invention, the pH of the liquid herbicide composition is adjusted. By doing so, it is possible to prepare a liquid herbicide composition that is easy to store for a long time by improving stability.
[71]
The liquid herbicide composition according to an embodiment of the present invention protects the sulfonylurea group of the pyridine sulfonylurea compound from hydrolysis, even though it is a liquid formulation by adjusting the pH range of the liquid herbicide composition including a buffer with a controlled pH. Thus, the stability of the liquid formulation can be secured by remarkably lowering the decomposition rate due to hydrolysis, and long-term storage can be facilitated. As described above, the present invention can solve a problem in which it is difficult to secure stability because most of the active ingredients are hydrolyzed because the conventional herbicide composition in a liquid formulation containing a small amount of active ingredients has a very high decomposition rate by hydrolysis.
Claim
[Claim 1]
An active ingredient comprising a pyridine sulfonyl urea compound represented by the following formula (1); And a buffer solution having a pH of 5.80 to 6.25. In Formula 1 , n is an integer of 1 to 3, R is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R'is hydrogen, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, A halogen 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 having 1 to 2 carbon atoms, or a halogen group.
[Claim 2]
The liquid herbicide composition of claim 1, wherein the buffer has a pH of 6.0 to 6.2.
[Claim 3]
The method of claim 1, wherein the buffer contains at least one selected from the group consisting of a phosphate-based buffer, a mixture of carbonic acid and sodium hydrogencarbonate (H 2 CO 3 /NaHCO 3 mixture), and a Bis-Tris solution. The liquid herbicide composition.
[Claim 4]
The method of claim 3, wherein the phosphate-based buffer is dipotassium hydrogen phosphate (K 2 HPO 4 ), potassium dihydrogen phosphate (KH 2 PO 4 ), disodium hydrogen phosphate (Na 2 HPO 4 ), and sodium dihydrogen phosphate (NaH 2 PO 4 ) A liquid herbicide composition comprising at least one selected from the group consisting of.
[Claim 5]
The liquid herbicide composition of claim 1, wherein the buffer solution has a concentration of 0.03 M to 0.2 M.
[Claim 6]
The liquid herbicide according to claim 1, wherein in Formula 1, n is an integer of 1 or 2, R is hydrogen or a methyl group, R'is hydrogen, a halogen group or a methyl group, and X and Y are each independently a methoxy group. Composition.
[Claim 7]
The method of claim 1, wherein the pyridinesulfonylurea compound represented by Formula 1 is N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(2-fluoro- 1-methoxyacetoxy-n-propyl)pyridine-3-sulfonamide, N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(2-fluoro-1 -Hydroxyacetoxy-n-propyl)pyridin-3-sulfonamide, N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(2-fluoro-1- (3-hydroxypropion)oxy-n-propyl)pyridin-3-sulfonamide, N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(2-fluoro -1-(3-methoxypropion)oxy-n-propyl)pyridine-3-sulfonamide, N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-4-methyl- 2-(2-Fluoro-1-methoxyacetoxy-n-propyl)pyridin-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 A liquid herbicide composition comprising at least one member selected from the group consisting of.
[Claim 8]
The liquid herbicide composition of claim 1, wherein the pyridine sulfonylurea compound represented by Formula 1 is a compound represented by Formula 2 below. [Formula 2]
[Claim 9]
The liquid herbicide composition of claim 1, wherein the active ingredient comprises 1 part by weight to 50 parts by weight based on 100 parts by weight of the liquid herbicide composition.
[Claim 10]
The liquid herbicide composition of claim 1, wherein the liquid herbicide composition further comprises a cryoprotectant, and the cryoprotectant comprises an alcohol-based compound.
[Claim 11]
The liquid herbicide composition of claim 10, wherein the cryoprotectant comprises at least one selected from the group consisting of propylene glycol, ethylene glycol, diethylene glycol, dipropylene glycol, tripropylene glycol, glycerin and isopropanol.
[Claim 12]
The liquid herbicide composition of claim 10, wherein the cryoprotectant comprises 0.01 parts by weight to 10.0 parts by weight based on 100 parts by weight of the liquid herbicide composition.
[Claim 13]
The liquid herbicide composition according to claim 1, wherein the liquid herbicide composition is a suspension concentrate (SC) formulation.