CROSS-REFERENCE TO RELATED APPLICATION
This application claims priority to and the benefit of Korean Patent
Application No. 10-2017-0153281, filed on November 16, 2017, the disclosure of
which is incorporated herein by reference in its entirety.
10 Technical Field
The present invention relates to a liquid herbicidal liquid composition
including an active herbicidal ingredient exhibiting excellent herbicidal activity.
【Background Art】
15 In crop cultivation, it is important to protect crops by controlling weeds that
inhibit the growth of crops. To reduce damage such as loss of crop growth or yield
due to weeds growing in a cultivation area, active herbicidal substances that are
capable of effectively controlling weeds and are safe for crops have been developed.
Many active herbicidal substances developed so far have been registered for specific
20 crops and are used for weed control. Such herbicidal active substances used for
control of weeds growing in the cultivation areas of specific crops are preferred to
have high herbicidal activity and a broad herbicidal spectrum and to be safe for the
environment and crops.
3
Meanwhile, herbicidal compositions including such active herbicidal
substances have been developed and used in formulations such as a wettable powder,
an emulsifiable concentrate, a water-dispersible granule, a granule, a suspension
concentrate, and the like. However, in the case of a wettable powder, an
5 emulsifiable concentrate, and a water-dispersible granule that are generally diluted
with water to predetermined concentrations to prepare sprayable solutions, there is a
problem that it is costly and time-consuming to uniformly spray the same over the
entire surface of a target paddy or field. Although the problems of a wettable
powder, an emulsifiable concentrate, and a water-dispersible granule can be
10 addressed by using a granule that can be directly used without being diluted with
water, such a granule includes a relatively low content of active herbicidal substances
based on a total amount of herbicide, should necessarily include an auxiliary agent
for forming an herbicide, is manufactured by a complex process including
pulverization, mixing, milling, granulation, drying, classification, and the like, and
15 has a problem such as occurrence of stains due to spraying.
To address such problems, a suspension concentrate formulation, a
manufacturing process of which is relatively simple and which is ecofriendly and
allows simple and efficient spraying, has been developed. However, in the case of a
liquid formulation such as a suspension concentrate, the stability of an herbicidal
20 composition is decreased when stored for a long time at high temperature because a
specific active ingredient exhibiting excellent herbicidal activity is decomposed by
heat and hydrolysis.
Therefore, there is an urgent need for research to improve the stability of an
herbicidal composition as a suspension concentrate formulation, which includes an
25 active ingredient exhibiting excellent herbicidal activity.
4
【Related Art Document】
【Patent Document】
Korean Patent No. 10-0399366
5
【Disclosure】
【Technical Problem】
Therefore, the present invention has been made in view of the above
problems, and it is one object of the present invention to provide an herbicidal liquid
10 composition including an active ingredient exhibiting excellent herbicidal activity,
and more particularly, to an herbicidal liquid composition having excellent stability
and thus being capable of being stored at high temperature for a long time even
though it is a liquid formulation.
15 【Technical Solution】
One aspect of the present invention provides 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:
20 [Formula 1]
5
wherein n represents an integer of 1 to 3, R is a hydrogen atom or a C1 to C4
alkyl group, R’ is a hydrogen atom, a C1 to C4 alkyl group, a C1 to C3 haloalkyl
group, a halogen group, or a C1 to C2 alkoxy group, and X and Y are each
5 independently a C1 to C2 alkyl group, a C1 to C2 alkoxy group, a C1 to C2
haloalkoxy group, or a halogen group.
【Advantageous Effects】
In accordance with the present invention, an herbicidal liquid composition
10 having improved stability and thus being capable of being stored for a long time
because hydrolysis of an active herbicidal ingredient is prevented even in a liquid
formulation can be provided.
【Modes of the Invention】
15 Now, the present invention will be described in more detail to help
understand the present invention. Terms or words used in the specification and the
following claims shall not be limited to common or dictionary meanings, and have
meanings and concepts corresponding to technical aspects of the embodiments of the
present invention so as to most suitably express the embodiments of the present
20 invention.
6
An herbicidal liquid composition of the present invention includes 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:
5 [Formula 1]
wherein n represents an integer of 1 to 3, R is a hydrogen atom or a C1 to C4
alkyl group, R’ is a hydrogen atom, a C1 to C4 alkyl group, a C1 to C3 haloalkyl
group, a halogen group, or a C1 to C2 alkoxy group, and X and Y are each
10 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.
15 Even more preferably, in Formula 1, n may be an integer of 1 or 2, R may be
methyl, R' may be a hydrogen atom, Cl, Br, or a methyl group, and X and Y may
each be methoxy.
The pyridine sulfonylurea compound, as an active ingredient, represented by
20 Formula 1 may be, for example, at least one selected from the group consisting of N-
7
[(4,6-dimethoxypyrimidine-2-yl)aminocarbonyl]-2-(2-fluoro-1-methoxyacetoxy-npropyl)pyridine-3-sulfonamide, N-[(4,6-dimethoxypyrimidine-2-yl)aminocarbonyl]-
2-(2-fluoro-1-hydroxyacetoxy-n-propyl)pyridine-3-sulfonamide, N-[(4,6-
dimethoxypyrimidine-2-yl)aminocarbonyl]-2-(2-fluoro-1-(3-hydroxypropion)oxy-n5 propyl)pyridine-3-sulfonamide, N-[(4,6-dimethoxypyrimidine-2-yl)aminocarbonyl]-
2-(2-fluoro-1-(3-methoxypropion)oxy-n-propyl)pyridine-3-sulfonamide, N-[(4,6-
dimethoxypyrimidine-2-yl)aminocarbonyl]-4-methyl-2-(2-fluoro-1-methoxyacetoxyn-propyl)pyridine-3-sulfonamide, N-[(4,6-dimethoxypyrimidine-2-
yl)aminocarbonyl]-4-chloro-2-(2-fluoro-1-methoxyacetoxy-n-propyl)pyridine-3-
10 sulfonamide, and N-[(4,6-dimethoxypyrimidine-2-yl)aminocarbonyl]-4-bromo-2-(2-
fluoro-1-methoxyacetoxy-n-propyl)pyridine-3-sulfonamide.
More preferably, the pyridine sulfonylurea compound, as an active
ingredient, represented by Formula 1 may be a compound (proposed ISO name:
flucetosulfuron) represented by Formula A below:
15 [Formula A]
The pyridine sulfonylurea compound represented by Formula 1 has excellent
herbicidal activity, but it is difficult to secure the stability thereof due to hydrolysis
20 of a sulfonylurea group in a liquid formulation. In particular, a decomposition rate
8
due to hydrolysis further increases with decreasing content of the pyridine
sulfonylurea compound represented by Formula 1, whereby it is difficult to secure
the stability of the compound in a liquid formulation.
Accordingly, the herbicidal composition, as a liquid formulation, of the
5 present invention includes a sulfosuccinate-based compound, as a surfactant, along
with the pyridine sulfonylurea compound, as an active herbicidal ingredient,
represented by Formula 1, whereby the herbicidal composition has improved stability
in a liquid formulation. Since a sulfosuccinate group of the surfactant protects a
sulfonylurea group of a pyridine sulfonylurea compound against hydrolysis, the
10 stability of the herbicidal composition may be secured even in a liquid formulation.
More particularly, the surfactant may include a sulfosuccinate-based
compound represented by Formula 2 below:
[Formula 2]
15
wherein M is at least one selected from the group consisting of Na, NH4, and
K, and R1 and R2 are each independently a C1 to C20 alkyl group, cycloalkyl group,
or aryl group.
More preferably, in Formula 2, M may be Na, and R1 and R2 may each
20 independently be a C4 to C10 alkyl group or cycloalkyl group.
9
The surfactant represented by Formula 2 may be, for example, at least one
compound selected from the group consisting of sodium dioctyl sulfosuccinate,
sodium diisobutyl sulfosuccinate, and sodium dicyclohexane sulfosuccinate, more
preferably sodium dioctyl sulfosuccinate or sodium diisobutyl sulfosuccinate.
5
An herbicidal liquid composition according to an embodiment of the present
invention may include 1 to 50 % by weight of the pyridine sulfonylurea compound,
as an active ingredient, represented by Formula 1. The pyridine sulfonylurea
compound may be included in an amount of, more preferably, 1.5 to 25 % by weight,
10 even more preferably, 3 to 10 % by weight. When the active ingredient is included
in an amount of less than 1 % by weight, the content of the active ingredient in the
herbicidal liquid composition is too low, whereby herbicidal activity may be
decreased. When the active ingredient is included in an amount of greater than
50 % by weight, a herbicidal effect is not significantly improved compared to the
15 content increase of the active ingredient, which may lead to an unnecessary increase
in manufacturing costs.
An herbicidal liquid composition according to an embodiment of the present
invention may include 1 to 7 % by weight of the sulfosuccinate-based compound as a
surfactant. The sulfosuccinate-based compound may be included in an amount of,
20 more preferably, 1 to 5 % by weight, even more preferably 3 to 5 % by weight.
When the sulfosuccinate-based compound as a surfactant is included in an amount of
less than 1 % by weight, the sulfonylurea group of the active ingredient may not be
protected in a liquid formulation and may be hydrolyzed, which may lead to a
decrease in stability. When the sulfosuccinate-based compound is included in an
25 amount of greater than 7 % by weight, a stability improvement effect is not
10
significantly improved compared to the content increase of the surfactant, and
viscosity increases, which may lead to a decrease in productivity.
An herbicidal liquid composition according to an embodiment of the present
5 invention further includes a buffer. The buffer serves to adjust the pH of the
herbicidal liquid composition. The pH of the herbicidal liquid composition may be
preferably 6 to 7. When the pH is within a range of 6 to 7, a decomposition rate of
the herbicidal liquid composition may be further decreased, and stability may be
further improved.
10
An herbicidal liquid composition according to an embodiment of the present
invention may further include an antifreezing admixture. The antifreezing
admixture may be included in an amount of 0.01 to 10 % by weight, more preferably
2 to 8 % by weight, even more preferably 2 to 4 % by weight. When the
15 antifreezing admixture is included within these ranges, an excellent freezing
prevention effect may be exhibited, and a decomposition rate of the herbicidal liquid
composition may be further decreased.
The antifreezing admixture may include a glycol-based compound or an
alcohol-based compound. In particular, the glycol-based compound may be
20 propylene glycol (P.G), ethylene glycol, diethylene glycol, dipropylene glycol,
tripropylene glycol, or the like, and the alcohol-based compound may be glycerin,
isopropanol, or the like. More preferably, the antifreezing admixture may include
propylene glycol.
11
An herbicidal liquid composition according to an embodiment of the present
invention may further include a thickener. The thickener may be included in an
amount of 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 thickener is included in these
5 ranges, a thickening effect may be improved, and a decomposition rate of the
herbicidal liquid composition may be further lowered.
The thickener is not specifically limited so long as it is generally used in the
related technical field. In particular, xanthan gum, bentonite, smectite clay,
montmorillonite, arabic gum, guar gum, a cellulosic compound, sodium alginate,
10 starch, or a mixture thereof may be used. More preferably, xanthan gum,
montmorillonite, or a mixture thereof may be used.
In accordance with an embodiment of the present invention, the herbicidal
liquid composition may further include, in addition to the above-described
15 components, a defoamer, a preservative, a stabilizer, a pigment, etc., as needed.
In accordance with an embodiment of the present invention, the herbicidal
liquid composition includes the pyridine sulfonylurea compound represented by
Formula 1, as an active ingredient, and a surfactant and may further include additives
20 such as an antifreezing admixture, a thickener, a defoamer, a preservative, and a
stabilizer. The remaining volume, other than the volumes of the additives, may be
filled with a buffer. In other words, the content of the buffer may be the remaining
content, other than the contents of the components, in 100 % by weight of the
herbicidal liquid composition.
25
12
In accordance with an embodiment of the present invention, a formulation of
the herbicidal liquid composition is not specifically limited so long as it is a liquid
formulation. In particular, the herbicidal liquid composition may be a solution
formulation present as a liquid or a suspension concentrate (SC) formulation, more
5 preferably SC formulation. Here, the SC formulation may be a water-dispersed
suspension formulation.
Even though the herbicidal liquid composition according to an embodiment
of the present invention is a liquid formulation, the sulfosuccinate-based compound
10 as a surfactant is included so that the sulfonylurea group of the pyridine sulfonylurea
compound may be protected against hydrolysis. Accordingly, the herbicidal liquid
composition exhibits excellent stability even in a liquid formulation, and may be
conveniently stored for a long time.
15 Hereinafter, specific embodiments of the present invention will be described.
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 accompanying claims are included in the present invention. Accordingly, the
following specific embodiments will be thoroughly described for illustrative
20 purposes, and processes and aspects will be provided for easy understanding.
The following examples are provided to describe to those of ordinary skill in
the art how provided compounds, compositions, and methods are made and evaluated,
only for illustrative purposes. Accordingly, the following examples are not
25 intended to limit the scope of what the inventors regard as the present invention.
13
There are many variations and combinations of conditions that may be utilized to
optimize reaction conditions, the concentrations of components, 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
5 scope of the present invention. Any combination of all possible variations is
included in the present invention unless otherwise indicated herein or otherwise
clearly contradicted by context
Example 1
10 Water was added to K2HPO4 and KH2PO4 to prepare a 1 L solution in total,
thereby preparing a 0.1 M phosphate buffer. Next, 3.0 % by weight of CR-DOS70P
(di(2-ethylhexyl)sulfosuccinate, sodium salt, Cas No. 577-11-7), 1.0 % by weight of
NK-SU500 (sucrose laurate, Cas No. 25339-99-5), and 0.2 % by weight of SAG-622
as a defoamer (manufactured by Momentive) were added to 65.8 % by weight of the
15 buffer, followed by sufficient mixing. In a state of being uniformly mixed, 10.0 %
by weight of 1-(3-{[(4,6-dimethoxy-pyrimidine-2-yl)carbamoyl]sulfamoyl}-2-
pyridinyl)-2-fluoropropyl methoxyacetate (flucetosulfuron, FTS) was added to the
mixture, followed by sufficient mixing using a stirrer. Glass beads were added to
the resultant mixture to perform pulverization. This pulverization was performed
20 until an average particle size reached 1 to 2 μm. As a result, a wet part was
prepared.
Next, 0.1 % by weight of X.G (xanthan gum, Cas No. 11138-66-2) and
0.2 % by weight of M.V [5-chloro-2-methyl-4-isothiazoline-3-one (Cas No. 26172-
55-4) and 2-methyl-4-isothiazoline-3-one (Cas No. 2682-20-4)] were added to 3.0 %
25 by weight of P.G (propylene glycol, Cas No. 57-55-6), followed by sufficiently
14
mixing while stirring. Next, 16.7 % by weight of a 0.1 M phosphate buffer were
added thereto, followed by sufficiently mixing while stirring. As a result, a
thickened part was prepared.
Next, 30 % by weight of the thickened part was added to 70 % by weight of
5 the wet part, followed by sufficiently mixing while stirring. As a result, an
herbicidal composition having a suspension concentrate formulation was prepared.
Example 2
An herbicidal composition having a suspension concentrate formulation was
10 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 sodium
dioctyl sulfosuccinate (DOS70P).
Example 3
15 An herbicidal composition having a suspension concentrate formulation was
prepared in the same manner as in Example 1, except that 3 % by weight of sodium
dicyclohexane sulfosuccinate (CR-DCHS) was used instead of 3 % by weight of
DOS70P.
20 Comparative Example 1
An herbicidal composition having a suspension concentrate 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.
25 Comparative Example 2
15
An herbicidal composition having a suspension concentrate formulation was
prepared in the same manner as in Example 1, except that 3 % by weight of
naphthalene sulfonic acid formalin condensate (NK-D425) was used instead of 3 %
by weight of DOS70P.
5
Comparative Example 3
An herbicidal composition having a suspension concentrate formulation was
prepared in the same manner as in Example 1, except that 3 % by weight of lignin
sulfonate (NK-SLS) was used instead of 3 % by weight of DOS70P.
10
Experimental Example: Evaluation of storage stability of herbicidal
liquid composition]
To evaluate storage stability of the herbicidal liquid compositions of
Examples 1 to 3 and Comparative Examples 1 to 3, about 100 g of each of the
15 samples was filled in a plastic bottle made of polyethylene (PE), followed by sealing.
Next, each of the bottles was stored in an oven maintained at 54(±2)°C for 4 weeks,
and then an area value of active ingredients was measured using HPLC
(manufactured by Waters) to evaluate a decomposition rate. Results are
summarized in Table 1 below.
20 HPLC analysis conditions were as follows:
Column: 100 mm × 4.6 mm i.d. “Capcell Pak” C18 column, 3 μm particles
Mobile Phase: acetonitrile/water (0.02 M ammonium acetate + 0.1 M acetic
acid) = 32/68
Flow: 1.0 mL/min.
25 Column Temperature: 30°C
16
Injection Volume: 10 μl
Detector Wavelength: 254 nm
Run time: 20 min.
5 【Table 1】
Decomposition rate (%) after storing for four weeks at
54°C
Example1 9.94
Example2 4.77
Example3 8.59
Comparative Example1 15.26
Comparative Example2 11.32
Comparative Example3 12.24
17
【CLAIMS】
【Claim 1】
An herbicidal liquid composition, comprising a pyridine sulfonylurea
compound, as an active ingredient, represented by Formula 1 below, a surfactant, and
5 a buffer, the surfactant comprising a sulfosuccinate-based compound,
[Formula 1]
wherein n represents an integer of 1 to 3,
R is a hydrogen atom or a C1 to C4 alkyl group,
10 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.
15 【Claim 2】
The herbicidal liquid composition according to claim 1, wherein the
surfactant comprises a sulfosuccinate-based compound represented by Formula 2
below:
[Formula 2]
18
wherein M is at least one selected from the group consisting of Na, NH4, and
K, and R1 and R2 are each independently a C1 to C20 alkyl group, cycloalkyl group,
or aryl group.
5
【Claim 3】
The herbicidal liquid composition according to claim 2, wherein, in Formula
2, M is Na, and R1 and R2 are each independently a C4 to C10 alkyl group or
cycloalkyl group.
10
【Claim 4】
The herbicidal liquid composition according to claim 1, wherein the
surfactant comprises at least one compound selected from the group consisting of
sodium dioctyl sulfosuccinate, sodium diisobutyl sulfosuccinate and sodium
15 dicyclohexane sulfosuccinate.
【Claim 5】
The herbicidal liquid composition according to claim 1, wherein the
sulfosuccinate-based compound is comprised in an amount of 1 to 7 % by weight.
20
【Claim 6】
19
The herbicidal liquid composition according to claim 1, 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
5 X and Y are each a methoxy group.
【Claim 7】
The herbicidal liquid composition according to claim 1, wherein the pyridine
sulfonylurea compound as an active ingredient is at least one selected from the group
10 consisting of N-[(4,6-dimethoxypyrimidine-2-yl)aminocarbonyl]-2-(2-fluoro-1-
methoxyacetoxy-n-propyl)pyridine-3-sulfonamide, N-[(4,6-dimethoxypyrimidine-2-
yl)aminocarbonyl]-2-(2-fluoro-1-hydroxyacetoxy-n-propyl)pyridine-3-sulfonamide,
N-[(4,6-dimethoxypyrimidine-2-yl)aminocarbonyl]-2-(2-fluoro-1-(3-
hydroxypropion)oxy-n-propyl)pyridine-3-sulfonamide, N-[(4,6-
15 dimethoxypyrimidine-2-yl)aminocarbonyl]-2-(2-fluoro-1-(3-methoxypropion)oxy-npropyl)pyridine-3-sulfonamide, N-[(4,6-dimethoxypyrimidine-2-yl)aminocarbonyl]-
4-methyl-2-(2-fluoro-1-methoxyacetoxy-n-propyl)pyridine-3-sulfonamide, N-[(4,6-
dimethoxypyrimidine-2-yl)aminocarbonyl]-4-chloro-2-(2-fluoro-1-methoxyacetoxyn-propyl)pyridine-3-sulfonamide, and N-[(4,6-dimethoxypyrimidine-2-
20 yl)aminocarbonyl]-4-bromo-2-(2-fluoro-1-methoxyacetoxy-n-propyl)pyridine-3-
sulfonamide.
【Claim 8】
20
The herbicidal liquid composition according to claim 1, wherein the pyridine
sulfonylurea compound as an active ingredient is comprised in an amount of 1 to
50 % by weight.
5 【Claim 9】
The herbicidal liquid composition according to claim 1, wherein the
herbicidal liquid composition is a suspension concentrate (SC) formulation.