KR20010051617A - Stabilized herbicide composition for dusting into paddy field and weeding method using the same - Google Patents

Abstract

PURPOSE: A paddy herbicide capable of preventing the degradation of foaming power generated during storage by using anhydrous ammonium alum as an inorganic acid in a conventional herbicide composition and a weeding method using the same are provided. Therefore, the herbicide has good diffusibility in a flooded paddy field such that a herbicide active ingredient will quickly, uniformly diffuse into the paddy field. CONSTITUTION: In a paddy herbicide containing a herbicide active ingredient, a surfactant, carbonate and a mixture of an organic acid and an inorganic acid, 5 to 30% by weight of anhydrous ammonium alum is used as an inorganic acid, wherein the herbicide active ingredient is 0.1 to 10% by weight of a sulfonyl urea-based herbicidal compound and 0.4 to 15% by weight of an annual herbicidal compound.

Description

Stabilized herbicide composition for dusting into paddy field and weeding method using the same

The present invention relates to a stable foamable herbicide composition for water supply and a weeding method capable of efficiently removing weeds by dropping it in fresh rice paddies to facilitate pharmaceutical application and to provide excellent integrity of the herbicidal active ingredient.

Conventionally, as a method of weeding in the early to middle stages of the rice harvesting, the herbicide component was sprayed as it was, or the granules or granules prepared with the solid carrier of the fine powder and other auxiliaries as it were, or diluted with a large amount of hydrating agent and sprayed with the herbicide component organically. The oil agent dissolved in the solvent or the fluidizing agent dispersed and suspended in water has been sprayed as it is.

However, in the application of granules, granules or hydrating agents, for example, using a heavy Niagara hose on a rice field or walking around in a rice field with a heavy spreader or granulator loaded with a medicament to spray 3 to 4 kg of medicament per 10 a The drug had to be sprayed uniformly, and even with the application of emulsions or glidants, the weight of the drug was reduced to some extent, but it was still required to spray while walking on the rice fields with a container for discharging a certain amount.

Accordingly, water herbicides that can solve the above-mentioned problems are disclosed in Japanese Patent Laid-Open Nos. 3-128301, 3-223203, 5-229903, 11-222403, and the like. That is, since the herbicidal active ingredient is moved to a target point by foaming by containing a herbicidal active ingredient, surfactant, a carbonate, and a water-soluble solid acid, the water herbicide for which the application | coating of a chemical | medical agent became easy to enter without paddy is disclosed.

However, these water-based herbicides usually contain non-moisture-proof materials because any amount of water can cause solid acids and carbonates to react, resulting in poor foaming power, and as a result, sufficient herbicidal effects cannot be achieved even when used in paddy fields under fresh water. The neutralization reaction is often initiated by trace amounts of moisture present in the raw materials or in the air in the container. When the neutralization reaction occurs, water is generated and the neutralization reaction proceeds more rapidly.

Therefore, a method of removing trace amounts of water present in these herbicides has been studied. As a result, a method of containing a desiccant such as a desiccant or a solid dehydrating agent has been developed (Japanese Patent Laid-Open Nos. 5-178701 and 5). -255003).

The present inventors also conducted a study to find a method that can prevent the deterioration of the foaming power that may occur during storage in the foaming water herbicides, the conventional herbicide active ingredients, surfactants, carbonates and mixtures of organic and inorganic acids In the herbicidal composition for effervescent water, it has been found that the above object can be achieved by using an ammonium alum as an inorganic acid.

Accordingly, it is an object of the present invention to provide a stabilized herbicidal herbicidal composition which is convenient for pharmaceutical application and which can provide excellent integrity of herbicidal active ingredients.

Another object of the present invention is to provide a weeding method which can efficiently remove weeds by using the above-mentioned foamable herbicide.

1 shows a tablet dropping point and a sampling point away from the dropping point in the dropping treatment of the herbicide of the present invention.

Figure 2 shows the tableting dropping point and the rice transplanting point of rice or weeds in the dropping treatment of the herbicide according to the present invention.

In order to achieve the above object, the stable herbicidal composition for foaming water according to the present invention is a conventional foaming water herbicide consisting of a herbicidal active ingredient, a surfactant, a carbonate and a mixture of an organic acid and an inorganic acid. It is characterized by containing in an amount of% by weight.

Hereinafter, the present invention will be described in more detail.

In general, foaming water herbicides absorb moisture when present in raw materials or air in sealed containers, and gradually neutralize the reaction, and the water produced by the reaction accelerates the reaction again, resulting in satisfactory foaming when the formulation is used. It does not cause the dissolution and diffusion of the herbicidal active ingredient and further has a problem that adversely affects the biological effect.

Therefore, in the present invention, in order to provide a stable foaming herbicide that does not reduce the foaming force due to the gas generated during storage, ammonium anhydrous alum was used in an amount of 5 to 30% by weight as an inorganic acid component of the foamable water herbicide composition.

In the stable foamable herbicidal herbicide composition of the present invention, for example, a mixture of a sulfonyl urea herbicidal compound and an annual herbicidal compound may be used as the herbicidal active ingredient, but is not limited thereto.

Although the kind of sulfonyl urea herbicidal compound used for the herbicide composition to which this invention is stable is not specifically limited, For example, Azimsulfuron (1- (4,6- dimethoxypyrimidin-2-yl)- 3- [1-methyl-4- (2-methyl-2H-tetraol-5-ylsulfonyl] urea), halosulfuron-methyl (methyl 3-chloro-5- (4,6-dimethoxypyrimidine -2-ylcarbamoylsulfamoyl) -1-methylpyrazole-4-carboxylate), bensulfuron-methyl (α- (4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl) -o Toluic acid), ethoxysulfuron (1- (4,6-dimethoxypyrimidin-2-yl) -3- (2-ethoxyphenoxysulfonyl) urea), imazosulfuron (1- (2- Chloroimidazole [1,2-α] pyridin-3-ylsulfonyl) -3- (4,6-dimethoxypyrimidin-2-yl) urea), pyrazosulfuron-methyl (ethyl 5- (4, 6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl) -1-methoxypyrazole-4-carboxylate) and cyclosulfamuron (1- [2- (cyclopropylcarbonyl) phenylsulfamoyl]- 3- (4,6-di Methoxypyrimidin-2-yl) urea), and the sulfonyl urea herbicidal compound is preferably used in an amount of 0.1 to 10% by weight based on the total weight of the herbicide composition. .

Although the kind of annual herbicidal compound is not specifically limited, For example, pyriminobac-methyl (methyl-2- (4,6-dimethoxy-2-pyrimidinyloxy) -6- (1-methoxyimino Ethyl) benzoate), sihalofop-butyl (butyl (R) -2- [4- (4-cyano-2-fluorophenoxy) phenoxy] propionate), indanophan ((RS) -2- [2- (3-chlorophenyl) -2,3-epoxypropyl] -2-ethylindan-1,3-dione) and oxazylclomepon (3- [1- (3,5-dichlorophenyl ) -1-methylethyl] -3,4-dihydro-6-methyl-5-phenyl-2H-1,3-oxazin-4-one). The content of the annual herbicidal compound is preferably an amount of 0.4 to 15% by weight based on the total weight of the herbicide composition.

The stable herbicidal water herbicide composition of the present invention contains surfactants, carbonates and organic acids contained in conventional foamable water preparations in addition to the inorganic acids and herbicidal active ingredients described above.

The surfactant is contained in an amount of 1 to 15% by weight based on the total weight of the herbicide composition, and the type thereof is not particularly limited, but may be suitably selected from nonionic surfactants or anionic surfactants. Specific examples of the surfactant include dioctylsulfosuccinate, naphthalenesulfonate formalin condensate, polyacrylate, sulfate alkyl, lignosulfonate, laurylsulfonate, polyalkylnaphthalenesulfonate, polyethylenenonylphenyl polymer, poly At least one member selected from the group consisting of oxyethylene styrylphenyl polymer and polyoxyethylene-polyoxypropylene.

In addition, the carbonate may be sodium carbonate, calcium carbonate, magnesium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate and ammonium bicarbonate in an amount of 10 to 40% by weight based on the total weight of the herbicide composition. Can be used.

In addition, the organic acid may be citric acid, malic acid, tartaric acid, succinic acid, maleic acid, phthalic acid, adipic acid and ethylenediaminetetraacetic acid (EDTA) of at least 10 to 20% by weight relative to the total weight of the herbicide composition Can be used in quantities.

The stable herbicidal water herbicide composition of the present invention may further contain an oil-absorbing carrier, other pesticide adjuvants, a water-soluble carrier and the like.

In particular, the oil-absorbing carrier can be used to solve the problem of eluting the oily substance as well as imparting the strength of the desired tablet when using the oily herbicidal active ingredient. The oil-absorbing carrier may be used as long as the oil-absorbing carrier has an oil absorption of 50% by weight or more and does not adversely affect the final produced tablet. Specifically, for example, white carbon, particulate amorphous silicon dioxide, and starch water Decomposition products, talc, diatomaceous earth, artificial compounds of diatomaceous earth and lime, mixtures of kaolinite and sericite, calcium silicate, hard calcium carbonate, hard calcium silicate, acidic white clay, powdered activated carbon, natural earth graphite, parite workpiece, ultrafine particle anhydrous Aluminum, ultrafine titanium oxide, basic magnesium carbonate, magnesium aluminate silicate, synthetic fillers of silica and alumina, hydrous magnesium silicate and mixtures thereof can be used. The amount of the oil absorbent carrier in the herbicide composition is preferably 1 to 10% by weight based on the total weight of the composition.

In the method for producing a stable foamable herbicide of the present invention, after mixing all the components uniformly by mixing the above components at the same time or by mixing any remaining components with any components previously mixed, the particle size of the mixture is 0.5 ~ 50㎛ Pulverize, compress, and dry to tablets to the appropriate size. At this time, the herbicidal active ingredient is preferably finely ground to a particle diameter of 0.1 ~ 5㎛ before mixing in order to increase the dispersibility in water. In addition, when producing tablets industrially, it is desirable to impart fluidity to the mixture to enable continuous compression molding.

Tablets prepared according to the present invention may have a variety of shapes and sizes, such as circular plate shape, rectangular plate shape, rectangular plate shape, rod shape, spherical shape, elliptic sphere shape according to the shape of the compression molding machine, diameter 1 ~ 6cm, thickness 0.1 ~ 2.0cm And 1 to 50 g in weight are advantageous in formulation and in drug application.

When the tablet of the present invention thus prepared is dropped into a freshwater paddy field, the herbicidal active ingredient is quickly and uniformly dispersed in the paddy field while gas is generated from the tablet by contact with water. For example, tablets administered to paddy water may disintegrate in about 15 minutes, based on a total weight of 25 grams, so that the herbicidal active ingredient may be uniformly dispersed in paddy water 6-8 hours after administration to paddy water. According to the present invention, it is possible to drop in freshwater paddy so that the herbicidal active ingredient is 10 to 1,000g per 10a of paddy field, and when the concentration of the herbicidal active ingredient is outside the above range, it is not preferable in terms of herbicidal effect and weakness against rice. not.

It is effective to apply the weeding method of the present invention in the early to middle stages of rice harvesting after 3 to 15 days of rice transplanting or 5 to 20 days in the case of a straight wave water. In addition to the simple application of herbicides in the herbicide active ingredients can be quickly and uniformly expanded in the rice paddy to remove weeds efficiently in a short time.

Hereinafter, the present invention will be described in more detail based on the following examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

EXAMPLES 1-6

After mixing the components shown in Table 1, mixed and pulverized and compression-molded at a pressure of 100 kg / ㎠ using a tableting machine, and then dried for 1 hour at 70 ℃ in a convection oven 3cm in diameter, 0.3cm in thickness and 5g in weight Was prepared. At this time, the herbicidal active ingredient is previously ground to a particle size of 0.1 ~ 5㎛ using a jet mill.

ingredient Example One 2 3 4 5 6 Azimsulfuron 0.6 0.45 Cyclosulfamyron 2.4 1.8 Halosulfuron-methyl 2.4 1.8 Pyriminobac-methyl 0.6 0.6 0.6 0.6 0.6 0.6 Sodium bicarbonate 42 42 42 42 42 42 Sodium carbonate 7 7 7 7 7 7 Sodium polyacrylate One One One One One One Dioctylsulfosuccinate sodium 3 3 3 3 3 3 Sodium sulfate alkyl One One One One One One Tartaric acid 15 15 15 15 15 15 Ammonium anhydrous 25 25 25 25 25 25

Example 7

Tablets having a diameter of 5 cm, a thickness of 0.8 cm, and a weight of 25 g were prepared by the same ingredients and methods as in Example 3 of Table 1.

Example 8

The components of Table 2 were mixed, pulverized, mixed and compression-molded at a pressure of 100 kg / cm 2 using a tableting machine, and then dried at 70 ° C. for 1 hour in a convection oven to have a diameter of 5 cm, a thickness of 0.8 cm, and a weight. 25 g tablets were prepared. At this time, halosulfuron-methyl and pyriminobac-methyl, which are herbicidal active ingredients, are previously ground to a particle diameter of 0.1 to 5 탆 using a jet mill.

ingredient Added amount (% by weight) Halosulfuron-methyl 2.4 Pyriminobac-methyl 0.6 Sodium bicarbonate 50 Sodium carbonate 7 Sodium polyacrylate One Dioctylsulfosuccinate sodium 3 Sodium sulfate alkyl One Ethylenediaminetetraacetic acid (EDTA) 10 Ammonium anhydrous 25

Example 9

Tablets having a diameter of 3 cm, a thickness of 0.3 cm, and a weight of 5 g were prepared by the same ingredients and methods as in Example 8.

[Comparative Examples 1-3]

Tablets were prepared in the same manner as in Example 1, except that the ingredients shown in Table 3 were used.

Comparative Example 1 Comparative Example 2 Comparative Example 3 Halosulfuron-methyl 2.4 2.4 2.4 Pyriminobac-methyl 0.6 0.6 0.6 Sodium bicarbonate 47 47 43 Sodium carbonate 7 7 7 Sodium polyacrylate 2 2 2 Dioctylsulfosuccinate sodium 5 5 5 Sodium sulfate One One One Tartaric acid 35 35 Succinic acid 35 Corn starch 4

Test Example 1 Stability Test

The tablets of Examples 1 and 8 and the tablets of Comparative Examples 1 to 3 were placed in a 15 cm x 15 cm aluminum pack and sealed. The sealed tablets were placed in a 40 ° C and 50 ° C thermostat, and the change of the wrapping paper was observed while storing for 90 days, and the results are shown in Table 4.

Example 1 Example 8 Comparative Example 1 Comparative Example 2 Comparative Example 3 40 ℃ No expansion No expansion No expansion 1hr 4hr 50 ℃ No expansion No expansion No expansion 0.5hr 2hr

As can be seen in Table 4, the tablets of Comparative Example 2 and Comparative Example 3 without using the absorbent showed a problem of expansion of the wrapping paper during storage. However, the tablets of Example 1 and Example 8 above were stable without expanding the wrapping paper even for more than 70 days. This is the same result as Comparative Example 1 using a moisture absorbent.

[Test Example 2]

One tablet prepared according to Example 3 was administered to a central point of a 5 cm freshwatered 3.3 m × 3.3 m test sphere, and A1, A2, A3 shown in FIG. 1 every 4, 8 and 12 hours after administration. Samples (water) were taken at, A4, B1, B2, B3, B4 and sample injection points. The concentrations of each of the sulfonyl urea herbicidal compounds and annual herbicidal compounds, which are herbicidal active ingredients, are determined by liquid chromatography (HPLC), and are shown in Table 5 below.

compound Collection point Concentration of herbicidal active ingredient (ppm) 3 hours later After 6 hours After 12 hours Sulfonyl Urea-Based Herbicides A1 0.061 0.066 0.065 A2 0.060 0.065 0.065 A3 0.065 0.065 0.065 A4 0.065 0.065 0.065 B1 0.064 0.064 0.064 B2 0.065 0.065 0.065 B3 0.065 0.065 0.065 B4 0.066 0.066 0.065 Dosing point 0.070 0.065 0.065 Annual herbicide compound A1 0.043 0.044 0.044 A2 0.042 0.048 0.044 A3 0.046 0.046 0.043 A4 0.050 0.050 0.045 B1 0.042 0.042 0.042 B2 0.045 0.045 0.044 B3 0.047 0.047 0.046 B4 0.044 0.044 0.045 Dosing point 0.061 0.056 0.054

As can be seen from Table 5, the herbicidal active ingredient in the tablet of the present invention was uniformly expanded at each point without any difference in the concentration in water, and there was almost no change in the concentration in water after 6 hours after the injection of the tablet.

[Test Example 3]

The tablets obtained in Examples 1 to 6, Example 9, and Comparative Example 1 were treated in the same manner as in Test Example 2, and the results of expansion for 6 hours after drug treatment were shown in Table 6.

Example Comparative Example 1 One 2 3 4 5 6 9 Input point One One One One One One One One A point average concentration 0.92 1.25 0.91 1.02 1.24 1.12 0.98 0.21 B point average concentration 0.9 0.85 1,15 0.98 1.18 1.1 0.81 0.31

From the results of Table 6, it can be seen that the addition of the moisture absorbent may adversely affect the expansion of the herbicidal active ingredient, the herbicide of the present invention can exhibit excellent expansion results.

[Test Example 4]

In the harrowed 1.5m × 1.5m test zone, 2.5 seedling 15cm seedlings are transferred to the 20, 40, 60, 80 and 100cm diagonally outward from the center point, and weeds (blood, tadpoles and gourds) in the same way as rice. This, mantis grass, coriander, peel grass, halal, and pots) was planted and freshwater depth was adjusted to 5 cm. After 15 days of locomotion, 1.1 g of the tablet prepared in Example 3 was dropped into the test zone central point (see FIG. 2). At this time, the leaf age of each weed was 2.5 leaf stage (12cm) of blood, 3cm of fern, 3cm of mantis grass, 3.5cm of water whisk, 3.5cm of peeling of grass, 1.5cm of tadpole, and 2.5cm of tadpole. After 30 days after dropping the tablets, the growth of weeds at each point was visually observed, and the growth inhibition of the weeds is shown in Table 7 below.

Type of weed Inhibition of growth of weeds (%) 20 cm 40 cm 60 cm 80 cm 100 cm blood 100 100 100 100 100 Tadpole 100 100 100 100 100 Mantis grass 85 85 85 80 80 Water pinnacle 100 100 100 100 100 Peel 95 95 90 85 85 All five 90 90 90 85 85 Clogs 100 100 100 95 100

As can be seen from Table 7, the tablet of the present invention was excellent in medicinal effects against various annual and perennial weeds. No damage to rice occurred.

[Test Example 5]

In the harrowed 6m × 8.3m test zone, the two-leaf 15cm seedlings are moved 100, 200, 300, 400 and 500cm diagonally outward from the center point, and various weeds Planted, mantis grass, whiskers, bark, barley, and viburnum). The freshwater depth was adjusted to 5 cm and one of the tablets prepared in Example 7 was dropped on the test point center point. At this time, the leaf age of each weed was the same as in the case of Test Example 4. Forty days after the tablets were dropped, the growth of weeds at each point was visually observed, and the growth inhibition of the weeds is shown in Table 8 below.

Type of weed Inhibition of growth of weeds (%) 100 cm 200 cm 300 cm 400 cm 500 cm blood 100 100 100 100 100 Tadpole 100 100 100 100 100 Mantis grass 90 90 80 80 80 Water pinnacle 100 100 100 100 100 Peel 95 90 85 80 80 All five 90 90 80 80 80 Clogs 100 100 100 95 100

[Test Example 6]

After dropping 20 foam tablets prepared in Example 7 to 300 pyeong (10a) weed-rich test, after 20 days and 40 days, various weeds (blood, tadpoles, mantis grass, coriander, respectively) , Peeling, scabbard and creeping buds) to observe the degree of growth is shown in Table 9 below.

Type of weed Inhibition of growth of weeds (%) After 20 days 40 days later blood 100 100 Tadpole 100 95 Mantis grass 90 80 Water pinnacle 100 90 Peel 95 80 All five 95 90 Clogs 100 95

As described above, since the foaming water herbicide according to the present invention does not cause a decrease in the foaming force due to the gas during storage, weeding active ingredients can be quickly and uniformly expanded in rice water to remove weeds in a short time. In particular, the herbicide of the present invention is superior to the herbicidal active ingredient expansion effect than the herbicide using a conventional absorbent.

Claims (8)

A foamable water herbicide composition containing a herbicidal active ingredient, a surfactant, a carbonate, and a mixture of an organic acid and an inorganic acid, wherein the inorganic acid herbicide is used in an amount of 5 to 30% by weight as an inorganic acid. The herbicidal composition of claim 1, wherein the herbicidal active ingredient is a mixture of 0.1 to 10 wt% of sulfonyl urea herbicidal compound and 0.4 to 15 wt% of annual herbicidal compound. The method of claim 2, wherein the sulfonyl urea herbicidal compound is azimsulfuron (1- (4,6-dimethoxypyrimidin-2-yl) -3- [1-methyl-4- (2-methyl -2H-tetraol-5-ylsulfonyl] urea), halosulfuron-methyl (methyl 3-chloro-5- (4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl) -1-methyl Pyrazole-4-carboxylate), bensulfuron-methyl (α- (4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl) -o-toluic acid), ethoxysulfuron (1- (4 , 6-dimethoxypyrimidin-2-yl) -3- (2-ethoxyphenoxysulfonyl) urea), imazosulfuron (1- (2-chloroimidazole [1,2-α] pyridine-3 -Ylsulfonyl) -3- (4,6-dimethoxypyrimidin-2-yl) urea), pyrazosulfuron-methyl (ethyl 5- (4,6-dimethoxypyrimidin-2-ylcarbamoyl) Sulfamoyl) -1-methoxypyrazole-4-carboxylate) and cyclosulfamuron (1- [2- (cyclopropylcarbonyl) phenylsulfamoyl] -3- (4,6-dimethoxypyrimidine- 2-yl) urea) 1 type selected from the group consisting of A stable foaming herbicide composition for water. The compound of claim 2, wherein the annual herbicidal compound is pyriminobac-methyl (methyl-2- (4,6-dimethoxy-2-pyrimidinyloxy) -6- (1-methoxyiminoethyl) benzoate ), Hahalopof-butyl (butyl (R) -2- [4- (4-cyano-2-fluorophenoxy) phenoxy] propionate), indanophan ((RS) -2- [ 2- (3-chlorophenyl) -2,3-epoxypropyl] -2-ethylindan-1,3-dione) and oxazylclomepon (3- [1- (3,5-dichlorophenyl) -1- Methylethyl] -3,4-dihydro-6-methyl-5-phenyl-2H-1,3-oxazin-4-one). The method of claim 1, wherein the surfactant is dioctylsulfosuccinate, naphthalenesulfonate formalin condensate, polyacrylate, sulfate alkyl, lignosulfonate, laurylsulfonate, polyalkylnaphthalenesulfonate, polyethylenenonylphenyl polymer At least one member selected from the group consisting of polyoxyethylene styrylphenyl polymer and polyoxyethylene-polyoxypropylene, and is contained in an amount of 1 to 15% by weight based on the total weight of the composition. The method according to claim 1, wherein the carbonate is at least one selected from the group consisting of sodium carbonate, calcium carbonate, magnesium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate and ammonium bicarbonate, 10 to 40 wt% based on the total weight of the composition. A stable foaming herbicide composition for water, characterized in that it is contained in an amount of. The organic acid of claim 1, wherein the organic acid is at least one selected from the group consisting of citric acid, malic acid, tartaric acid, succinic acid, maleic acid, phthalic acid, adipic acid, and ethylenediaminetetraacetic acid (EDTA), based on the total weight of the composition. A stable foaming herbicide composition for water, characterized in that it is contained in an amount by weight. The herbicidal tablet for effervescent water according to claim 1 is dropped into freshwater paddy so that the herbicidal active ingredient is 10 to 1,000 g per paddy field 10a.