KR100378555B1 - Granular pesticide formulation of impregnation type comprising sulfonylurea - Google Patents

Abstract

According to the present invention, after dissolving a sulfonylurea pesticide using a high boiling petroleum aromatic hydrocarbon or a mixed solvent in which a fixed amount of a heterocyclic compound is mixed with the solvent, the liquid is adsorbed on an adsorptive carrier. It is related with the adsorption type granular pesticide preparation characterized by the above-mentioned. According to the present invention, it is possible to dissolve a sufficient amount of sulfonylurea pesticides in a solvent while maintaining the stability of the main component, and the sulfonylurea pesticides can be put into practical use in the formulation of adsorptive granules.

Description

GRANULAR PESTICIDE FORMULATION OF IMPREGNATION TYPE COMPRISING SULFONYLUREA}

The present invention relates to an adsorption type granulation (Impregnation Type) pesticide preparation of sulfonylurea-based pesticides, which is manufactured using a solvent in which a pesticide containing a sulfonylurea structure (hereinafter referred to as "sulfonylurea-based pesticide") in chemical structure is soluble. . More specifically, the present invention dissolves sulfonylurea pesticides by using a high boiling point petroleum aromatic hydrocarbon capable of dissolving sulfonylurea pesticides or a mixed solvent in which a predetermined amount of heterocyclic compound is mixed with the solvent. After adsorb | sucking, this liquid is made to adsorb | suck to an adsorptive support | carrier, and it is related with the adsorption type granular pesticide preparation characterized by the above-mentioned.

Granular formulations of agrochemicals can generally be divided into extrusion, coating and adsorption depending on the preparation method. Extrude type is a method of mixing minerals (bentonite, talc, etc.), auxiliaries, surfactants, etc. with pesticide raw materials, kneading with water and extruding with extruder. For products containing sulfonylurea pesticides Almost all of them have used this method. The coating method is a method of attaching an adhesive to sand and then coating a solid pesticide on it. The adsorption type (Impregnation Type) is a method of adsorbing a liquid state obtained by dissolving a liquid raw material or a solid raw material in a solvent to an adsorption carrier (zeolite) capable of adsorbing. Among the above methods, there are various economic advantages such as the simplest production process of the adsorption type and the low cost of auxiliary materials, and many products have been developed and produced by the adsorption method. However, in the case of a product containing sulfonylurea pesticides, there is a problem of selecting a solvent capable of dissolving a solid raw material due to the characteristics of the sulfonylurea pesticide, or decomposing a main component in the product even if the solvent can be dissolved. Until now, it has been known that development of adsorption granules is practically impossible for products containing sulfonylurea pesticides. Due to the above problems, among the many pesticide products currently registered and marketed in Korea, when sulfonyl urea-based pesticides are developed as an adsorbent granulation formulation, pyrazo sulfuronethyl and non-sulfonylurea-based sulfonyl urea-based pesticides It is only a combination of pesticides, mololinate. The reason for this is that only a limited amount of sulfonylurea pesticide raw material can be dissolved in the liquid molinate raw material, or even if dissolved, the main ingredient in the product is unstable in the sulfonylurea pesticide except for pyrazosulfuronethyl. The development of adsorptive granules of sulfonyl urea pesticides other than the product has been known to be impossible.

The present invention relates to a pesticide preparation prepared by dissolving a sulfonylurea pesticide used for weed control in order to solve the above problems by using a suitable solvent and stabilizer and then adsorbing on an adsorptive carrier. Unlike other granule formulations, which are complex in process, it is possible to obtain economical adsorbents having a simple production process and inexpensive materials.

The present inventors first select a solvent that can dissolve a certain amount of the sulfonylurea pesticide raw material, and also mixed the specific solvent or other solvent in a certain ratio while checking the stability of the main ingredient for the product made by dissolving the solvent. It was found that the main components of the pesticides in the product were significantly stabilized when the mixed solvent was prepared. In addition, through the addition test of the stabilizer found a way to stabilize the main component more, and came to the step that can be put to practical use immediately.

Thus, according to the present invention there is provided a preparation of adsorptive granules of a product comprising a sulfonylurea pesticide.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments.

Sulfonyl urea-based pesticides are commonly referred to as pesticides with the following chemical structures among the main components of the pesticides, and are generally developed and used as pesticides for weed control. The sulfonylurea pesticides currently registered and used in Korea include bensulfuronmethyl, ethoxysulfuronethyl, cynosulfuron, azimsulfuron, imazosulfuron, pyrazosulfuronethyl, cyclosulfuronmethyl, halosulfuronmethyl and fura. Self-sulfuron etc. are mentioned.

In order to develop an adsorption type granule, first, it is necessary to dissolve the sulfonylurea pesticide, which is a solid as a raw material. Since the solubility of the sulfonylurea pesticide raw material for each solvent is different, it was decided to select a solvent having a certain level of dissolving power in order to focus on the practical application to the product. The content of sulfonylurea pesticides contained per 100 g of pesticide product was dissolved in 6 g-8 g of each solvent and tested for dissolution. As a result, a heterocyclic compound such as N-methyl-2-pyrrolidone, sulfolane, gamma-butylolactone, cyclohexanone, dioxane, morpholine, etc., as a solvent capable of dissolving a sulfonylurea pesticide raw material, High boiling point petroleum aromatic hydrocarbons, formamide, di-methylformamide and the like.

In order to examine the possibility of practical application to adsorptive granules using the above solvent, a certain amount of sulfonylurea pesticide raw material was dissolved in each solvent, and then ethoxylated soybean oil which is commonly used as a water stabilizer was mixed in a conventional amount. A liquid semifinished product was obtained. The liquid semi-finished product was adsorbed onto zeolite, which is an adsorption carrier, to obtain a product, and then the change of the main component in the product was investigated under constant abuse test conditions. In the case of solvents other than petroleum aromatic hydrocarbons, it was found that the main components of sulfonylurea pesticides were unstable in the product, and thus, it was not suitable for use as a solvent when developing as an adsorbent granule. It has been found that the main ingredient in the product is stable while being soluble in sulfonylurea pesticides.

Petroleum-based aromatic hydrocarbons are part of a variety of substances derived from the distillation of crude oil. Preferred aromatic hydrocarbons for use in the present invention include carbon atoms of 9 to 13 (C ₉ to C ₁₃ ), boiling point range of 150 to 280 ° C, aromatic content ( Aromatic content) is a solvent having conditions such as 95% or more. Some solvents differ depending on the type of sulfonylurea pesticides, but in particular, solvents having 11 to 12 carbon atoms (C ₁₁ to C ₁₂ ) mainly have a boiling point of 220 ° C to 280 ° C and an aromatic content of 95% or more. It is preferable to use this because it is good, but is not limited thereto. Fractions containing the carbon number of the petroleum-based aromatic hydrocarbons of 6 to ₈ (C ₆ ~C 8) is mainly and solvency for a sulfonylurea-based pesticide base agent, but is somewhat inappropriate for use in an actual production site strong-volatile flash point is lowered, Fractions containing mainly ₁₄ or more carbon atoms (C ₁₄ ) have little solubility and cannot be used as solvents.

On the other hand, natural zeolites, which are inhalation carriers, have various types depending on the place of production and minerals, and most of them are currently used for pesticides in Korea, where they are heated at high temperature and inhaled at 10% to 13%. If 100g of product is made, the amount of liquid adsorbed cannot be more than 10g. Therefore, when the sulfonyl urea-based pesticides are developed in the form of adsorptive granules, there is a problem in that the product should be capable of dissolving sulfonyl urea in a limited amount of solvent to exhibit a biological effect. However, when petroleum-based aromatic hydrocarbons are used alone, some of the sulfonylurea pesticides may not have sufficient solubility of the solvent to dissolve contents that may have a biological effect, and in particular, different from sulfonyl urea pesticides. In the case of dissolving two pesticide raw materials only in petroleum-based aromatic hydrocarbons when developing a mixture containing pesticides at the same time, it is preferable to mix some of the solvents having excellent solubility because the dissolving power of petroleum-based aromatic hydrocarbons may not be sufficient. Therefore, a mixture of cyclohexanone, gamma-butyrolactone, N-methyl-2-pyrrolidone, dioxane, formamide and the like in a certain amount mixed with petroleum-based aromatic hydrocarbons with low stability but excellent solubility in the product A solvent was prepared and the sulfonylurea pesticide raw material was dissolved in the mixed solvent.

After the adsorption of the pesticide-dissolved solution was adsorbed on the adsorption carrier, the stability of the main component was tested under constant abuse conditions.The smaller the proportion of the solvent added to the petroleum aromatic hydrocarbon, the more the main component was stabilized. In the mixing ratio of 0.1 to 42 parts by weight of the solvent per part by weight, it was found that there was almost no difference in the stability of the main component and when using petroleum aromatic hydrocarbons alone.

In the above experiments, the sulfonylurea pesticide was developed as an adsorbent granule, and the result was obtained up to the level that can be put to practical use. Considering the difference in solvent dissolving power and the difference in the stability of the main component, the test of the third stabilizer was examined. Sulfonylurea-based pesticides generally have better solubility and stability of the main components under conditions where the hydrogen ion concentration of the solution is more alkaline than those under acidic conditions. Therefore, surfactants or isopropylamines or benzyls exhibiting alkalinity to change the solution to alkaline conditions. Alkaline organic compounds such as amine and triethanolamine were added to the above mixed solvents, and the stability of the main components in the product was tested. As a result, it was found that when 1 to 15 parts by weight of the stabilizer was added per 100 parts by weight of the petroleum aromatic hydrocarbon, the main component was more stabilized than when it was not added.

The chemical name of the main component of the sulfonylurea pesticide used in the present invention is as follows, but is not particularly limited thereto.

(A) 3- (4,6-dimethoxypyrimidin-2-yl) -1- (2-ethoxyphenoxysulfonyl) urea

(B) 1- (4,6-dimethoxypyrimidin-2-yl) -3- [1-methyl-4- (2-methyl-2H-tetra-5-yl) pyrazol-5-ylsulfonyl Urea

Hereinafter, the difference between the stability test of the main component of each mixing ratio and the addition of the stabilizer in each of the single solvent and the mixed solvent according to the present invention will be described with specific experimental examples.

Example 1 (comparative)

Simultaneously dissolve 0.046 g of main component (A) and 0.034 g of main component (B) in 4 g of gamma-butyl lactone, and then mix 3 g of ethoxylated soybean oil as an adjuvant to obtain a liquid semi-finished product. Then, the mixture was adsorbed onto 92.92 g of zeolite (95% or more of 14 to 42 taylor mesh, manufactured by Wangpyo Chemical Co., Ltd.) as an adsorptive carrier to obtain an adsorbent granule of sulfonyl urea-based pesticide. Table 1 shows the mixing ratios of the components.

Example 2-4 (comparative) and Example 5

Sulfonyl in the same manner as in Example 1 except for using cyclohexanone, sulfolane, formamide and petroleum aromatic hydrocarbons (trade name Solveso-200, manufactured by Exxon Chemical Korea) instead of gamma-butyl lactone. Adsorption granules of urea-based pesticides were obtained. Table 1 shows the mixing ratios of the components.

Example Example 1 (comparative) Example 2 (comparative) Example 3 (comparative) Example 4 (comparative) Example 5 Manufacturing prescription Pesticide Ingredients (A) 0.046 0.046 0.046 0.046 0.046 Pesticide Ingredients (B) 0.034 0.034 0.034 0.034 0.034 Gamma-butyrolactone 4.0 - - - - Cyclohexanone - 5.0 - - - Sulfolane - - 4.0 - - Formamide - - - 5.5 - Aromatic hydrocarbons - - - - 6.0 Ethoxylated Soybean Oil 3.0 3.0 3.0 3.0 3.0 Zeolite 92.92 91.92 92.92 91.42 90.92

The products obtained in Example 1-5 were put into a thermostat at 40 ° C., respectively, and the contents of the main components were examined after 4 weeks, 8 weeks, and 12 weeks. This was compared with the initial main component content to calculate the decomposition ratio of the main component, the results are shown in Table 2.

Test result Decomposition ratio of the main component (%) Main ingredient (A) Main ingredient (B) Example 4 weeks later 8 weeks later 12 weeks later 4 weeks later 8 weeks later 12 weeks later Example 1 (comparative) 76.0 90.7 - 32.4 85.2 - Example 2 (comparative) 12.4 25.7 35.9 11.6 22.9 30.6 Example 3 (comparative) 49.1 76.8 - 12.7 29.8 55.2 Example 4 (comparative) 28.2 56.9 - 36.1 72.3 - Example 5 (invention) 4.2 7.8 14.2 4.6 9.5 14.7

Example 6

After mixing gamma-butyrolactone in a ratio of 95: 5 with petroleum aromatic hydrocarbon (trade name Solvesso-200, product of Exxon Chemical Korea) to obtain a mixed solution, the main component (A) was 0.046 g, Main ingredient b) 0.034 g was dissolved. Subsequently, 3 g of ethoxylated soybean oil was mixed with this solution as an adjuvant to obtain a liquid semi-finished product, and then adsorbed onto 92.92 g of zeolite (95% or more of 14-42 taylor mesh, Kwang-Pyo Chemical Co., Ltd.) as an adsorption carrier. Adsorption granules of urea-based pesticides were obtained. The mixing ratio of each component is shown in Table 3.

Examples 7-9

As in Example 6 except that the mixing ratio of petroleum aromatic hydrocarbon (trade name Solvesso-200, product of Exxon Chemical Korea) and gamma-butyrolactone is 90:10, 80: 20, 70: 30, respectively. The adsorption granulation of sulfonyl urea pesticides was obtained by the method. The mixing ratio of each component is shown in Table 3.

Example Example 6 Example 7 Example 8 Example 9 Manufacturing prescription Pesticide Main Ingredient (A) 0.046 0.046 0.046 0.046 Pesticide Main Ingredient (B) 0.034 0.034 0.034 0.034 Gamma-butyrolactone 0.2 0.4 0.8 1.2 Aromatic hydrocarbons 3.8 3.6 3.2 2.8 Ethoxylated Soybean Oil 3.0 3.0 3.0 3.0 Zeolite 92.92 92.92 92.92 92.92

The products obtained in Example 6-9 were put in a thermostat at 40 ° C., respectively, and the contents of the main components were examined after 4 weeks, 8 weeks, and 12 weeks. This was compared with the initial main component content to calculate the decomposition ratio of the main component, the results are shown in Table 4.

Test result Decomposition ratio of the main component (%) Main ingredient (A) Main ingredient (B) Example 4 weeks later 8 weeks later 12 weeks later 4 weeks later 8 weeks later 12 weeks later Example 6 5.4 8.2 13.1 5.9 10.9 15.2 Example 7 6.3 10.6 16.2 6.9 10.4 15.8 Example 8 7.8 10.4 19.7 4.8 14.2 17.6 Example 9 14.7 25.0 39.2 7.8 15.1 26.9

Example 10

Cyclohexanone was mixed with a petroleum aromatic hydrocarbon (trade name Solvesso-200, manufactured by Exxon Chemical Korea) at a ratio of 90:10 to obtain a mixed solution, and then 546 g of the mixed solution contained 0.046 g of the main component (a) and the main component ( B) 0.034 g was dissolved. Subsequently, 3 g of ethoxylated soybean oil was mixed with this solution as an adjuvant to obtain a liquid semi-finished product, and then adsorbed onto 91.92 g of zeolite (at least 95% of 14-42 taylor mesh, manufactured by Wangpyo Chemical Co., Ltd.) as an adsorptive carrier. Adsorption granules of urea-based pesticides were obtained. Table 5 shows the mixing ratio of each component.

Examples 11-12

Adsorption granulation of a sulfonyl urea-based pesticide was obtained in the same manner as in Example 10 except that the mixing ratio of petroleum aromatic hydrocarbon and cyclohexanone was set to 80:20 and 70:30, respectively. Table 5 shows the mixing ratio of each component.

Example Example 10 Example 11 Example 12 Manufacturing prescription Pesticide Main Ingredient (A) 0.046 0.046 0.046 Pesticide Main Ingredient (B) 0.034 0.034 0.034 Cyclohexanone 0.5 1.0 1.5 Aromatic hydrocarbons 4.5 4.0 3.5 Ethoxylated Soybean Oil 3.0 3.0 3.0 Zeolite 91.92 91.92 91.92

The products obtained in Examples 10-12 were put in a thermostat at 40 ° C., respectively, and the contents of the main components were examined after 4 weeks, 8 weeks, and 12 weeks. This was compared with the initial main component content to calculate the decomposition ratio of the main component, the results are shown in Table 6.

Test result Decomposition ratio of the main component (%) Main ingredient (A) Main ingredient (B) Example 4 weeks later 8 weeks later 12 weeks later 4 weeks later 8 weeks later 12 weeks later Example 10 4.5 7.9 11.6 3.9 10.9 13.6 Example 11 5.9 8.2 14.5 4.4 9.1 14.1 Example 12 5.2 13.2 18.3 4.9 10.4 15.7

Example 13

0.046 g of main component (a) of sulfonyl urea pesticide in 4 g of a mixed solution of petroleum aromatic hydrocarbon (trade name Solvesso-200, manufactured by Exxon Chemical Korea) at a ratio of 95: 5 and gamma-butyrolactone, B) Dissolve 0.034 g at the same time, mix 0.5 g of alkaline surfactant (trade name NK-ME-160, manufactured by Koseal Co., Ltd.) and ethoxylated soybean oil as an adjuvant to obtain a liquid semi-finished product. Adsorption type granules of sulfonyl urea-based pesticides were obtained by adsorbing onto 92.42 g of zeolite (more than 95% of 14-42 taylor mesh, manufactured by Wangpyo Chemical Co., Ltd.). Table 7 shows the mixing ratio of each component.

Example 14-15

Example 14, except that the mixing ratio of the petroleum aromatic hydrocarbon and gamma-butylolactone is 90:10, and Example 14, except that benzylamine is used instead of the surfactant. Example 15 was carried out in the same manner as in 13. Table 7 shows the mixing ratio of each component.

Example Example 13 Example 14 Example 15 Manufacturing prescription Pesticide Main Ingredient (A) 0.046 0.046 0.046 Pesticide Main Ingredient (B) 0.034 0.034 0.034 Gamma-butyrolactone 0.2 0.4 0.4 Aromatic hydrocarbons 3.8 3.6 3.6 Surfactants 0.5 0.5 - Benzylamine - - 0.5 Ethoxylated Soybean Oil 3.0 3.0 3.0 Zeolite 92.42 92.42 92.42

The products obtained in Examples 13-15 were placed in a thermostat at 40 ° C., respectively, and the contents of the main components were examined after 4 weeks, 8 weeks, and 12 weeks. This was compared with the initial main component content to calculate the decomposition ratio of the main component, the results are shown in Table 8.

Test result Decomposition ratio of the main component (%) Main ingredient (A) Main ingredient (B) Example 4 weeks later 8 weeks later 12 weeks later 4 weeks later 8 weeks later 12 weeks later Example 13 2.1 4.2 9.5 2.9 3.7 8.7 Example 14 3.6 7.7 10.1 3.0 6.6 9.4 Example 15 5.0 10.4 13.1 2.7 6.4 10.2

As can be seen from the above experimental results, according to the present invention, it is possible to dissolve a sufficient amount of sulfonylurea pesticides in a solvent while maintaining the stability of the main component, and thus, more economically, sulfonylurea pesticides can be used as The significance can be found in that the formulation can be put to practical use.

Claims (12)

After dissolving 0.4-4.0 weight part of sulfonylurea pesticides in 100 weight part of high boiling petroleum type aromatic hydrocarbons whose carbon number is 9-13, boiling point is 150-280 degreeC, and aromatic content is 95% or more, this liquid phase 2.32-6.59 An adsorption type granular agrochemical preparation comprising adsorbing 90 parts by weight to 90.12 to 95.68 parts by weight of an adsorptive carrier. delete delete delete delete delete delete delete The liquid phase is a sulfonylurea-based pesticide dissolved in a mixed solvent of the high boiling petroleum aromatic hydrocarbon and the heterocyclic compound, and the mixing ratio of the heterocyclic compound is 100% by weight of the high boiling petroleum aromatic hydrocarbon. 0.1-45 parts by weight per part, wherein the heterocyclic compound is gamma-butyrolactone, N-methyl-2-pyrrolidone, cyclohexanone, dioxane, sulfolane or morpholine Pesticide formulations. 10. The hydrogen ion concentration of the solution according to claim 1 or 9 is adjusted using an alkaline surfactant or a stabilizer of a third component which is an alkaline organic compound selected from isopropylamine, benzylamine and triethanolamine. Adsorption granulated pesticide formulation. 10. The adsorptive granulated agrochemical preparation according to claim 1 or 9, wherein the pesticide is a weed control pesticide. 12. The adsorptive granulated pesticide preparation according to claim 11, wherein the pesticide is a pesticide for weed control of water.