Title of the invention: Controlled dissolution pesticide granules and method for manufacturing the same
Technical field
[One]
Mutual citation with related applications
[2]
This application claims the benefit of priority based on Korean Patent Application No. 10-2018-0113216 filed on September 20, 2018, and all contents disclosed in the documents of the Korean patent application are included as part of this specification.
[3]
[4]
Technical field
[5]
The present invention relates to a controlled dissolution type pesticide granules and a method of manufacturing the same.
[6]
Background
[7]
In the recent agricultural environment where the returning farming population is decreasing and aging is aging, labor saving in the cultivation management of crops has become a very urgent problem. Control, which is one of the most important tasks in cultivation management, can be roughly divided into pests and weeds. For the control work, it is necessary to apply and use pesticides effective against the target diseases and weeds in a timely manner throughout the cultivation period. Usually, a control system is formed by spraying and using several times.
[8]
Since the number of pesticide spraying operations and the types of drugs are large, a lot of effort is required. For example, in the case of water rice, there are drugs used for disinfection of seeds during sowing and germination, drugs for seedling death combination, blast disease from seedling to ear forming period to harvesting period, and drugs used against weeds, ferns, paperback diseases, etc. There are herbicides that are used for, blood, sedge fruits, flowers and weeds. As such, there are many types and frequency of control work, which is an obstacle to the establishment of a labor-saving cultivation system.
[9]
In such a current situation, the inventors of the present invention have a control method capable of ending the spraying and use of various pesticides several times during the cultivation period by spraying and using it at the time of sowing or transplanting the seedlings only once. I thought that it was an ideal labor saving control method in the case of using.
[10]
In order to realize this control method, the dissolution or release of pesticides of different types into the environment (hereinafter referred to as dissolution) is suppressed until the necessary time, and the dissolution of the pesticide active ingredient is initiated promptly at the appropriate time. In addition, pesticide granules that have the function of sustaining the dissolution of the active ingredient of the pesticide during the necessary period are necessary.
[11]
In Japanese Laid-Open Patent Publication No. Hei 6-9303, a coated pesticide granule coated with pesticide particles with a multi-layered coating comprising a layer of a super absorbent swellable material and an olefin-based polymer layer, and in Japanese Laid-Open Patent Publication No. , Coated pesticide granules are disclosed in which pesticide particles are coated with a multilayer film comprising a mixture layer of an olefin-based resin and an alkali water-soluble polymer.
[12]
However, none of the coated pesticide granules could completely inhibit the dissolution of the active pesticide ingredient during the dissolution suppression period. That is, in conventional pesticide granules, there is always an elution of some pesticide active ingredients into the environment within a predetermined dissolution suppression period, and in other words, leakage of pesticide active ingredients. Thus, when a large amount of the covered pesticide granules were used at the same time as sowing or transplanting the seedlings, a growth disorder (weak harm) occurred. Therefore, it was impossible to use the coated pesticide granules containing all or most of the pesticide active ingredients required during the cultivation period from sowing to harvesting at the same time as sowing or transplanting seedlings. For this reason, it has not been too early to achieve significant labor savings in pesticide spraying operations.
[13]
In other words, when pesticides have an incomplete timed dissolution function, use of them at once involves a risk of weakening, and thus, in reality, the ideal labor-saving control method has not been realized.
[14]
[15]
In particular, in the cultivation of agricultural crops, the above-mentioned risks need to be completely avoided, as the good and bad growth in the early stages of cultivation greatly affects the crop, as it has long been referred to as ``seedo cultivation''. There is. In addition, in the case of normal one-year crops such as water paddy, especially failure is not allowed.
[16]
In this way, the development of a technology that improves the dissolution inhibiting function of the time-limited dissolution coated pesticide granules, that is, the development of a technology that completely or minimally reduces the leakage of the pesticide active ingredient into the environment during the dissolution suppression period, has led to the establishment of a labor-saving cultivation method. It's a task for you.
[17]
In addition, since the coating pesticide granules require additional equipment for forming the coating layer, the production cost is high, and even if a high degree of dissolution control is realized, the economical burden is high, and thus practical use may be difficult.
[18]
[19]
Accordingly, the inventors of the present invention are capable of manufacturing dissolution-controlled pesticide granules at low cost in order to solve the conventional problems, while reducing environmental pollution due to low toxicity and biodegradability, and a dissolution-controlled type that can realize high-level dissolution control. We want to provide pesticide granules.
[20]
[21]
[Prior technical literature]
[22]
[Patent Literature]
[23]
Republic of Korea Patent Publication No. 10-0399366 (announced on September 15, 2003)
[24]
Japanese Unexamined Patent Application Publication No. Hei 6-9303 (published on January 18, 1994)
[25]
Japanese Unexamined Patent Application Publication No. Hei 6-9304 (published on January 18, 1994)
[26]
Detailed description of the invention
Technical challenge
[27]
The problem to be solved of the present invention is to provide a controlled dissolution type pesticide granule and a method for producing the same, which has low environmental pollution due to its low toxicity and biodegradability characteristics, can realize high dissolution control, and can be manufactured at low cost.
[28]
Means of solving the task
[29]
The present invention is a controlled-release agrochemical granule comprising an agrochemical active ingredient, a natural wax and a pH adjusting agent, wherein the agrochemical active ingredient comprises a pyridine sulfonylurea compound represented by the following formula (1), a salt or a stereochemical isomer thereof, and the The natural wax contains 2 to 8% by weight based on the total weight of the pesticide granules, and the pesticide granules provide a controlled-release pesticide granule having a pH of 4 to 6 in a 1% by weight suspension in water.
[30]
[Formula 1]
[31]

[32]
In Chemical Formula 1,
[33]
n represents an integer of 1 to 3,
[34]
R is hydrogen or an alkyl group having 1 to 4 carbon atoms,
[35]
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,
[36]
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]
[38]
In addition, the present invention, 1) forming a mixture by mixing a pyridine sulfonyl urea compound represented by the following formula (1), a salt thereof, or an agrochemical active ingredient containing a stereochemical isomer, a natural wax and a pH adjusting agent; 2) preparing a mixture paste by stirring the mixture in a solvent; And 3) assembling and drying the mixture paste.
[39]
[Formula 1]
[40]

[41]
In Chemical Formula 1,
[42]
n represents an integer of 1 to 3,
[43]
R is hydrogen or an alkyl group having 1 to 4 carbon atoms,
[44]
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,
[45]
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.
[46]
In addition, the present invention provides a method for cultivating agricultural crops using the dissolution-controlled pesticide granules.
[47]
Effects of the Invention
[48]
According to the dissolution-controlled pesticide granules of the present invention and the production method thereof, environmental pollution is small due to low toxicity and biodegradability characteristics, high dissolution control can be realized, and dissolution-controlled pesticide granules can be manufactured at low cost.
[49]
Brief description of the drawing
[50]
The following drawings attached to the present specification illustrate specific embodiments of the present invention, and serve to further understand the technical idea of ​​the present invention together with the content of the above-described invention. It is limited and should not be interpreted.
[51]
1 is a graph showing the dissolution degree (%) in water after 72 hours of dissolution-controlled pesticide granules of Example 1 and Comparative Example 1. FIG.
[52]
Mode for carrying out the invention
[53]
Hereinafter, the present invention will be described in more detail to aid understanding of the present invention. At this time, terms or words used in the present specification and claims should not be construed as being limited to a conventional or dictionary meaning, and the inventor appropriately defines the concept of terms in order to describe his own invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of ​​the present invention based on the principle that it can be done.
[54]
[55]
The present invention relates to a dissolution-controlled pesticide granule and a method for manufacturing the same, which has less environmental pollution due to its low toxicity and biodegradability, and can realize high-level dissolution control, and can be manufactured at low cost, and a method of manufacturing the same. It aims to provide.
[56]
[57]
Hereinafter, the dissolution-controlled pesticide granules of the present invention and a method of manufacturing the same will be described in detail.
[58]
[59]
Dissolution control type pesticide granulation
[60]
[61]
The dissolution-controlled pesticide granules of the present invention may contain an agrochemical active ingredient, a natural wax and a pH adjuster, and the pesticide active ingredient may include a pyridine sulfonylurea compound represented by the following formula (1), a salt or a stereochemical isomer thereof. The natural wax may be included in 2 to 8% by weight based on the total weight of the pesticide granules, and the pesticide granules may be in a pH of 4 to 6 in a 1% by weight suspension in water.
[62]
[Formula 1]
[63]

[64]
In Chemical Formula 1,
[65]
n may represent an integer of 1 to 3,
[66]
R may be hydrogen or an alkyl group having 1 to 4 carbon atoms,
[67]
R'may be 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,
[68]
Each of X and Y may independently be 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.
[69]
[70]
Hereinafter, each constituent component and a dissolution control function of the dissolution-controlled pesticide granule of the present invention will be specifically examined.
[71]
[72]
1) Pesticide active ingredient
[73]
[74]
The pesticide active ingredient of the controlled dissolution type pesticide granule of the present invention includes a pyridine sulfonylurea compound represented by the following formula (1), which is known to be useful as a herbicide for treatment before and/or after germination in rice agriculture, a salt or a stereochemical isomer thereof. It is characterized by being able to.
[75]
[Formula 1]
[76]

[77]
In Chemical Formula 1,
[78]
n may represent an integer of 1 to 3,
[79]
R may be hydrogen or an alkyl group having 1 to 4 carbon atoms,
[80]
R'may be 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,
[81]
Each of X and Y may independently be 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.
[82]
[83]
Specifically, in Formula 1, n may be an integer of 1 or 2, R may be a hydrogen or a methyl group, R′ may be a hydrogen, a halogen group or a methyl group, and X and Y may each be a methoxy group. have.
[84]
[85]
More specifically, in Formula 1, n may be an integer of 1 or 2, R may be a methyl group, R′ may be hydrogen, Cl, Br or a methyl group, and X and Y may each be a methoxy group. have.
[86]
[87]
In addition, the pyridinesulfonylurea compound represented by Formula 1 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-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)aminocarbonyl] -4-bromo-2-(2-fluoro-1-methoxyacetoxy-n-propyl)pyridine-3-sulfonamide.
[88]
[89]
More specifically, the pyridinesulfonylurea compound represented by Formula 1 may be a compound of Formula 2 [ISO proposal name: flucetosulfuron].
[90]
[Formula 2]
[91]

[92]
[93]
The flucetosulfuron is safe for these crops when treated with soil or foliage for rice, wheat, barley (appropriate dosage: 10 to 40 g ai/ha) and turf (appropriate dosage: 50 to 200 g ai/ha), It is known to have excellent herbicidal effect on a wide range of weeds such as broadleaf weeds, herbaceous weeds, sedge weeds, annual and perennial weeds.
[94]
[95]
Further, when formulating the controlled-dissolution agrochemical granules of the present invention, in addition to the pyridine sulfonylurea compound represented by the general formula (1), one or two or more other agricultural chemical active ingredients may be optionally mixed. The pesticide active ingredient that can be mixed may include, but is not limited to, a general herbicidal active ingredient, an insecticidal active ingredient, a bactericidal active ingredient, or an active ingredient for controlling plant growth.
[96]
[97]
When the dissolution-controlled pesticide granule of the present invention is used, the solubility in water (25° C.) is 100 ppm or more, more preferably 500 ppm or more, and even when a relatively high pesticide active ingredient is used, dissolution control becomes possible. As an agricultural chemical active ingredient with relatively high solubility, specifically, a neonicotinoid compound can be exemplified, and more specifically, nitenpyram, imidacloprid, acetamiprid, thiamethoxam, crotianidine, thia Cloprid, dinotephran, and the like can be preferably illustrated.
[98]
[99]
On the other hand, it is preferable that the dissolution-controlled pesticide granules of the present invention contain 0.1 to 0.4% by weight, more specifically 0.2% to 0.3% by weight of the total weight of the pesticide active ingredient.
[100]
When the dissolution-controlled pesticide granules of the present invention contain the pesticide active ingredient in the content ratio within the above range, a sufficient control effect can be obtained, and at the same time, the dissolution of the pesticide active ingredient can be effectively inhibited.
[101]
[102]
2) Natural wax
[103]
[104]
The dissolution-controlled pesticide granules of the present invention use natural wax, not synthetic plastic resin, unlike the dissolution control method of conventional pesticide granules, so that environmental pollution is small and high level of dissolution control is realized due to the low toxicity and biodegradability characteristics of natural wax. Characterized in that.
[105]
[106]
Specifically, the natural wax used in the present invention is characterized in that the melting point is 70 to 90 ℃, specifically 75 to 85 ℃.
[107]
In the case of using a natural wax having a melting point within the above range, the natural wax melts by heat generated during the assembly and drying process of the pesticide granule and fills the voids in the pesticide granule, thereby controlling the disintegration of the granule in water to elute the active pesticide ingredient. Can be controlled.
[108]
If the melting point is too low, the natural wax may be denatured due to heat generated during the assembly and drying process of the pesticide granule, or the wax may spill out of the granule and be lost, and the wax may spill out depending on the environment during the storage process. have. If the melting point is too high, the natural wax does not melt due to heat generated in the assembly and drying process of the pesticide granule, so that it may not have a dissolution control function.
[109]
[110]
Specifically, the natural wax that can be used in the present invention is beeswax (Bees Wax), lanolin (Lanolin; Wool Wax), animal natural wax such as whale wax and tallow; Alternatively, it may include one or more vegetable natural waxes such as Carnauba wax, Candelilla Wax, Rice Wax, and Japanese wax, and more specifically, stability against heat and Carnauba wax is most preferred in terms of its melting point. On the other hand, the melting point of the carnauba wax is about 80 to 85 ℃.
[111]
[112]
In addition, it is preferable that the dissolution-controlled pesticide granules of the present invention contain 2 to 8% by weight, specifically 3 to 5% by weight, based on the total weight of the natural wax.
[113]
If it is contained in less than the above range, the pesticide active ingredient is released in a relatively short period of time, so that the possibility of promoting weakening is high, and if it exceeds the above range, the release of the active ingredient is excessively suppressed to obtain a sufficient effect of controlling harmful organisms. It may not be possible.
[114]
[115]
On the other hand, the dissolution-controlled pesticide granules of the present invention may further include a coating layer containing natural wax on all or part of the granule surface by melting the natural wax component in the pesticide granule. In this case, within a predetermined dissolution inhibiting period, some pesticides There may be an advantage that the leakage of the active ingredient into the environment is further suppressed.
[116]
[117]
3) pH adjuster
[118]
[119]
The pyridine sulfonylurea compound represented by the general formula (1), which is an active pesticide ingredient of the present invention, has a property of ionizing hydrogen atoms of the sulfonamide group by desorbing it, and therefore has a characteristic of lowering the water solubility under acidic conditions.
[120]
[121]
Accordingly, the dissolution-controlled pesticide granules of the present invention further include a pH adjusting agent to control the dissolution by adjusting the pH of the granules.
[122]
[123]
Specifically, the pH adjusting agent used in the dissolution-controlled pesticide granules of the present invention may include organic acids such as acetic acid, citric acid, ascorbic acid, sorbic acid, succinic acid, fumaric acid, oleic acid and benzoic acid; Or it may be an inorganic acid such as phosphoric acid, hydrochloric acid and sulfuric acid.
[124]
[125]
More specifically, the present invention may use phosphoric acid, and more specifically, phosphoric acid 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 ) It may be one or more selected from the group consisting of.
[126]
[127]
On the other hand, it is preferable that the dissolution-controlled pesticide granules of the present invention comprise 10 to 25% by weight, specifically 10 to 20% by weight, or 10 to 15% by weight of the pH adjusting agent based on the total weight of the pesticide granules. When the pH adjuster is included in the content ratio within the above range, a sufficient control effect can be obtained, and at the same time, suppression of the dissolution of the active pesticide component can be effectively achieved.
[128]
[129]
The dissolution-controlled pesticide granules of the present invention are characterized in that by including the pH adjusting agent, pH 4 to 6, more specifically pH 5 to 6 in a 1% by weight suspension in water.
[130]
In the present invention, '1% by weight of suspension in water' refers to a suspension in which 1% by weight of a controlled-release pesticide granule is suspended in 99% by weight of water.
[131]
When the pH in the 1% by weight suspension in water is less than the above range, the release of the active ingredient is excessively suppressed, so that sufficient harmful organism control effect may not be obtained. There is a problem that it is released to, and the possibility that the weakening is promoted increases.
[132]
[133]
4) Other additives
[134]
[135]
In addition, the dissolution-controlled pesticide granules according to the present invention may further include a solid carrier, a surfactant, a solvent, a dispersant, a wetting agent, a thickener, a binder, or an adjuvant, in addition to the above components.
[136]
[137]
What can be used as a solid carrier is natural minerals such as quartz, clay, silica sand, kaolinite, pyrophyllite, talc, bentonite, acid clay, attapulgite, zeolite, and diatomaceous earth; Inorganic salts such as calcium carbonate, ammonium sulfate, sodium sulfate, and potassium chloride; Organic solid carriers such as synthetic silicic acid, synthetic silicate, starch, cellulose, and plant powder; Plastic carriers such as polyethylene, polypropylene, and polyvinylidene chloride; Urea, inorganic hollow bodies, plastic hollow bodies, fumed silica (white carbon), and the like.
[138]
Each of the carriers may be used alone or in combination of two or more, and the blending ratio is generally 0.1 to 95% by weight, preferably 1 to 90% by weight, more preferably May be in the range of 10 to 90% by weight.
[139]
[140]
What is possible as a solvent include alcohols and glycols and ethers and esters thereof such as aromatic hydrocarbons such as xylene mixtures or substituted naphthalene ethanol, ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether; Ketones such as cyclohexanone; Strong polar solvents such as N-methyl-2-pyrrolidone, dimethylsulfoxide or dimethyl formamide; Epoxidized or non-epoxidized vegetable oils such as epoxidized coconut oil or soybean oil; Or water.
[141]
[142]
As the dispersing agent, anionic dispersants such as salts of lignin sulfonic acid, salts of naphthalene sulfonic acid, salts of lauryl sulfate, salts of lauryl sulfonic acid, salts of polyoxyalkylene alkyl aryl ether sulfates, salts of polyoxyalkylene alkyl ether sulfates, Polyoxyalkylene alkyl aryl ether, polyoxyalkylene alkyl ether, and the like are exemplified.
[143]
[144]
Examples of wetting agents include anionic wetting agents such as sodium lauryl sulfate, salts of polyoxyalkylene alkyl phenyl ether sulfonic acids, salts of dialkyl sulfosuccinates, salts of dialkyl naphthalene sulfonic acids, salts of polyoxyalkylene alkyl ether sulfates, and acetylene series. Various types of compounds, such as nonionic surfactants or urea complexes of nonionic surfactants, can be used.
[145]
[146]
The wetting agent and dispersing agent are not limited to those described above, and a suitable one may be used among nonionic surfactants and anionic surfactants, and cationic surfactants may also be used in some cases.
[147]
[148]
What is possible as a thickener is divided into polysaccharides such as homo and heterosaccharides, and inorganic substances such as montmorillorite, smectite, sepiolite, hectorite, and hydrophilic/hydrophobic silica. For example, furan gum may be used as a homozygous saccharide, and guar gum, xanthan gum, and wellan gum may be exemplified as a heterozygous saccharide.
[149]
[150]
Available as binders are starch, dextrin, alpha starch, sodium alginate, gum arabic, gelatin, lignin sulfonate, glucose, sorbitol, polyethylene glycol, hydroxypropyl cellulose (HPC). ), hydroxypropyl methyl cellulose, and polyvinyl pyrrolidone.
[151]
[152]
Adjuvant is a substance that is added in the preparation stage or diluted in the preparation stage of the spray solution to increase drug efficacy. Typically, anionic surfactants, cationic surfactants, and nonionic surfactants are typical.
[153]
Substances that can be used as adjuvants include salts of dialkyl sulfosuccinates, acetylene-based nonionic surfactants, polyoxyalkylene alkyl ethers, polyoxyalkylene alkylphenol ethers, polyoxyethylene alkylamines, ethoxylated sorbitan Ester, polyoxyethylene fatty acid ester, polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer, alkoxylated trisiloxane, and the like.
[154]
[155]
Each of the additives may be used alone or in combination of two or more, and the blending ratio is generally 0.01 to 30% by weight, preferably 0.01 to 20% by weight, more preferably based on the total weight of the dissolution-controlled pesticide granule. Preferably, it may be in the range of 0.01 to 15% by weight.
[156]
[157]
5) Dissolution control function
[158]
[159]
The dissolution-controlled pesticide granules of the present invention have a timed dissolution control-type sustained-release function.
[160]
[161]
The time-limited dissolution control type sustained-release function is a dissolution pattern that is composed of a dissolution suppression period in which the dissolution of the pesticide active ingredient is suppressed for a certain period of time after use, and a dissolution start point and dissolution duration that initiates and continues rapid dissolution after a certain period Means function.
[162]
Specifically, the period from after use until about 20% by weight of the pesticide active ingredient in the pesticide granule is eluted in the external environment is the dissolution control period, and the period until about 100% by weight is eluted beyond 20% by weight. In the case of a duration, it means a function of realizing a dissolution pattern in which the ratio of the dissolution suppression period/dissolution duration is 0.2 or more.
[163]
[164]
The dissolution-controlled pesticide granule of the present invention has a timed dissolution control type sustained release function by natural wax, and has an excellent timed dissolution function in which leakage of the pesticide active ingredient during the dissolution inhibition period is significantly suppressed.
[165]
[166]
Specifically, the dissolution-controlled pesticide granules of the present invention are characterized in that the dissolution degree of the pesticide active ingredient after 72 hours is 10 to 20%, specifically 10 to 15%, and the dissolution duration of the pesticide active ingredient of the pesticide granule is It is characterized in that it is 200 to 300 hours, specifically 250 to 300 hours. The dissolution duration refers to a period in which the dissolution degree of the agricultural chemical active ingredient reaches 90 to 100%, specifically 95 to 100%, after the start of dissolution.
[167]
[168]
As described above, the dissolution-controlled pesticide granules of the present invention inhibit the dissolution of the pesticide active ingredient during the dissolution inhibiting period, and the dissolution lasts for a certain period of time or longer after the initiation of dissolution. Or, even if it is used at the same time as transplanting, it does not cause growth disorder (weakness) at the beginning of cultivation. In addition, the agrochemical active ingredient contained in addition to the pyridine sulfonylurea compound represented by the formula (1) as the agrochemical active ingredient of the present invention is similarly controlled so that the number of spraying and use of pesticides can be reduced, and their work can be significantly reduced I can.
[169]
[170]
Therefore, when the present invention is used, an ideal labor saving control method for agricultural work can be realized.
[171]
[172]
Dissolution control type pesticide granule manufacturing method
[173]
[174]
In addition, the present invention provides a method for producing a controlled-release pesticide granule capable of producing a controlled-release pesticide granule at low cost.
[175]
[176]
Pesticide granules can be obtained by granulating a raw material containing an active pesticide ingredient as an essential ingredient. Examples of such a granulation method include an extrusion granulation method, a coating granulation method, and an adsorption granulation method. In the present invention, among these granulation methods, it is characterized by the extrusion granulation method.
[177]
[178]
Hereinafter, the method for producing a controlled dissolution pesticide granule according to the present invention will be examined in detail.
[179]
[180]
The method for producing a controlled dissolution agrochemical granule according to the present invention comprises: 1) a pyridine sulfonyl urea compound represented by the following formula (1), a salt thereof, or an agrochemical active ingredient including a stereochemical isomer, a natural wax, and a pH adjusting agent to form a mixture. step; 2) preparing a mixture paste by stirring the mixture in a solvent; And 3) assembling and drying the mixture paste, and the drying temperature may be 75 to 100°C.
[181]
[Formula 1]
[182]

[183]
[184]
In Formula 1, n may represent an integer of 1 to 3,
[185]
R may be hydrogen or an alkyl group having 1 to 4 carbon atoms,
[186]
R'may be 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,
[187]
Each of X and Y may independently be 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.
[188]
[189]
The dissolution-controlled pesticide granules of the present invention may be prepared using an extrusion granulator by a wet granulation method, and one or more active pesticides, natural waxes, pH adjusters, solid carriers, and other additives are added to uniformly mix them with a solvent in a mixture obtained. As an auxiliary component of the liquid and an appropriate amount of water, it is kneaded into a paste type, and then dried after assembling using an extrusion granulator equipped with a screen having a diameter of 0.5 to 3 mm, specifically 0.5 to 1.5 mm Can be manufactured.
[190]
[191]
On the other hand, the pyridine sulfonyl urea compound represented by Formula 1, which is an agrochemical active ingredient of the present invention, does not have high thermal stability, and requires careful control of the drying temperature, and the drying temperature of the present invention is 75 to 100°C, specifically Is characterized in that it may be 75 to 90 ℃, more specifically 80 to 90 ℃.
[192]
If the drying temperature is too low, the drying time may be too long and productivity may decrease, and the longer the time until the water is completely removed after drying, the greater the amount of active pesticides moving from the inside of the granule to the outside during the manufacturing process, controlling the dissolution. There may be a problem that the function is impaired. Conversely, if the drying temperature is too high, the stability of the pesticide active ingredient may be poor, and sufficient control effects may not be expected.
[193]
[194]
The dissolution-controlled pesticide granules of the present invention obtained by the above production method may have an average particle diameter in the range of typically 0.5 to 3 mm, specifically 0.5 to 1.5 mm.
[195]
[196]
In addition, the present invention can provide a method for cultivating agricultural crops using a controlled-release pesticide granule, and is used by spraying the controlled-release pesticide granule onto the soil and water, and the leaves and stems of the crop.
[197]
The elution-controlled pesticide granules are not limited to target crops, and in addition to rice, leafy vegetables such as cabbage, lettuce, spinach, root vegetables such as radish, carrot, fruit vegetables such as tomatoes, cucumbers, and pumpkins, rice, pulses, corn, potatoes, and legumes , Craft crops, flowers, etc.
[198]
[199]
As described above, the present invention can provide a controlled-dissolution pesticide granule and a method for producing the same, which can be produced at low cost, with less environmental pollution due to low toxicity and biodegradability, and high dissolution control can be realized.
[200]
[201]
Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily implement the present invention. However, the present invention may be implemented in various different forms and is not limited to the embodiments described herein.
[202]
[203]
Example 1
[204]
1.FTS (flucetosulfuron) 0.25 parts by weight, sodium ligno sulfonate (Sodium Ligno Sulfonate; SLS; cas no. 8061-51-6) 3 parts by weight, potassium dihydrogen phosphate (KH 2 PO 4 ) 10 parts by weight, cana After mixing 3 parts by weight of Carnauba Wax and 79.75 parts by weight of Pyrophyllite (PLW; cas no. 12269-78-2), pulverization was performed using an air-mill.
[205]
2. A homogeneous solution was prepared by mixing 10 parts by weight of NK-PVA25 (a 40% by weight aqueous solution of PVAc) with 18 parts by weight of water.
[206]
3. After putting the pulverized product of 1 into the solution made in 2 and kneading, granulation using an extruder granulator, and drying using a fluidized bed dryer at 80° C. for 30 minutes to prepare 100 g (100 parts by weight) of pesticide granules. .
[207]
[208]
Example 2
[209]
In Example 1, a pesticide granule was prepared in the same manner as in Example 1, except that 5 parts by weight of Carnauba Wax and 77.75 parts by weight of Pyrophyllite were used.
[210]
[211]
Example 3
[212]
Except that in Example 1, 5 parts by weight of Carnauba Wax , 20 parts by weight of potassium dihydrogen phosphate (KH 2 PO 4 ), and 67.75 parts by weight of Pyrophyllite were used. Pesticide granules were prepared in the same manner as in 1.
[213]
[214]
Comparative Example 1
[215]
In Example 1, a pesticide granule was prepared in the same manner as in Example 1, except that Carnauba Wax was not used and 82.75 parts by weight of Pyrophyllite was used.
[216]
[217]
Comparative Example 2
[218]
In Example 1, a pesticide granule was prepared in the same manner as in Example 1, except that 1 part by weight of Carnauba Wax and 81.75 parts by weight of Pyrophyllite were used.
[219]
[220]
Comparative Example 3
[221]
In Example 1, a pesticide granule was prepared in the same manner as in Example 1, except that 10 parts by weight of Carnauba Wax and 72.75 parts by weight of Pyrophyllite were used.
[222]
[223]
Comparative Example 4
[224]
Pesticide granules were prepared in the same manner as in Example 1, except that potassium dihydrogen phosphate (KH 2 PO 4 ) was not used in Example 1, and 89.75 parts by weight of pyrophyllite was used.
[225]
[226]
[Table 1]
Carnauba Wax Content KH 2 PO 4 content Drying temperature PH in 1% suspension in water
Example 1 3 parts by weight 10 parts by weight 80 ℃ 6.0
Example 2 5 parts by weight 10 parts by weight 80 ℃ 6.0
Example 3 5 parts by weight 20 parts by weight 80 ℃ 5.5
Comparative Example 1 - 10 parts by weight 80 ℃ 6.0
Comparative Example 2 1 part by weight 10 parts by weight 80 ℃ 6.0
Comparative Example 3 10 parts by weight 10 parts by weight 80 ℃ 6.0
Comparative Example 4 3 parts by weight - 80 ℃ 7.0
[227]
[228]
Experimental example
[229]
The physical properties of the Examples and Comparative Examples were measured, and the results are shown in Fig. 1 and Tables 2 and 3.
[230]
[231]
1) Water dissolution experiment
[232]
In order to measure the dissolution degree of the controlled-dissolution pesticide granules prepared in each Example and Comparative Example in water, 0.6 mg of the controlled-dissolution pesticide granules of each Example and Comparative Example were added to a glass bottle containing 250 ml of distilled water, and allowed to stand under the conditions of 20°C. . After a certain period of time (4 hours, 72 hours, 288 hours, 336 hours), 1 ml of the solution was sampled using a micropipette in the middle of the vial. After adding 1 ml of acetonitrile to the sampled solution, filtering was performed, the amount of a pesticide active ingredient (FTS) was measured. The amount of the pesticide active ingredient in water was measured using high performance liquid chromatography (486 tunable UV/VIS detector manufactured by Waters), and the results are shown in Fig. 1 and Table 2 and Table 3.
[233]
Dissolution in water (%) = (X / Y) × 100
[234]
(X: Amount of active pesticides dissolved in water after a certain period of time, Y: Total amount of active pesticides contained in pesticide granules before dissolution in water)
[235]
[236]
1-1) Comparison according to the presence or absence of natural wax
[237]
As shown in FIG. 1, the pesticide granules of Example 1 using natural wax have a dissolution rate in water of about 12.2% after 72 hours, whereas the pesticide granules of Comparative Example 1 without natural wax dissolution rate in water after 72 hours. Was found to be 97%.
[238]
Through this, it was confirmed that the pesticide granules of Example 1 using natural wax had an excellent dissolution control function.
[239]
[240]
1-2) Comparison according to the amount of natural wax used
[241]
[Table 2]
Natural wax usage Dissolution of flucetosulfuron in water (%)
4 hrs 72 hrs 288 hrs
Example 1 3 parts by weight 2.49 12.2 97.7
Example 2 5 parts by weight 4.48 15.5 97.9
Comparative Example 1 - 69 97 99.9
Comparative Example 2 1 part by weight 12.0 46.6 99.8
Comparative Example 3 10 parts by weight 3.75 18.44 90.7
[242]
[243]
As shown in Table 2, in Examples 1 and 2 using an appropriate amount of natural wax, a high degree of dissolution control is realized at about 12 to 15% in water after 72 hours, and the dissolution rate in water after 288 hours is about 98%. It was confirmed that after spraying the pesticide granules, the active ingredient continued to dissolve for a certain period necessary for farming.
[244]
On the other hand, Comparative Example 1, which did not use natural wax at all, showed that the dissolution rate in water after 4 hours was 69%, and the dissolution rate in water after 72 hours was 97%, so that dissolution control was not at all, and a small amount of natural wax was used. Comparative Example 2 confirmed that the dissolution control function was not excellent at about 46% in water after 72 hours.
[245]
On the other hand, in Comparative Example 3, the granules were floating on the surface of the water, so it was impossible to measure the elution degree in water under the same conditions. So, the glass bottle was inverted several times, forcibly dropped below the water surface, and then the measurement test was conducted. It can be seen that the dissolution control function is deteriorated compared to the Example even though the measurement test was performed by changing the conditions so that the dissolution degree can be measured as described above, and the granules floated on the surface of the water, so that the same conditions as in Examples 1 and 2. Comparative Example 3, which is a degree in which it is impossible to measure the elution degree in water, is not preferable because there is a concern of weakening when used in an actual paddy field.
[246]
[247]
1-3) Comparison of pesticide granules according to pH in 1% by weight suspension in water
[248]
[Table 3]
PH in 1% suspension in water Dissolution of flucetosulfuron in water (%)
4 hrs 72 hrs 336 hrs
Example 1 6 2.49 12.2 99.8
Example 3 5.5 3.5 17.1 89.6
Comparative Example 4 7 24 97.0 99.7
[249]
[250]
As shown in Table 3, the pesticide granules of Example 1 with a pH of 6 and Example 3 with a pH of 5.5 in a 1% by weight suspension in water have a high degree of dissolution control, but that of Comparative Example 4 with a pH of 7. It was confirmed that the dissolution control function of the pesticide granules was not realized.
[251]
This is due to the fact that the water solubility of flucetosulfuron, which is an active pesticide ingredient of the present invention, decreases with acidic conditions, and it was confirmed that the weakly acidic pesticide granules had a high degree of dissolution control function.
[252]
[253]
The above description of the present invention is for illustrative purposes only, and those of ordinary skill in the art to which the present invention pertains will be able to understand that other specific forms can be easily modified without changing the technical spirit or essential features of the present invention. will be. Therefore, it should be understood that the embodiments described above are illustrative and non-limiting in all respects.
Claims
[Claim 1]
As a dissolution-controlled pesticide granule comprising an agrochemical active ingredient, a natural wax and a pH adjusting agent, the pesticide active ingredient includes a pyridine sulfonylurea compound represented by the following Formula 1, a salt or stereochemical isomer thereof, and the natural wax It contains 2 to 8% by weight based on the total weight of the granules, and the pesticide granules are pH 4 to 6 in a 1% by weight suspension in water. In Formula 1 , n represents 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]
According to claim 1, wherein the pesticide active ingredient is contained in 0.1 to 0.4% by weight based on the total weight of the pesticide granules controlled dissolution type pesticide granules.
[Claim 3]
The method of claim 1, wherein the agrochemical active ingredient is 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-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-methoxy Propion)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)aminocarbonyl]-4-bromo-2 -(2-Fluoro-1-methoxyacetoxy-n-propyl) pyridine-3-sulfonamide, the dissolution control type pesticide granules containing at least one selected from the group consisting of.
[Claim 4]
According to claim 1, The melting point of the natural wax is 70 to 90 ℃ controlled dissolution type pesticide granules.
[Claim 5]
The method of claim 1, wherein the natural wax is an animal natural wax; Or a controlled-release pesticide granule containing at least one vegetable natural wax.
[Claim 6]
According to claim 1, The pesticide granule dissolution control type pesticide granules further comprising a coating layer containing natural wax on all or part of the surface.
[Claim 7]
According to claim 1, wherein the pH control agent is a controlled-release pesticide granules containing 10 to 25% by weight based on the total weight of the pesticide granules.
[Claim 8]
According to claim 1, wherein the pH adjusting agent is an organic acid containing at least one selected from the group consisting of acetic acid, citric acid, ascorbic acid, sorbic acid, succinic acid, fumaric acid, oleic acid and benzoic acid; Or a controlled-release pesticide granule containing an inorganic acid containing at least one selected from the group consisting of phosphoric acid, hydrochloric acid and sulfuric acid.
[Claim 9]
The method of claim 8, wherein the phosphoric acid 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 ) Dissolution-controlled pesticide granules containing one or more selected from the group consisting of.
[Claim 10]
The method of claim 1, wherein the pesticide granule further comprises one or more additives selected from the group consisting of a solid carrier, a surfactant, a solvent, a dispersant, a wetting agent, a thickener, a binder, and an adjuvant.
[Claim 11]
The controlled dissolution type pesticide granule according to claim 1, wherein the degree of dissolution in water after 72 hours of the pesticide active ingredient of the pesticide granule is 10 to 20%.
[Claim 12]
The controlled-release pesticide granule according to claim 1, wherein the duration of dissolution of the active pesticide ingredient of the pesticide granule is 200 to 300 hours.
[Claim 13]
1) forming a mixture by mixing a pyridine sulfonylurea compound represented by the following formula (1), a salt thereof, or an agrochemical active ingredient including a stereochemical isomer, a natural wax, and a pH adjusting agent; 2) preparing a mixture paste by stirring the mixture in a solvent; And 3) granulating and drying the mixture paste. In Formula 1 , n represents 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 14]
The method of claim 13, wherein the drying temperature is 75 to 100°C.
[Claim 15]
A method of cultivating agricultural crops using the controlled-release pesticide granules according to any one of claims 1 to 12.