Aqueous suspension formulation with excellent stability after frozen storage.

Abstract

To provide an aqueous suspension formulation that exhibits high suspension stability after thawing following long-term frozen storage, and even if a sedimentation layer forms, it can be redispersed by several inverted shakings, preventing the formation of undispersed material resulting from the formation of a hard sedimentation layer. [Means] To provide an aqueous suspension formulation comprising 2 to 50 parts by weight of a solid pesticide active ingredient under 1 atmosphere and 20°C conditions, polyoxyethylene styrene-phenyl ether, polyoxyylene alkylene branched decyl ether, sodium salt of lignin sulfonic acid, and water.

Description

Technical Field

[0001] The present invention relates to an aqueous suspension preparation having excellent suspension stability and redispersibility at room temperature after long-term frozen storage.

Background Art

[0002] Aqueous suspension preparations have been the subject of much research and various preparations have been developed because they do not generate powdering during use and are highly safe because they are water-based. However, aqueous suspension preparations have problems such that during storage, the pesticidal active ingredient and auxiliary ingredients dispersed in water separate and sediment, and in some cases, the sediment solidifies and redispersion becomes difficult. Therefore, in order to prevent the above separation and sedimentation and obtain a stable preparation under various storage conditions, many studies have been conducted as exemplified below.

[0003] JP-A-5-43401 (Patent Document 1) proposes an aqueous suspension pesticidal preparation characterized by containing a pesticidal active ingredient that is a solid at room temperature and is poorly water-soluble or water-insoluble, a lignin sulfonate, an alkyl sulfate ester salt, and an anti-settling agent. JP-A-2006-169167 (Patent Document 2) proposes an aqueous suspension preparation characterized by containing a pesticidal active ingredient, crystalline cellulose, a surfactant, and water. JP-A-2010-163402 (Patent Document 3) proposes an aqueous suspension preparation characterized by containing a) a pesticidal active ingredient and b) guanidine or a water-soluble salt of guanidine. JP-A-2002-293702 (Patent Document 4) proposes an aqueous suspension preparation for direct spraying on paddy fields under flooded conditions, characterized by comprising a herbicidal active ingredient having a solubility in water at 20°C of 100 ppm or less, modified polyvinyl alcohol, and water. JP-A-2011-168517 (Patent Document 5) proposes an aqueous suspension preparation characterized by comprising a pesticidal active ingredient, polyvinyl alcohol, methyl cellulose and / or hydroxypropyl methyl cellulose, a surfactant, and water. Japanese Patent Publication No. 2012-219054 (Patent Document 6) proposes an aqueous suspension formulation characterized by comprising an active pesticide component, octenyl succinate esterified sodium starch, a polyhydric alcohol with 6 or fewer carbon atoms, and ion-exchanged water, and having a formulation viscosity (at 20°C) of 200 to 1200 mPa·s during manufacturing.

[0004] The aqueous suspension formulation described in Patent Document 1 contains "lignin sulfonate, alkyl sulfate ester salt, and settling inhibitor," thereby suppressing the growth of micronized pesticide active ingredient particles even after storage under high temperature conditions (50°C for 1 month). The aqueous suspension formulation described in Patent Document 2 contains "crystalline cellulose and surfactant," providing excellent redispersibility, allowing for easy dispersion of precipitates formed by suspended particles after long-term storage (20°C for 90 days or 40°C for 90 days). The aqueous suspension formulation described in Patent Document 3 contains "guanidine or a water-soluble salt of guanidine," resulting in excellent suspension properties after long-term storage (20°C for 90 days or 40°C for 90 days) and suppressing the growth of pesticide active ingredient particles. Patent Documents 1, 2, and 3 aim to provide formulations that remain stable even after storage at high temperatures or room temperature.

[0005] On the other hand, the aqueous suspension formulation of Patent Document 4 contains "modified polyvinyl alcohol," which prevents aggregation of the dispersed phase even when stored under conditions that would cause freezing (7 times the cycle of 40°C for 7 days → -10°C for 7 days). The aqueous suspension formulation of Patent Document 5 contains "polyvinyl alcohol, methylcellulose and / or hydroxypropyl methylcellulose, and a surfactant," which exhibits excellent suspension stability, preventing separation and sedimentation of pesticide active ingredient particles even when stored under conditions with large temperature changes between high and low temperatures (6 times the cycle of 50°C for 7 days → -10°C for 7 days). The aqueous suspension formulation of Patent Document 6 contains "octenyl succinate esterified sodium starch," and by setting the viscosity of the formulation during manufacturing to 200-1200 mPa·s, it exhibits excellent suspension stability and handling properties even after storage under high and low temperature conditions (4 times the cycle of 50°C for 15 days → room temperature for 1 day → -15°C for 15 days). These patent documents 4, 5, and 6 are inventions aimed at creating stable formulations even when stored under short-term alternation of high and low temperature conditions.

[0006] However, in actual storage of aqueous suspension formulations, depending on the region, storage may be expected for longer than 15 days and at temperatures below -15°C, but previous patent documents have not disclosed the effectiveness under these assumed storage conditions. Furthermore, even if a formulation exhibits excellent suspension stability without separation or sedimentation after storage under high or low temperature conditions, there is a problem in that the active ingredients of pesticides do not redisperse after thawing at room temperature following frozen storage. For this reason, there is a need for aqueous suspension formulations that exhibit excellent suspension stability and redispersibility after thawing at room temperature under conditions such as long-term frozen storage in warehouses in regions with severe cold. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 5-43401 [Patent Document 2] Japanese Patent Publication No. 2006-169167 [Patent Document 3] Japanese Patent Publication No. 2010-163402 [Patent Document 4] Japanese Patent Publication No. 2002-293702 [Patent Document 5] Japanese Patent Publication No. 2011-168517 [Patent Document 6] Japanese Patent Publication No. 2012-219054 [Overview of the project] [Problems that the invention aims to solve]

[0008] The present invention aims to solve the above-mentioned problems. Specifically, it aims to provide an aqueous suspension formulation that has excellent suspension stability, such that after long-term frozen storage, the dispersed phases, such as pesticide active ingredients and auxiliary ingredients, do not form a settling layer after thawing at room temperature, and even if a settling layer does form, it has excellent redispersibility. [Means for solving the problem]

[0009] The inventors diligently conducted research to achieve the above objective. As a result, they discovered that an aqueous suspension formulation consisting of a solid pesticide active ingredient, polyoxyethylene styrene-phenyl ether, polyoxyalkylene branched decyl ether, sodium salt of lignin sulfonic acid, and water, under conditions of 2 to 50 parts by weight at 1 atmosphere and 20°C, can achieve the above objective, thus completing the present invention. In other words, the present invention is as follows [1] to [5]. [1] An aqueous suspension formulation comprising 2 to 50 parts by weight of a solid pesticide active ingredient under 1 atmosphere and 20°C conditions, polyoxyethylene styrene-phenyl ether, polyoxyalkylene branched decyl ether, sodium salt of lignin sulfonic acid, and water. [2] The aqueous suspension formulation according to [1], characterized in that the HLB of polyoxyethylene styrene-phenyl ether is 10 to 12. [3] The aqueous suspension formulation according to [2], characterized in that the HLB of the polyoxyalkylene branched decyl ether is 12 to 13. [4] A method for spraying an aqueous suspension formulation, characterized by spraying an aqueous suspension formulation consisting of a solid pesticide active ingredient, polyoxyethylene styrene phenyl ether, polyoxyalkylene branched decyl ether, sodium salt of lignin sulfonic acid, and water, either undiluted or diluted 1.5 to 5000 times with water under 1 atmosphere and 20°C conditions. [5] The method of use described in [4], characterized in that the method of use is one of the following: spraying using a sprayer, spraying from the air using a helicopter or drone, dripping onto the paddy field by attaching it to a rice transplanter, spraying using a radio-controlled board, dripping onto the flooded paddy field by shaking a container from the levee, treating by letting it flow with the inflow of water from the water inlet, drenching the soil in a seedling tray, soaking the seeds, spraying the seeds using a sprayer or the like, or dripping onto the seeds. [Effects of the Invention]

[0010] The aqueous suspension formulation of the present invention provides excellent suspension stability and redispersibility effects upon thawing at room temperature after long-term frozen storage.

Mode for Carrying Out the Invention

[0011] Hereinafter, details such as the components constituting the aqueous suspension formulation of the present invention and the preparation method of the formulation will be described.

[0012] <Components> (1) Pesticide active ingredient The pesticide active ingredient used in the present invention may be any one generally used as an active ingredient of pesticides, such as insecticides, fungicides, herbicides, etc. that are solid under the conditions of 1 atm and 20 °C. Also, two or more kinds of pesticide active ingredients may be used in combination.

[0013] Examples of such active ingredients include, as insecticidal active ingredients, components that act on nerves and muscles, components that act on growth and development (such as tebufenozide), components that act on respiration, components that act on the midgut, non-specific or components with unknown action mechanisms.

[0014] Examples of fungicidal active ingredients include, for example, components that act on nucleic acid synthesis metabolism, components that act on the cytoskeleton and motor proteins, components that act on sterol biosynthesis in the cell membrane (such as imibenconazole), components that act on respiration, components that act on amino acid and protein biosynthesis, components that act on signal transduction, components that act on lipid biosynthesis or transport / structure or function of the cell membrane, components that act on sterol biosynthesis in the cell membrane, components that act on cell wall biosynthesis, components that act on melanin biosynthesis in the cell wall, components that act on induction of host plant resistance, multi-site contact active ingredients, and components with unknown action mechanisms.

[0015] Examples of herbicidal active ingredients include, for example, components that inhibit photosynthetic electron transfer systems, components that inhibit photosynthetic pigment biosynthesis, components that inhibit amino acid biosynthesis, components that inhibit fatty acid synthesis (such as ipfencarbazone), components that inhibit cell division, components that disrupt auxin action, etc.

[0016] The specific individual pesticidal active ingredients included herein are described, for example, in "Pesticide Handbook 2021 Edition" (published by the Japan Plant Protection Association, Inc.), "SHIBUYA INDEX 18th Edition" (published by the SHIBUYA INDEX Research Group), "The Pesticide Manual 19th Edition" (published by the British Crop Protection Council), etc. In addition, as the pesticidal active ingredient used in the present invention, pesticidal active ingredients that are known or developed in the future other than those described above can also be applied.

[0017] The above pesticidal active ingredient is 2 to 50 parts by weight in 100 parts by weight of the aqueous suspension formulation.

[0018] (2) Polyoxyethylene styrenated phenyl ether The polyoxyethylene styrenated phenyl ether used in the present invention is a nonionic surfactant in which hydrophilic polyoxyethylene and hydrophobic styrenated phenyl are bonded, and is characterized by having particularly excellent emulsifying power and dispersing power. Generally, it is used as an emulsifier for emulsion polymerization in resin production, etc., a dispersant for pigments, and a dispersant / emulsifier for pesticidal active ingredients. In the aqueous suspension formulation, it exhibits a dispersing action and a wetting action, and also contributes to good redispersibility after long-term frozen storage by the dispersing and wetting actions in the present invention.

[0019] The amount of polyoxyethylene styrene-phenyl ether added is preferably 0.1 to 5.0 parts by weight per 100 parts of aqueous suspension formulation, from the standpoint of the above-mentioned effects. Furthermore, HLB is a numerical representation of the balance between hydrophilicity and hydrophobicity of a nonionic surfactant, and in this invention, it is preferably 10 to 12. Regarding this HLB range, generally, polyoxyethylene styrene-phenyl ether exhibits stronger solvent properties than surfactant properties at low HLB levels, and its fluidity decreases as the HLB increases. As a surfactant, it exerts dispersion and wetting effects, and maintains these dispersion and wetting effects from the frozen state to the thawed state. Therefore, the effects of this invention are maximized at an HLB of 10 to 12, where fluidity at low temperatures is high.

[0020] (3) Polyoxyalkylene branched decyl ether The polyoxyalkylene branched decyl ether used in this invention is a nonionic surfactant formed by the bonding of a hydrophilic polyoxyalkylene and a hydrophobic branched decyl ether. It has the characteristics of good surface tension reduction ability, penetrating power, and resistance to solidification even at low temperatures. It is generally used in detergents for clothing, dishes, and machinery. In aqueous suspension formulations, it has a wetting effect. In this invention, in addition to its excellent wetting effect, its good fluidity at low temperatures contributes to good redispersibility after long-term frozen storage.

[0021] The amount of polyoxyalkylene branched decyl ether added is preferably 0.1 to 5.0 parts by weight per 100 parts of the aqueous suspension formulation, from the viewpoint of the above-mentioned effects. Furthermore, the HLB is preferably 12 to 13. Regarding this HLB range, the HLB of commonly available polyoxyalkylene branched decyl ether is generally 12 to 15 from the viewpoint of its functionality as a surfactant and workability. Since a lower HLB indicates higher fluidity at low temperatures, the effects of the present invention are maximized at an HLB of 12 to 13.

[0022] (4) Sodium salt of ligninsulfonic acid The sodium salt of ligninsulfonic acid used in this invention is classified as an anionic surfactant and is a type of industrial lignin. Industrial lignin is lignin that is isolated from natural lignin, which is a major component in plants such as conifers and broad-leaved trees, using various processing methods such as the sulfite process and the Kraft process, and then handled industrially. Here, natural lignin is a polymer formed when lignin monomers called monolignols are polymerized by enzymes in the plant body.

[0023] There are three types of monolignols, but because of the multiple bonding sites in the monolignols, the resulting natural lignin has a wide variety of structures, making it an extremely complex compound, and its complete chemical structure has yet to be elucidated. Furthermore, the structure differs depending on the type of plant from which it is extracted. For this reason, the chemical structure of industrial lignin, which is derived from this natural lignin, has not been clearly identified, and the name of industrial lignin is often derived from the processing method used to obtain natural lignin, or from the name of the developer of that processing method.

[0024] There are dozens of methods for processing natural lignin, and even with the same processing method, the structure of industrial lignin changes depending on the processing conditions. Considering the differences in natural lignin as well, there are a vast number of industrial lignins with different structures. Generally, water-soluble industrial lignin has a dispersing effect in aqueous suspension formulations. Furthermore, water-soluble industrial lignin with anionic sulfonic acid groups contains cationic substances such as sodium, potassium, calcium, and magnesium as pairs with the sulfonic acid group.

[0025] The sodium salt of lignin sulfonic acid used in this invention refers to industrial lignin that is water-soluble, contains sulfonic acid groups, and contains sodium as a salt. These salts have a very large polymer backbone, yet possess water-soluble properties. Due to the electrostatic repulsion caused by the sulfonic acid groups, they exhibit excellent dispersion properties, suppress aggregation of suspended particles during thawing after freezing, and contribute to good redispersibility after long-term frozen storage.

[0026] The amount of sodium salt of ligninsulfonic acid added is preferably 0.5 to 10.0 parts by weight per 100 parts of the aqueous suspension formulation, considering the above effects and economic efficiency.

[0027] The three surfactants mentioned above are known as general surfactants, and focusing on their fluidity and dispersion properties at low temperatures, using only one type makes it impossible to obtain an aqueous suspension formulation with excellent suspension stability and redispersibility upon thawing after long-term storage under freezing conditions, which is the problem that the present invention attempts to solve.

[0028] From the viewpoint of fluidity at low temperatures and excellent dispersion properties due to its polymer backbone, polyoxyethylene styrene-phenyl ether, polyoxyalkylene branched decyl ether, and sodium salt of lignin sulfonic acid were selected and combined. This combination not only effectively wets and disperses pesticide active ingredient particles in water, but also exhibits good wetting and dispersion effects without forming a hard sedimentary layer due to aggregation of pesticide active ingredient particles during thawing after enduring the harsh conditions of long-term storage under freezing conditions, resulting in excellent suspension stability and redispersibility.

[0029] (5) Other ingredients In addition to the essential components listed above, auxiliary agents may be added to the aqueous suspension formulation of the present invention as needed. These may include ethylene glycol, propylene glycol, glycerin, etc. as antifreeze; xanthan gum, guar gum, Wella gum, carboxymethylcellulose, hydroxypropylcellulose, colloidal hydrated aluminum silicate, colloidal hydrated magnesium silicate, colloidal hydrated aluminum magnesium silicate, etc. as thickeners; silicone-based or fatty acid-based substances, etc. as defoamers; potassium sorbate, p-chloro-metaxylenol, p-butyl oxybenzoate, 1,2-benzoisothiazole-3(2H)-one, 3-iodo-2-propynyl butylcarbamate, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, etc. as preservatives; and antioxidants, UV inhibitors, crystal precipitation inhibitors, etc., as stabilizers for the active pesticide components. The auxiliary agents that can be used in this invention are not limited to the examples given above.

[0030] <Method for preparing aqueous suspension formulations> The method for preparing the aqueous suspension formulation of the present invention is not particularly limited, but it can be prepared by, for example, the following method.

[0031] The active pesticide component, polyoxyethylene styrene phenyl ether, polyoxyalkylene branched decyl ether, sodium salt of ligninsulfonic acid, water, and other auxiliary agents are added and mixed. The active pesticide component may be pre-pulverized using a jet pulverizer or the like, or the mixture may be prepared by wet grinding using glass beads or the like after adding and mixing the active pesticide component, polyoxyethylene styrene phenyl ether, polyoxyalkylene branched decyl ether, sodium salt of ligninsulfonic acid, water, and other auxiliary agents.

[0032] <How to use aqueous suspension formulations> The aqueous suspension preparation prepared as described above can be applied in various ways, such as spraying the undiluted solution or a solution diluted 1.5 to 5000 times with water onto the foliage of crops and weeds using a sprayer; spraying from the air using a helicopter or drone; dripping onto paddy fields by attaching it to a rice transplanter; spraying using a radio-controlled board; dripping onto flooded paddy fields by shaking a container from the levees; applying it with the flow of water entering from the water inlet; drenching the soil in seedling trays; soaking seeds; spraying seeds using a sprayer; or dripping onto seeds. [Examples]

[0033] The present invention will be further described in detail by the following examples, but the present invention is not limited to these. Therefore, by substituting various pesticide active ingredients and preparing them in the same manner as in the following examples, an aqueous suspension formulation can be obtained that exhibits excellent suspension stability and redispersibility when thawed at room temperature after long-term frozen storage.

[0034] The examples were prepared based on the compositions listed in Table 1, and the comparative examples on Table 2. In the examples, "parts" all refer to parts by weight. The detailed manufacturing methods for aqueous suspension formulations of various pesticide active ingredients are as follows.

[0035] <Ipfencarbazone 40% Containing Agent> [Example 1] 43.5 parts water, 40.0 parts ibuphencarbazone (pesticide active ingredient), 1.0 part polyoxyethylene styrene-phenyl ether (HLB: 10.6), 0.5 parts polyoxyalkylene branched decyl ether (HLB: 12.4), and 5.0 parts sodium ligninsulfonate were added and mixed using a TK Homo Mixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Then, the mixture was wet-milled using hard glass beads with a Labstar Mini LMZ015 (manufactured by Ashizawa Finetech Co., Ltd.), and further, 10.0 parts of a 2% xanthan gum aqueous solution were added and the mixture was thoroughly stirred with a Three One Motor (manufactured by HEIDON) to obtain the aqueous suspension formulation of the present invention.

[0036] [Example 2] 43.5 parts water, 40.0 parts ibuphencarbazone (pesticide active ingredient), 1.0 part polyoxyethylene styrene-phenyl ether (HLB: 11.7), 0.5 parts polyoxyalkylene branched decyl ether (HLB: 12.8), and 5.0 parts sodium ligninsulfonate were added and mixed using a TK Homo Mixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Then, the mixture was wet-milled using hard glass beads with a Labstar Mini LMZ015 (manufactured by Ashizawa Finetech Co., Ltd.), and further, 10.0 parts of a 2% xanthan gum aqueous solution were added and the mixture was thoroughly stirred with a Three One Motor (manufactured by HEIDON) to obtain the aqueous suspension formulation of the present invention.

[0037] [Example 3] 43.5 parts water, 40.0 parts ibuphencarbazone (pesticide active ingredient), 1.0 part polyoxyethylene styrene-phenyl ether (HLB: 10.6), 0.5 parts polyoxyalkylene branched decyl ether (HLB: 13.3), and 5.0 parts sodium ligninsulfonate were added and mixed using a TK Homo Mixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Then, the mixture was wet-milled using hard glass beads with a Labstar Mini LMZ015 (manufactured by Ashizawa Finetech Co., Ltd.), and further, 10.0 parts of a 2% xanthan gum aqueous solution were added and the mixture was thoroughly stirred with a Three One Motor (manufactured by HEIDON) to obtain the aqueous suspension formulation of the present invention.

[0038] [Example 4] 43.5 parts water, 40.0 parts ibuphencarbazone (pesticide active ingredient), 1.0 part polyoxyethylene styrene-phenyl ether (HLB: 17.5), 0.5 parts polyoxyalkylene branched decyl ether (HLB: 14.5), and 5.0 parts sodium ligninsulfonate were added and mixed using a TK Homo Mixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Then, the mixture was wet-milled using hard glass beads with a Labstar Mini LMZ015 (manufactured by Ashizawa Finetech Co., Ltd.), and further, 10.0 parts of a 2% xanthan gum aqueous solution were added and the mixture was thoroughly stirred with a Three One Motor (manufactured by HEIDON) to obtain the aqueous suspension formulation of the present invention.

[0039] [Example 5] 24.0 parts water, 40.0 parts ibuphencarbazone (pesticide active ingredient), 0.5 parts polyoxyethylene styrene-phenyl ether (HLB: 10.6), 0.5 parts polyoxyalkylene branched decyl ether (HLB: 14.5), and 10.0 parts sodium ligninsulfonate were added and mixed using a TK Homo Mixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Then, the mixture was wet-milled using hard glass beads with a Labstar Mini LMZ015 (manufactured by Ashizawa Finetech Co., Ltd.), and further, 10.0 parts 2% xanthan gum aqueous solution, 10.0 parts 3% colloidal hydrated aluminum silicate suspension, and 5.0 parts propylene glycol were added and thoroughly stirred with a Three One Motor (manufactured by HEIDON) to obtain the aqueous suspension formulation of the present invention.

[0040] [Comparative Example 1] 48.5 parts water, 40.0 parts ibuphencarbazone (pesticide active ingredient), 1.0 part polyoxyethylene styrene-phenyl ether (HLB: 10.6), and 0.5 parts polyoxyalkylene branched decyl ether (HLB: 12.4) were added and mixed using a TK Homo Mixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Then, the mixture was wet-milled using hard glass beads with a Labstar Mini LMZ015 (manufactured by Ashizawa Finetech Co., Ltd.), and further, 10.0 parts of a 2% xanthan gum aqueous solution were added and the mixture was thoroughly stirred with a Three One Motor (manufactured by HEIDON) to obtain the aqueous suspension formulation of the present invention.

[0041] [Comparative Example 2 (Based on Patent Document 2)] 44.5 parts water, 40.0 parts ibuphencarbazone (pesticide active ingredient), 3.0 parts polyoxyalkylene branched decyl ether (HLB: 12.4), 2.0 parts sodium ligninsulfonate, and 1.0 part crystalline cellulose were added and mixed using a TK Homo Mixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Then, the mixture was wet-milled using hard glass beads with a Labstar Mini LMZ015 (manufactured by Ashizawa Finetech Co., Ltd.), and further, 10.0 parts of a 2% xanthan gum aqueous solution were added and the mixture was thoroughly stirred with a Three One Motor (manufactured by HEIDON) to obtain the aqueous suspension formulation of the present invention.

[0042] [Comparative Example 3] 44.0 parts water, 40.0 parts ibuphencarbazone (pesticide active ingredient), 1.0 part polyoxyethylene styrene-phenyl ether (HLB: 10.6), and 5.0 parts sodium ligninsulfonate were added and mixed using a TK Homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Then, the mixture was wet-milled using hard glass beads with a Labstar Mini LMZ015 (manufactured by Ashizawa Finetech Co., Ltd.), and further, 10.0 parts of a 2% xanthan gum aqueous solution were added and the mixture was thoroughly stirred with a Three One Motor (manufactured by HEIDON) to obtain the aqueous suspension formulation of the present invention.

[0043] [Comparative Example 4] 43.5 parts water, 40.0 parts ibuphencarbazone (pesticide active ingredient), 1.0 part polyoxyethylene styrene-phenyl ether (HLB: 13.0), 0.5 parts polyoxyalkylene branched decyl ether (HLB: 12.4), and 5.0 parts calcium ligninsulfonate were added and mixed using a TK Homo Mixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Then, the mixture was wet-milled using hard glass beads with a Labstar Mini LMZ015 (manufactured by Ashizawa Finetech Co., Ltd.), and further, 10.0 parts of a 2% xanthan gum aqueous solution were added and the mixture was thoroughly stirred with a Three One Motor (manufactured by HEIDON) to obtain the aqueous suspension formulation of the present invention.

[0044] [Comparative Example 5] 48.0 parts water, 40.0 parts ibuphencarbazone (pesticide active ingredient), 1.0 part polyoxyethylene / polyoxypropylene block polymer, and 1.0 part naphthalene sulfonic acid formalin condensate soda were added and mixed using a TK Homo Mixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Then, the mixture was wet-milled using hard glass beads with a Labstar Mini LMZ015 (manufactured by Ashizawa Finetech Co., Ltd.), and further, 10.0 parts of a 2% xanthan gum aqueous solution were added and the mixture was thoroughly stirred with a Three One Motor (manufactured by HEIDON) to obtain the aqueous suspension formulation of the present invention.

[0045] [Comparative Example 6 (Based on Patent Document 1)] 42.3 parts water, 40.0 parts ibuphencarbazone (pesticide active ingredient), 0.1 parts sodium alkyl sulfate, 2.5 parts sodium ligninsulfonate, and 0.1 parts dimethylpolysiloxane were added and mixed using a TK Homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Then, the mixture was wet-milled using hard glass beads with a Labstar Mini LMZ015 (manufactured by Ashizawa Finetech Co., Ltd.), and further, 10.0 parts propylene glycol and 5.0 parts 2% xanthan gum aqueous solution were added, and the mixture was thoroughly stirred with a Three One Motor (manufactured by HEIDON) to obtain an aqueous suspension formulation.

[0046] [Comparative Example 7] 45.4 parts water, 40.0 parts ibuphencarbazone (pesticide active ingredient), 2.0 parts polyoxyethylene styrenated phenyl ether (HLB: 13.0), 1.5 parts polyoxyethylene alkyl ether, and 10.0 parts propylene glycol were added and mixed using a TK Homo Mixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Then, the mixture was wet-milled using hard glass beads with a Labstar Mini LMZ015 (manufactured by Ashizawa Fine Tech Co., Ltd.), and further, 1.0 part polyvinyl alcohol and 0.1 parts diutan gum were added, and the mixture was thoroughly stirred with a Three One Motor (manufactured by HEIDON) to obtain an aqueous suspension formulation.

[0047] [Comparative Example 8 (Based on Patent Document 4)] 42.0 parts water, 40.0 parts ibuphencarbazone (pesticide active ingredient), 5.0 parts cation-modified polyvinyl alcohol, and 3.0 parts propylene glycol were added and mixed using a TK Homo Mixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Then, the mixture was wet-milled using hard glass beads with a Labstar Mini LMZ015 (manufactured by Ashizawa Fine Tech Co., Ltd.), and further, 10.0 parts of a 2% xanthan gum aqueous solution were added and the mixture was thoroughly stirred with a Three One Motor (manufactured by HEIDON) to obtain an aqueous suspension formulation.

[0048] <Imibenconazole 20% Containing Agent> [Example 6] 64.8 parts water, 20.0 parts imibenconazole (pesticide active ingredient), 2.0 parts polyoxyethylene styrene-phenyl ether (HLB: 10.6), 0.2 parts polyoxyalkylene branched decyl ether (HLB: 12.8), and 3.0 parts sodium ligninsulfonate were added and mixed using a TK Homo Mixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Then, the mixture was wet-milled using hard glass beads with a Labstar Mini LMZ015 (manufactured by Ashizawa Finetech Co., Ltd.), and further, 10.0 parts of a 2% xanthan gum aqueous solution were added and the mixture was thoroughly stirred with a Three One Motor (manufactured by HEIDON) to obtain the aqueous suspension formulation of the present invention.

[0049] [Example 7] 66.4 parts water, 20.0 parts imibenconazole (pesticide active ingredient), 0.5 parts polyoxyethylene styrene-phenyl ether (HLB: 10.6), 1.0 part polyoxyalkylene branched decyl ether (HLB: 12.4), 2.0 parts sodium ligninsulfonate, and 0.1 parts dimethylpolysiloxane were added and mixed using a TK Homo Mixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Then, the mixture was wet-milled using hard glass beads with a Labstar Mini LMZ015 (manufactured by Ashizawa Finetech Co., Ltd.), and further, 10.0 parts of a 2% xanthan gum aqueous solution were added and the mixture was thoroughly stirred with a Three One Motor (manufactured by HEIDON) to obtain the aqueous suspension formulation of the present invention.

[0050] [Comparative Example 9] 66.0 parts water was mixed with 20.0 parts imibenconazole (pesticide active ingredient), 1.0 part polyoxyalkylene tridecyl ether, and 3.0 parts special polycarboxylic acid type surfactant, and mixed using a TK Homo Mixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Then, the mixture was wet-milled using hard glass beads with a Labstar Mini LMZ015 (manufactured by Ashizawa Finetech Co., Ltd.), and 10.0 parts of 2% xanthan gum aqueous solution were added. The mixture was then thoroughly stirred with a Three One Motor (manufactured by HEIDON) to obtain an aqueous suspension formulation.

[0051] [Comparative Example 10] 66.0 parts water was mixed with 20.0 parts imibenconazole (pesticide active ingredient), 1.0 part polyoxyalkylene oleyl cetyl ether, and 3.0 parts alkylammonium chloride, and mixed using a TK Homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Then, the mixture was wet-milled using hard glass beads with a Labstar Mini LMZ015 (manufactured by Ashizawa Finetech Co., Ltd.), and 10.0 parts of 2% xanthan gum aqueous solution were added. The mixture was then thoroughly stirred with a Three One Motor (manufactured by HEIDON) to obtain an aqueous suspension formulation.

[0052] [Comparative Example 11 (Based on Patent Document 3)] 62.6 parts water was mixed with 20.0 parts imibenconazole (pesticide active ingredient), 2.0 parts polyoxyethylene arylphenyl ether, 0.4 parts guanidine sulfamate, and 5.0 parts propylene glycol, and mixed using a TK Homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Then, the mixture was wet-milled using hard glass beads with a Labstar Mini LMZ015 (manufactured by Ashizawa Finetech Co., Ltd.), and 10.0 parts of a 2% xanthan gum aqueous solution was added. The mixture was then thoroughly stirred with a Three One Motor (manufactured by HEIDON) to obtain an aqueous suspension formulation.

[0053] <Tebufenozide 30% Containing Agent> [Example 8] 55.5 parts water, 30.0 parts tebufenozide (pesticide active ingredient), 1.0 part polyoxyethylene styrene-phenyl ether (HLB: 10.6), 0.5 parts polyoxyalkylene branched decyl ether (HLB: 12.4), and 3.0 parts sodium ligninsulfonate were added and mixed using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Then, 10.0 parts of a 3% colloidal hydrated aluminum silicate suspension were added and the mixture was thoroughly stirred using a Three One Motor (manufactured by HEIDON) to obtain the aqueous suspension formulation of the present invention.

[0054] [Example 9] 53.0 parts water, 30.0 parts tebufenozide (pesticide active ingredient), 1.0 part polyoxyethylene styrene-phenyl ether (HLB: 11.7), 1.0 part polyoxyalkylene branched decyl ether (HLB: 12.4), and 5.0 parts sodium ligninsulfonate were added and mixed using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Then, 10.0 parts of a 2% xanthan gum aqueous solution were added and the mixture was thoroughly stirred with a Three One Motor (manufactured by HEIDON) to obtain the aqueous suspension formulation of the present invention.

[0055] [Comparative Example 12 (Based on Patent Document 5)] 56.3 parts water, 30.0 parts tebufenozide (pesticide active ingredient), 2.0 parts polyoxyethylene styrene-phenyl ether (HLB: 13.0), 0.5 parts sodium alkylbenzene sulfonate, 1.0 part polyvinyl alcohol, and 0.2 parts methylcellulose were added and mixed using a TK Homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Then, the mixture was wet-milled using hard glass beads with a Labstar Mini LMZ015 (manufactured by Ashizawa Finetech Co., Ltd.), and further, 10.0 parts of 2% xanthan gum aqueous solution were added and the mixture was thoroughly stirred with a Three One Motor (manufactured by HEIDON) to obtain an aqueous suspension formulation.

[0056] [Comparative Example 13 (Based on Patent Document 6)] 62.4 parts water, 30.0 parts tebufenozide (pesticide active ingredient), 3.5 parts octenyl succinate sodium starch, 4.0 parts propylene glycol, and 0.1 parts dimethylpolysiloxane were added and mixed using a TK Homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Subsequently, the mixture was wet-milled using hard glass beads with a Labstar Mini LMZ015 (manufactured by Ashizawa Finetech Co., Ltd.) to obtain an aqueous suspension formulation.

[0057] Next, the usefulness of the aqueous suspension formulation of the present invention will be demonstrated by test examples. In this test, in order to confirm the excellent suspension stability and redispersibility after thawing at room temperature following long-term frozen storage, suspension stability (uniformity of the liquid), number of redispersions (number of shakes until the liquid becomes uniform), and 63 μm sieve residue (amount of undispersed material on a 63 μm sieve after the liquid is discharged from the container onto a 63 μm sieve after shaking) were evaluated.

[0058] [Test Example 1] Suspension Stability Test The aqueous suspension formulation was filled into 100 mL poly bottles immediately after manufacturing, stored under frozen storage conditions (-20°C for 90 days), and then left to stand at room temperature for 1 day. After the storage test, the height (cm) of the suspension layer and the total layer in the aqueous suspension formulation was measured, and the suspension stability (%) was calculated using the following formula. A higher value for suspension stability (%) indicates higher uniformity and stability of the liquid.

[0059]

number

[0060] [Test Example 2] Number of redistributions After the suspension stability test described above, the suspension formulation was shaken inverted at a rate of once every 2 seconds until it became uniform, and the number of shakes was measured. A smaller number of redispersion cycles indicates a softer suspension layer and higher redispersibility.

[0061] [Test Example 3] 63μm sieve residue This test is performed after the above redispersion count test, once the liquid has become homogeneous. The entire aqueous suspension formulation is discharged from the container so that it passes through a 63 μm sieve. After the entire amount has passed through, the amount of undispersed material remaining on the sieve is evaluated. The less undispersed material there is, the higher the redispersibility. The evaluation criteria are as follows.

[0062] (Evaluation Criteria) [Table 1]

[0063] The results of Test Examples 1 to 3 are shown in Table 2 (Examples) and Table 3 (Comparative Examples).

[0064] [Table 2]

[0065] [Table 3]

[0066] <Explanation of the table> Tables 1 and 2 show that Practical Examples 1-9, containing polyoxyethylene styrene-phenyl ether, polyoxyalkylene branched decyl ether, and sodium salt of ligninsulfonic acid, demonstrated excellent results in all aspects, including suspension stability, number of redispersions, and 63 μm sieve residue, after thawing at room temperature following long-term frozen storage. On the other hand, Comparative Examples 1-13, which did not contain any of these three, showed problematic results in one or more aspects. Comparative Examples 6-8 and 11-13, manufactured based on Patent Documents 1-6, also showed low suspension stability, and in some cases, redispersion was impossible due to a hard sedimentation layer, resulting in generally problematic results during long-term frozen storage.

[0067] Furthermore, in the examples, Examples 1-3 and 5-9, which used polyoxyethylene styrene-phenyl ether with an HLB of 10-12, showed improved suspension stability compared to Example 4, which had an HLB greater than 12. In addition, Examples 1, 2, and 5-9, which used polyoxyalkylene branched decyl ether with an HLB of 12-13, showed improved suspension stability compared to Example 3, which had an HLB greater than 13.

[0068] Based on the above, to obtain an aqueous suspension formulation that exhibits excellent suspension stability and redispersibility of the dispersion when thawed at room temperature after long-term frozen storage, it is effective to include three components: polyoxyethylene styrene-phenyl ether, polyoxyalkylene branched decyl ether, and sodium salt of ligninsulfonic acid. Furthermore, it was found that a polyoxyethylene styrene-phenyl ether with an HLB of 10-12 and a polyoxyalkylene branched decyl ether with an HLB of 12-13 is an even more effective method.

Claims

1. An aqueous suspension formulation comprising 2 to 50 parts by weight of a solid pesticide active ingredient under 1 atmosphere and 20°C conditions, polyoxyethylene styrene-phenyl ether, polyoxyylene alkylene branched decyl ether, sodium salt of lignin sulfonic acid, and water.

2. The aqueous suspension formulation according to claim 1, characterized in that the HLB of the polyoxyethylene styrene-phenyl ether is 10 to 12.

3. The aqueous suspension formulation according to claim 2, characterized in that the HLB of the polyoxylen branched decyl ether is 12 to 13.

4. A method for spraying an aqueous suspension formulation, characterized by spraying an aqueous suspension formulation consisting of a solid pesticide active ingredient, polyoxyethylene styrene-phenyl ether, polyoxyalkylene branched decyl ether, sodium salt of lignin sulfonic acid, and water, either undiluted or diluted 1.5 to 5000 times with water under 1 atmosphere and 20°C conditions.

5. The method of use according to claim 4, characterized in that the method of use is one of the following: spraying using a sprayer, spraying from the air using a helicopter or drone, dripping onto the paddy field by attaching it to a rice transplanter, spraying using a radio-controlled board, dripping onto the flooded paddy field by shaking a container from the levee, treating by letting it ride on the flow of water flowing in from the water inlet, drenching the soil in a seedling tray, soaking the seeds, spraying the seeds using a sprayer or the like, or dripping onto the seeds.

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