Aqueous suspension agrochemical composition comprising natural rubber

Abstract

The present invention addresses the problem of providing an aqueous suspension agrochemical composition containing natural rubber, the aqueous suspension agrochemical composition having improved resistance to rain and capable of satisfactorily enhancing agrochemical effects. The present invention relates to an aqueous suspension agrochemical composition (excluding compositions for treating seeds) containing an agrochemical active ingredient, natural rubber, a surfactant, and water, the aqueous suspension agrochemical composition being characterized in that the weight ratio between the agrochemical active ingredient and the natural rubber is 100:3 to 1:3.

Description

Aqueous suspension-type pesticide composition containing natural rubber

[0001] The present invention relates to an agricultural chemical composition. More particularly, the present invention relates to an aqueous suspension-type agricultural chemical composition containing natural rubber.

[0002] In recent years, environmental problems caused by microplastics have arisen, and efforts to achieve the Sustainable Development Goals (SDGs) (commonly known as the Global Goals) are being called for. This calls for the development of environmentally friendly pesticide formulations (pesticide compositions) that use natural materials.

[0003] The pesticide formulation may contain a binder as a material, and various binders have been reported so far (see, for example, Patent Document 1).

[0004] Among these, depending on the binder used, there is a problem that when an aqueous suspension pesticide composition is sprayed on a plant, for example, the pesticidal active ingredient dissolves in water and is washed away by exposure to rain, and the desired effect cannot be fully exhibited. This problem is particularly noticeable in the case of an aqueous suspension pesticide composition containing a pesticidal active ingredient with high water solubility.

[0005] JP 2012-184209 A

[0006] An object of the present invention is to provide an environmentally friendly aqueous suspension concentrate pesticide composition that has improved rain resistance, excellent pesticidal activity, and is suited to social issues.

[0007] As a result of extensive research, the present inventors have discovered that by incorporating a certain amount of natural rubber as a binder, it is possible to obtain an aqueous suspension concentrate pesticidal composition that is able to suppress runoff from plant matter (e.g., leaves and stems) due to rainfall and thereby exert excellent pesticidal activity, thereby completing the present invention. Specifically, the present invention is as follows: [1] An aqueous suspension concentrate pesticidal composition comprising a pesticidal active ingredient, natural rubber, a surfactant, and water, characterized in that the weight ratio of the pesticidal active ingredient to the natural rubber is 100:3 to 1:3 (hereinafter referred to as the "aqueous suspension concentrate pesticidal composition of the present invention" or "composition of the present invention"). [2] The aqueous suspension concentrate pesticidal composition according to [1], wherein the pesticidal active ingredient has a melting point of 80°C or higher. [3] The aqueous suspension concentrate pesticidal composition according to either [1] or [2], wherein the water solubility of the pesticidal active ingredient at 20°C is 0.1 to 100 ppm. [4] The aqueous suspension concentrate pesticide composition according to any one of [1] to [3], wherein the water solubility of the pesticidal active ingredient at 20°C is 0.5 to 20 ppm. [5] The aqueous suspension concentrate pesticidal composition according to any one of [1] to [4], wherein the pesticidal active ingredient is at least one selected from the group consisting of impirfluxam, pyridaclomethyl, mandestrobin, and oxazosulfil. [6] The aqueous suspension concentrate pesticidal composition according to any one of [1] to [5], wherein the surfactant is at least one selected from the group consisting of lignin sulfonate and polyoxyethylene tristyryl phenyl ether phosphate ester salt. [7] The aqueous suspension concentrate pesticidal composition according to any one of [1] to [6], wherein the weight ratio of the pesticidal active ingredient to the natural rubber is 20:1 to 1:2. [8] The pesticidal composition according to any one of [1] to [7], which contains, per weight of the pesticidal composition, 1 to 50% by weight of the pesticidal active ingredient, 0.03 to 40% by weight of the natural rubber, 0.1 to 10% by weight of the surfactant, and 20 to 90% by weight of the water. [9] The pesticidal composition according to any one of [1] to [8], which is for foliar application.

[10] A method for controlling pests, comprising spraying an aqueous dilution obtained by diluting the aqueous suspension concentrate of any one of [1] to [9] with water to foliage of plants.

[11] A method for producing the aqueous suspension concentrate of any one of [1] to [9], comprising a step of adding natural rubber to a suspension containing a pesticidal active ingredient, a surfactant, and water.

[12] Use of natural rubber for producing the aqueous suspension concentrate of any one of [1] to [9] for pest control.

[13] Use of the aqueous suspension concentrate of any one of [1] to [9] for pest control.

[0008] The aqueous suspension concentrate pesticidal composition of the present invention (excluding the seed treatment composition) contains natural rubber, a natural material, and is therefore expected to contribute to solving social issues as an environmentally friendly composition. Furthermore, even when the aqueous suspension concentrate pesticidal composition of the present invention contains a pesticidal active ingredient with high water solubility, the pesticidal active ingredient is unlikely to be washed out of the plant by rainfall or watering during cultivation after spraying on the plant (e.g., leaves or stems), and the pesticidal activity effect can be fully exerted without being significantly affected by rainfall or watering, because the pesticidal active ingredient is rain-resistant.

[0009] The "pesticidally active ingredient" used in the present invention includes, for example, active ingredients used in the control of pests, specifically pest insects, plant diseases, weeds, and plant growth regulation in the cultivation of agricultural crops. The composition of the present invention contains one or more pesticidal active ingredients. Examples of such pesticidal active ingredients include insecticidal active ingredients, acaricidal active ingredients, nematicidal active ingredients, fungicidal active ingredients, herbicidal active ingredients, and plant growth regulator active ingredients. In particular, insecticidal active ingredients, acaricidal active ingredients, nematicidal active ingredients, and fungicidal active ingredients are preferred.

[0010] From the viewpoint of improving handleability during production, the pesticidal active ingredient of the present invention is preferably an pesticidal active ingredient having a melting point of 80° C. or higher. Examples of such pesticidal active ingredients having a melting point of 80° C. or higher include the following:

[0011] As the insecticidal, acaricidal or nematicidal active ingredient having a melting point of 80°C or higher, for example, the following ingredients may be appropriately selected: deltamethrin, tralomethrin, acrinathrin, propoxur, isoprocarb, thiodicarb, XMC, carbaryl, pirimicarb, carbofuran, acephate, trichlorfon, tetrachlorvinphos, diflubenzuron, chlorfluazuron, lufenuron, hexaflumuron, flufenoxuron, flucycloxuron, cyromazine, diafenthiuron, hexythiazox, novaluron, teflubenzuron , triflumuron, imidacloprid, acetamiprid, clothianidin, nitenpyram, thiamethoxam, dinotefuran, thiacloprid, spinosad, flubendiamide, chlorantraniliprole, cyantraniliprole, tetraniliprole, cyclaniliprole, fipronil, ethiprole, spirotetramat, spiromesifen, spirodiclofen, spiropydione, triflumezopyrim, sulfoxaflo le, abamectin, emamectin benzoate, lepimectin, milbemectin, pymetrozine, pyrifluquinazone, clofentezine, hexythiazox, etoxazole, chlorfenapyr, cartap, thiocyclam, bensultap, buprofezin, chromafenozide, methoxyfenozide, tebufenozide, amitraz, fluacrypyrim, bifenazate, fenpyroximate, pyridaben, tolfenpyra d, indoxacarb, oxazosulfil, metaflumizone, cyenopyrafen, piflubumid, flonicamid, broflanilide, fluxametamide, flupirimine, flometoquin, benzpyrimoxane, hydramethylnon, sulfluramide, boric acid, beta-cyfluthrin, thioxazafen, afidopiropen, fluazaindolizine, fluopyram, isocycloceram, ginpropylpiridaz, and cyclobutrifluram.

[0012] As the fungicidal active ingredient having a melting point of 80°C or higher, for example, the following ingredients may be appropriately selected: inpirfluxam, fenpyrazamine, mandestrobin, benomyl, carbendazim, thiabendazole, thiophanate methyl, diethofencarb, procymidone, iprodione, vinclozolin, diniconazole, epoxiconazole, tebuconazole, difenoconazole, cyproconazole, triadimefon, furametpyr, mepronil, flutolanil, thifluzamide, and fosetyl Aluminum, pyrimethanil, mepanipyrim, fludioxonil, fenpiclonil, blasticidin S, kasugamycin, polyoxin, validamycin, azoxystrobin, kresoxim-methyl, metominostrobin, chlorothalonil, mancozeb, captan, folpet, tricyclazole, pyroquilon, probenazole, fthalide, cymoxanil, dimethomorph, famoxadone, oxolinic acid, fluazinam, ferimzone, diclocymet, orysastrobin, isotianil, tiadinil, thiuram, fluoxastrobin, fenamidon, pyribencarb, fenbuconazole, hexacona azole, imibenconazole, ipconazole, metconazole, simeconazole, hydroxyisoxazole, pencycuron, fluopicolide, pyriophenone, isofetamide, fluopyram, thifluzamide, fluxapyroxad, isopyrazam, penflufen, penthiopyrad, boscalid, pyraziflumide, cyazofamid, amisulbrom, ametoctrazine, mepanipyrim, oxathiapiproline, triforine, fenarimol, oxpoconazole fumarate, fenhexamid, pyributicarb, benthiavalicarb isopropyl, mandipropamid, tolprocarb, acibenzolar-S-methyl, fosetylAluminum, flusulfamide, fluthianil, diclobenthiazox, tebufloquine, picarbutrazox, ziram, iminoctadine albesilate, iminoctadine acetate, dithianon, fluorimide, benzovindiflupyr, prothioconazole, carboxin, pydiflumetofen, flutriafol, triticonazole, fluquinconazole, methyltetraprole, fenpicoxamide, sedaxane, isoflucipram, silthiofam, bixafen, dimoxystrobin, pyridaclomethyl, ipflufenoquin, bromuconazole, triadimenol, florylpicoxamide, fluoxapiproline, ethaboxam, quinofumelin, aminopyrifen, mefentrifluconazole, flufenoxadiazam, and fluoxythioconazole.

[0013] As herbicidal active ingredients having a melting point of 80°C or higher, for example, the following ingredients may be appropriately selected: atrazine, metribuzin, fluometuron, isoproturon, bromoxynil, ioxynil, 2,4-D and its salts or esters, dicamba and its salts, mecoprop, bensulfuron methyl, metsulfuron methyl, nicosulfuron, primisulfuron methyl, cyclosulfamuron, imazosulfuron, propyrisulfuron, sulfosulfuron, imazapyr, imazaquin, imazethapyr, bispyribac-sodium salt, acifluorfen, acifluorfen sodium salt, paraquat, paraquat dichloride, flumetsulam, triflusulfuron methyl, fenoxaprop-P-ethyl, Diflufenican, norflurazon, isoxaflutole, glufosinate and its salts, glyphosate and its salts, bentazon, mefenacet, propanil, fluthiacet-methyl, flumiclorac-pentyl, flumioxazin, bromobutide, pentoxazone, fenquinotrione, pyraclonil, metazosulfuron, pyrimisulfan, triafamone, tefuryltrione, tolpyralate, pyroxasulfone, fenoxasulfone, ipfencarbazone, cyclopyrimorate, florpyrauxifenbenzyl, cloransulam, diclosulam, imazamox, and chlorimuron-ethyl.

[0014] As plant growth regulating active ingredients having a melting point of 80°C or higher, for example, the following ingredients may be appropriately selected: maleic hydrazide, chlormequat chloride, gibberellic acid, mepiquat chloride, thidiazuron, inabenfide, paclobutrazol, AVG, uniconazole P, and prohexadione calcium.

[0015] From the viewpoint of rain resistance, i.e., resistance to being washed away by rainfall or watering, the pesticidal active ingredient of the present invention preferably has a water solubility at 20°C of 0.1 to 100 ppm, more preferably 0.1 to 50 ppm, and even more preferably 0.5 to 20 ppm.

[0016] The pesticidal active ingredient of the present invention is preferably at least one compound selected from the group consisting of impirfluxam, pyridaclomethyl, mandestrobin and oxazosulfil.

[0017] The composition of the present invention preferably contains 1 to 50% by weight, and more preferably 10 to 40% by weight, of the total amount of pesticidal active ingredients per weight of the composition of the present invention, where, unless otherwise specified, the weight % is calculated per weight of the composition of the present invention.

[0018] The composition of the present invention contains one or more natural rubbers as an adjuvant that acts as a binder. The use of natural rubber enables the formulation to be environmentally friendly. Natural rubber refers to a substance containing cis-1,4-polyisoprene, which is derived from the sap of rubber trees. Here, the general definition of natural rubber broadly includes not only unmodified products derived from natural products, but also modified products whose chemical structure has been modified by graft modification with acrylic monomers or the like. However, in the present invention, from the perspective of providing an environmentally friendly pesticide composition, the natural rubber defined herein does not include these chemically structurally modified modified products.

[0019] On the other hand, a substance obtained by simply adding a stabilizer such as an anticoagulant (e.g., ammonia) to rubber tree sap may also be included in the natural rubber of the present invention. It may also be derived from natural rubber latex (the rubber component in natural rubber latex). The natural rubber latex is not particularly limited, and examples include field latex (raw latex extracted by tapping rubber trees), high ammonia latex (high ammonia natural rubber latex), wax ammonia latex (wax ammonia natural rubber latex), centrifugal concentrated latex, and deproteinized latex obtained by treating natural rubber latex with surfactants, enzymes, etc. Such natural rubber latex may be selected from one or a combination of two or more of these. Such natural rubber latex is commercially available, and specific examples thereof include SeLatex (registered trademark) 6111 (manufactured by Sumitomo Rubber Industries, Ltd.), SeLatex (registered trademark) 1101 (manufactured by Sumitomo Rubber Industries, Ltd.), ULACOL (registered trademark) (manufactured by Resitex Co., Ltd.), LA-LATEX (manufactured by Resitex Co., Ltd.), HA-LATEX (manufactured by Resitex Co., Ltd.), and UNIMAC LATEX (manufactured by Unimac Rubber Co., Ltd.), but are not limited to these.

[0020] The composition of the present invention is an aqueous suspension concentrate (also called SC) in which solid particles of an agrochemically active ingredient are suspended in water, and the natural rubber is present in the composition in a state of being suspended (dispersed) in water. The use of natural rubber as a binder in the composition of the present invention can improve rain resistance compared to when synthetic products or other natural materials are used.

[0021] The weight ratio of the pesticidal active ingredient to the natural rubber is from 100:3 to 1:3, and preferably from 20:1 to 1:2. The composition of the present invention preferably contains 0.03 to 40% by weight, more preferably 0.1 to 40% by weight, even more preferably 1 to 40% by weight, and most preferably 1.5 to 40% by weight of the natural rubber based on the weight of the composition of the present invention.

[0022] The composition of the present invention contains one or more surfactants. Examples of surfactants used in the present invention include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. In the composition of the present invention, anionic surfactants are particularly preferred.

[0023] Examples of such anionic surfactants include sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates include naphthalene sulfonates and their formaldehyde condensates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyldiphenyl ether disulfonates, α-olefin sulfonates, lignin sulfonates, polyoxyethylene alkylphenyl ether sulfonates, and dialkyl sulfosuccinates. Examples of sulfates include alkyl sulfates, polyoxyethylene alkyl ether sulfates, and polyoxyethylene alkylphenyl ether sulfates. Examples of phosphates include polyoxyethylene alkylaryl ether phosphates and polyoxyethylene tristyrylphenyl ether phosphates. Examples of carboxylates include fatty acid salts and polycarboxylates.

[0024] Examples of such nonionic surfactants include polyoxyethylene alkyl ethers, polyoxypropylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene distyrylphenyl ethers, polyoxyethylene tristyrylphenyl ethers, sucrose fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, alkyl alkanolamides, polyoxyethylene polyoxypropylene block copolymers, alkyl polyglycosides, and acrylic copolymers.

[0025] Such cationic surfactants include, for example, alkylamine salts and quaternary ammonium salts.

[0026] Such amphoteric surfactants include, for example, alkyl betaines.

[0027] From the viewpoint of storage stability of the formulation, the surfactant is preferably at least one selected from the group consisting of lignin sulfonate and polyoxyethylene tristyryl phenyl ether phosphate.

[0028] Examples of lignin sulfonates used in the present invention include sodium lignin sulfonate, potassium lignin sulfonate, calcium lignin sulfonate, and ammonium lignin sulfonate, with sodium lignin sulfonate being preferred. The weight-average molecular weight of the lignin sulfonate used in the present invention is typically in the range of 2,000 to 15,000. The weight-average molecular weight of the lignin sulfonate used in the present invention refers to the relative molecular weight using sodium polystyrene sulfonate as the standard substance, and can be measured by gel permeation chromatography (GPC). Commercially available lignin sulfonates can be used. Examples of commercially available lignin sulfonates include REAX 85A (sodium lignin sulfonate, manufactured by Ingevity), REAX 907 (sodium lignin sulfonate, manufactured by Ingevity), REAX 910 (sodium lignin sulfonate, manufactured by Ingevity), Polyfon F (sodium lignin sulfonate, manufactured by Ingevity), Newkalgen RX-B (sodium lignin sulfonate, manufactured by Takemoto Yushi Co., Ltd.), and Polyfon H (sodium lignin sulfonate, manufactured by Ingevity).

[0029] The polyoxyethylene tristyrylphenyl ether phosphate salt used in the present invention may be a commercially available product, such as Soprofol FL (manufactured by Solvay Nicca), Soprofol FLK (manufactured by Solvay Nicca), STEPFAC TSP PE-K (manufactured by STEPAN), and Newkalgen FS-3PG (manufactured by Takemoto Yushi Co., Ltd.).

[0030] The composition of the present invention preferably contains 0.1 to 10% by weight, more preferably 2 to 10% by weight, of surfactants in total, based on the weight of the composition of the present invention.

[0031] The composition of the present invention contains water. The water used in the composition of the present invention is not particularly limited, and examples thereof include water used in ordinary aqueous suspension pesticide compositions, such as tap water, well water, and ion-exchanged water.

[0032] The composition of the present invention preferably contains 20 to 90% by weight, and more preferably 25 to 80% by weight, of water based on the weight of the composition of the present invention.

[0033] The composition of the present invention may further contain one or more formulation adjuvants used in conventional aqueous pesticide compositions, such as thickeners, antifoaming agents, preservatives, antifreeze agents, and pH adjusters.

[0034] Examples of such thickeners include natural polysaccharides such as xanthan gum, rhamsan gum, locust bean gum, guar gum, carrageenan, welan gum, alginic acid, alginates, and tragacanth gum; mineral powders such as aluminum silicate, magnesium aluminum silicate, smectite, bentonite, hectorite, synthetic hydrous silica, and dry silica; and alumina sol. Commercially available thickeners can be used as they are. Examples of such thickeners include Kelzan (CP Kelco product name) and Kelzan S PLUS (CP Kelco product name), which are xanthan gums; Veegum R (Vanderbilt product name), which is magnesium aluminum silicate; and Aerosil 200 (Nippon Aerosil product name), which is dry silica. These thickeners can be used alone or in combination. When the composition of the present invention contains a thickener, the total content thereof is preferably 0.01 to 5% by weight, more preferably 0.1 to 1% by weight, based on the weight of the composition of the present invention.

[0035] Examples of such defoaming agents include silicone-based defoaming agents. The defoaming agents may be used alone or in combination. When the composition of the present invention contains defoaming agents, the total content thereof is preferably 0.01 to 3 wt % based on the weight of the composition of the present invention.

[0036] Examples of such preservatives include p-hydroxybenzoic acid esters, salicylic acid derivatives, and isothiazolinone preservatives. These preservatives can be used alone or in combination. When the composition of the present invention contains preservatives, the total content thereof is preferably 0.005 to 1 wt % based on the weight of the composition of the present invention.

[0037] Examples of such antifreezing agents include ethylene glycol, propylene glycol, urea, and glycerin. These antifreezing agents can be used alone or in combination. When the composition of the present invention contains an antifreezing agent, the total content thereof is preferably 1 to 20 wt % based on the weight of the composition of the present invention.

[0038] Examples of such pH adjusters include citric acid monohydrate, carboxylic acids such as acetic acid and sorbic acid and their salts, phosphoric acid and its salts, sulfuric acid and its salts, and boric acid and its salts. When the composition of the present invention contains pH adjusters, the total content thereof is preferably 0.01 to 10 wt % based on the weight of the composition of the present invention.

[0039] The composition of the present invention can be produced using a pesticide active ingredient, natural rubber, a surfactant, water, and, if necessary, formulation adjuvants such as a thickener, an antifoaming agent, a preservative, an antifreeze agent, and a pH adjuster, and the production method thereof is not particularly limited.

[0040] A method for producing the composition of the present invention includes a step of adding natural rubber to a suspension containing a pesticidal active ingredient, a surfactant, and water. More specifically, the method includes a first step of producing a suspension containing a pesticidal active ingredient, a surfactant, and water, and a second step of adding natural rubber to the suspension and uniformly mixing the mixture. The first step includes, for example, mixing the pesticidal active ingredient, the surfactant, and, if necessary, formulation adjuvants such as an antifoaming agent and an antifreeze agent with water, and then pulverizing the resulting mixture using a wet grinder such as a bead mill to obtain a suspension with an average particle size of the pesticidal active ingredient of 10 μm or less, preferably 5 μm or less. In the first step, the resulting mixture may be further suspended (dispersed) using a disper mill or the like. In the present invention, particle size refers to the volume median diameter. The volume median diameter refers to the particle size at a cumulative frequency of 50% in a volume-based frequency distribution, and can be determined by wet measurement using a laser diffraction particle size distribution analyzer. More specifically, the object to be measured is dispersed in water and measured using the device. As such a laser diffraction particle size analyzer, a Mastersizer 3000 manufactured by Malvern Instruments is used. The second step includes adding natural rubber, and if necessary, formulation adjuvants such as thickeners, preservatives, and pH adjusters, to the suspension obtained in the first step and mixing them uniformly. In the second step, natural rubber-containing latex can also be used instead of natural rubber itself.

[0041] The composition of the present invention can be applied to paddy fields, fields, orchards, lawns, non-agricultural lands, etc. in the same manner as for conventional aqueous suspension pesticide compositions. It can be applied by diluting the composition of the present invention with water and spraying the resulting aqueous dilution on plants growing in the above-mentioned locations. The preferred method for spraying the aqueous dilution is foliage spraying using a known sprayer. Furthermore, the preferred application form of the composition of the present invention is not seed treatment.

[0042] By applying the composition of the present invention to plants, pests can be controlled.

[0043] When the pesticide active ingredient contains an insecticidal active ingredient, acaricidal active ingredient or nematicidal active ingredient, such pests include, but are not limited to, harmful arthropods such as harmful insects and harmful mites, nematodes and other nematodes, and harmful mollusks.

[0044] When a fungicidal active ingredient is contained as the pesticidal active ingredient, such harmful organisms include, but are not limited to, plant pathogenic microorganisms such as fungi, oomycetes, Phytomyxea, and bacteria. Examples of fungi include Ascomycota, Basidiomycota, Blasocladiomycota, Chytridiomycota, Mucoromycota, and Olpidiomycota.

[0045] When the pesticide contains a herbicidal active ingredient, such harmful organisms include weeds. In the present invention, the term "weeds" refers to plants whose growth is undesirable in a given location.

[0046] The present invention will now be described in more detail with reference to Production Examples and Comparative Examples, but the present invention is not limited to these examples.

[0047] First, a production example and a comparative production example of an aqueous suspension concentrate pesticidal composition will be shown.

[0048] Details of the products described in the Production Examples and Comparative Production Examples are given below. Inpirfluxam: Water solubility at 20°C 16.4 ppm, melting point 104°C. Pyridaclomethyl: Water solubility at 20°C 0.8 ppm, melting point 174°C. Newkalgen RX-B: Sodium lignosulfonate, manufactured by Takemoto Yushi Co., Ltd. Propylene glycol: manufactured by ADEKA Corporation XIAMETER ACP-1500 Silicone compound: Silicone antifoaming agent, manufactured by Dow Corning Toray Co., Ltd. Proxel GXL(S): Preservative containing 1,2-benzisothiazolin-3-one as the active ingredient, manufactured by Lonza Corporation Kelzan S Plus: Xanthan gum, manufactured by CP Kelco Corporation Veegum R: Magnesium aluminum silicate, manufactured by Vanderbilt Co., Ltd. 35% sulfuric acid: manufactured by Kaname Pharmaceutical Co., Ltd. ULACOL (registered trademark): Aqueous dispersion containing 60% by weight of unmodified natural rubber, manufactured by Resitex Corporation. Nalstar MR-174: Aqueous dispersion containing 50% by weight of synthetic rubber (carboxy-modified methyl methacrylate-butadiene copolymer), manufactured by Nippon A&L Co., Ltd.

[0049] Production Example 1 17.7 parts by weight of inpirfluxam, 17.7 parts by weight of pyridaclomethyl, 4 parts by weight of Newkalgen RX-B (manufactured by Takemoto Yushi Co., Ltd.), 5 parts by weight of propylene glycol (manufactured by ADEKA Corporation), 0.1 part by weight of XIAMETER ACP-1500 Silicone Compound (manufactured by Dow Corning Toray Co., Ltd.), and 41.7 parts by weight of ion-exchanged water were mixed to obtain a mixture (i). The obtained mixture (i) was wet-pulverized using a horizontal bead mill (DYNO-MILL KDL, manufactured by WILLY A. BACHOFEN AG Maschinenfabrik) to obtain a suspension (i). Separately, 0.2 parts by weight of Proxel GXL(S) (manufactured by Lonza), 0.1 parts by weight of Kelzan S Plus (manufactured by CP Kelco), and 0.2 parts by weight of Veegum R (manufactured by Vanderbilt) were added to 9.5 parts by weight of ion-exchanged water, and the resulting mixture was stirred for 2 hours to obtain a uniform mixture (ii). This mixture (ii) was mixed with the previously obtained suspension (i), 0.1 parts by weight of XIAMETER ACP-1500 Silicone Compound (manufactured by Dow Corning Toray Co., Ltd.), 0.4 parts by weight of 35% sulfuric acid (manufactured by Kaname Chemical Co., Ltd.), and 3.3 parts by weight of ULACOL (registered trademark) (manufactured by Regitex Co., Ltd.) to obtain a composition (1) of the present invention consisting of the components shown in Table 1. The unit of the numerical value of each component shown in Table 1 is % by weight when the total amount of the aqueous suspension concentrate pesticidal composition is taken as 100% by weight.

[0050] Production Example 2 17.7 parts by weight of inpirfluxam, 17.7 parts by weight of pyridaclomethyl, 4 parts by weight of Newkalgen RX-B (manufactured by Takemoto Yushi Co., Ltd.), 5 parts by weight of propylene glycol (manufactured by ADEKA Corporation), 0.1 part by weight of XIAMETER ACP-1500 Silicone Compound (manufactured by Dow Corning Toray Co., Ltd.), and 36.7 parts by weight of ion-exchanged water were mixed to obtain a mixture (iii). The obtained mixture (iii) was wet-pulverized using a horizontal bead mill (DYNO-MILL KDL, manufactured by WILLY A. BACHOFEN AG Maschinenfabrik) to obtain a suspension (ii). Separately, 0.2 parts by weight of Proxel GXL(S) (manufactured by Lonza), 0.1 parts by weight of Kelzan S Plus (manufactured by CP Kelco), and 0.2 parts by weight of Veegum R (manufactured by Vanderbilt) were added to 9.5 parts by weight of ion-exchanged water, and the resulting mixture was stirred for 2 hours to obtain a uniform mixture (iv). Mixture (iv) with the previously obtained suspension (ii), 0.1 parts by weight of XIAMETER ACP-1500 Silicone Compound (manufactured by Dow Corning Toray Co., Ltd.), 0.4 parts by weight of 35% sulfuric acid (manufactured by Kaname Chemical Co., Ltd.), and 8.3 parts by weight of ULACOL (registered trademark) (manufactured by Regitex Co., Ltd.) was mixed to obtain a composition (2) of the present invention consisting of the components shown in Table 1.

[0051] Production Example 3 17.7 parts by weight of inpirfluxam, 17.7 parts by weight of pyridaclomethyl, 4 parts by weight of Newkalgen RX-B (manufactured by Takemoto Yushi Co., Ltd.), 5 parts by weight of propylene glycol (manufactured by ADEKA Corporation), 0.1 part by weight of XIAMETER ACP-1500 Silicone Compound (manufactured by Dow Corning Toray Co., Ltd.), and 28.3 parts by weight of ion-exchanged water were mixed to obtain a mixture (v). The obtained mixture (v) was wet-pulverized using a horizontal bead mill (DYNO-MILL KDL, manufactured by WILLY A. BACHOFEN AG Maschinenfabrik) to obtain a suspension (iii). Separately, 0.2 parts by weight of Proxel GXL(S) (manufactured by Lonza), 0.1 parts by weight of Kelzan S Plus (manufactured by CP Kelco), and 0.2 parts by weight of Veegum R (manufactured by Vanderbilt) were added to 9.5 parts by weight of ion-exchanged water, and the resulting mixture was stirred for 2 hours to obtain a uniform mixture (vi). Mixture (vi) with the previously obtained suspension (iii), 0.1 parts by weight of XIAMETER ACP-1500 Silicone Compound (manufactured by Dow Corning Toray Co., Ltd.), 0.4 parts by weight of 35% sulfuric acid (manufactured by Kaname Chemical Co., Ltd.), and 16.7 parts by weight of ULACOL (registered trademark) (manufactured by Regitex Co., Ltd.) was mixed to obtain a composition (3) of the present invention consisting of the components shown in Table 1.

[0052] Preparation Example 4: 17.7 parts by weight of inpirfluxam, 17.7 parts by weight of pyridaclomethyl, 4 parts by weight of Newkalgen RX-B (Takemoto Yushi Co., Ltd.), 5 parts by weight of propylene glycol (ADEKA Corporation), 0.1 part by weight of XIAMETER ACP-1500 Silicone Compound (Dow Corning Toray Co., Ltd.), and 23.3 parts by weight of ion-exchanged water were mixed to obtain a mixture (vii). The obtained mixture (vii) was wet-pulverized using a horizontal bead mill (DYNO-MILL KDL, WILLY A. BACHOFEN AG Maschinenfabrik) to obtain a suspension (iv). Separately, 0.2 parts by weight of Proxel GXL(S) (manufactured by Lonza), 0.1 parts by weight of Kelzan S Plus (manufactured by CP Kelco), and 0.2 parts by weight of Veegum R (manufactured by Vanderbilt) were added to 6.2 parts by weight of ion-exchanged water, and the resulting mixture was stirred for 2 hours to obtain a uniform mixture (viii). This mixture (viii) was mixed with the previously obtained suspension (iv), 0.1 parts by weight of XIAMETER ACP-1500 Silicone Compound (manufactured by Dow Corning Toray Co., Ltd.), 0.4 parts by weight of 35% sulfuric acid (manufactured by Kaname Chemical Co., Ltd.), and 25 parts by weight of ULACOL (registered trademark) (manufactured by Regitex Co., Ltd.) to obtain a composition (4) of the present invention consisting of the components shown in Table 1.

[0053] Comparative Production Example 1 17.7 parts by weight of inpirfluxam, 17.7 parts by weight of pyridaclomethyl, 4 parts by weight of Newkalgen RX-B (manufactured by Takemoto Yushi Co., Ltd.), 5 parts by weight of propylene glycol (manufactured by ADEKA Corporation), 0.1 part by weight of XIAMETER ACP-1500 Silicone Compound (manufactured by Dow Corning Toray Co., Ltd.), and 45 parts by weight of ion-exchanged water were mixed to obtain a mixture (ix). The obtained mixture (ix) was wet-pulverized using a horizontal bead mill (DYNO-MILL KDL, manufactured by WILLY A. BACHOFEN AG Maschinenfabrik) to obtain a suspension (v). Separately, 0.2 parts by weight of Proxel GXL(S) (manufactured by Lonza), 0.1 parts by weight of Kelzan S Plus (manufactured by CP Kelco), and 0.2 parts by weight of Veegum R (manufactured by Vanderbilt) were added to 9.5 parts by weight of ion-exchanged water, and the resulting mixture was stirred for 2 hours to obtain a uniform mixture (x). Mixture (x) with the previously obtained suspension (v), 0.1 parts by weight of XIAMETER ACP-1500 Silicone Compound (manufactured by Dow Corning Toray Co., Ltd.), and 0.4 parts by weight of 35% sulfuric acid (manufactured by Kaname Chemical Co., Ltd.) was mixed to obtain a comparative composition (1) consisting of the components shown in Table 1.

[0054] Comparative Production Example 2 17.7 parts by weight of inpirfluxam, 17.7 parts by weight of pyridaclomethyl, 4 parts by weight of Newkalgen RX-B (manufactured by Takemoto Yushi Co., Ltd.), 5 parts by weight of propylene glycol (manufactured by ADEKA Corporation), 0.1 part by weight of XIAMETER ACP-1500 Silicone Compound (manufactured by Dow Corning Toray Co., Ltd.), and 43.3 parts by weight of ion-exchanged water were mixed to obtain a mixture (xi). The obtained mixture (xi) was wet-pulverized using a horizontal bead mill (DYNO-MILL KDL, manufactured by WILLY A. BACHOFEN AG Maschinenfabrik) to obtain a suspension (vi). Separately, 0.2 parts by weight of Proxel GXL(S) (manufactured by Lonza), 0.1 parts by weight of Kelzan S Plus (manufactured by CP Kelco), and 0.2 parts by weight of Veegum R (manufactured by Vanderbilt) were added to 9.5 parts by weight of ion-exchanged water, and the resulting mixture was stirred for 2 hours to obtain a homogeneous mixture (xii). Mixture (xii) with the previously obtained suspension (vi), 0.1 parts by weight of XIAMETER ACP-1500 Silicone Compound (manufactured by Dow Corning Toray Co., Ltd.), 0.4 parts by weight of 35% sulfuric acid (manufactured by Kaname Chemical Co., Ltd.), and 1.7 parts by weight of ULACOL (registered trademark) (manufactured by Regitex Co., Ltd.) to obtain a comparative composition (2) consisting of the components shown in Table 1.

[0055] Comparative Production Example 3: 17.7 parts by weight of inpirfluxam, 17.7 parts by weight of pyridaclomethyl, 4 parts by weight of Newkalgen RX-B (manufactured by Takemoto Yushi Co., Ltd.), 5 parts by weight of propylene glycol (manufactured by ADEKA Corporation), 0.1 part by weight of XIAMETER ACP-1500 Silicone Compound (manufactured by Dow Corning Toray Co., Ltd.), and 35 parts by weight of ion-exchanged water were mixed to obtain a mixture (xiii). The obtained mixture (xiii) was wet-pulverized using a horizontal bead mill (DYNO-MILL KDL, manufactured by WILLY A. BACHOFEN AG Maschinenfabrik) to obtain a suspension (vii). Separately, 0.2 parts by weight of Proxel GXL(S) (manufactured by Lonza), 0.1 parts by weight of Kelzan S Plus (manufactured by CP Kelco), and 0.2 parts by weight of Veegum R (manufactured by Vanderbilt) were added to 9.5 parts by weight of ion-exchanged water, and the resulting mixture was stirred for 2 hours to obtain a uniform mixture (xiv). Mixture (xiv) with the previously obtained suspension (vii), 0.1 parts by weight of XIAMETER ACP-1500 Silicone Compound (manufactured by Dow Corning Toray Co., Ltd.), 0.4 parts by weight of 35% sulfuric acid (manufactured by Kaname Yakuhin Co., Ltd.), and 10 parts by weight of Narstar MR-174 (manufactured by Nippon A&L Co., Ltd.) to obtain a comparative composition (3) consisting of the components shown in Table 1.

[0056] Next, test examples will be shown for the water resistance (rain resistance) of the composition of the present invention.

[0057] Test Example 1: Plastic pots were filled with soil, wheat seeds were sown therein, and the plants were grown in a greenhouse. Wheat leaves were then cut to a length of 4 cm from the tip. Next, the aqueous suspension pesticide compositions obtained in Preparation Examples 1 to 4 and Comparative Preparation Examples 1 to 3 were each diluted 2000 times with water. Using a micropipettor (manufactured by Eppendorf), 4 μL of the resulting water dilution was dripped onto the center of the cut wheat leaf surface and allowed to air-dry. Next, the wheat leaf surface was rinsed by pouring 50 mL of water onto the wheat leaf surface directly above the treated area with the water dilution using an electric pipettor (manufactured by Eppendorf). All of the water used for rinsing was collected in a plastic cup. The amount of active ingredient present in the collected water was quantified by LC / MS, and the residual rate of the active ingredient was calculated using the following formula: The amount of active ingredient applied to the wheat leaf surface in equation 1 was calculated by applying 4 μL of the diluted solution to the center of the wheat leaf surface after cutting, and then immediately rinsing the wheat leaf surface by using an electric pipettor (Eppendorf) to pour 50 mL of acetonitrile directly above the treated area of ​​the wheat leaf surface. All of the acetonitrile used for rinsing was collected in a plastic cup, and the amount of active ingredient present in the collected acetonitrile was quantified by LC / MS. The higher the retention rate, the less likely it was to be washed away by water and the higher its rain resistance. The results are shown in Table 1.

[0058]

[0059] "Binder component / pesticidally active ingredient" refers to the weight percentage of natural rubber or synthetic rubber relative to the pesticidal active ingredient.

[0060] As shown in Table 1, the composition of the present invention has a high retention rate of the pesticidal active ingredient and improved rain resistance. In particular, when the composition contains a pesticidal active ingredient with high water solubility, the degree of improvement in rain resistance is greater.

[0061] According to the present invention, an environmentally friendly aqueous suspension concentrate pesticidal composition containing natural rubber, a natural material, can be provided. Furthermore, the present invention also provides an aqueous suspension concentrate pesticidal composition that can significantly inhibit runoff from treated plants (e.g., leaves or stems) due to water such as rainfall or sprinkling, and has excellent pesticidal activity.

Claims

1. It contains pesticide active ingredients, natural rubber, surfactants, and water. The aforementioned pesticide active ingredient is at least one selected from the group consisting of impulfluxam, pyridaclomethyl, mandestrobin, and oxazosulfyl. An aqueous suspension pesticide composition characterized in that the weight ratio of the pesticide active ingredient to the natural rubber is 100:3 to 1:

3.

2. The aqueous suspension pesticide composition according to claim 1, wherein the surfactant is at least one selected from the group consisting of lignin sulfonates and polyoxyethylene tristyrylphenyl ether phosphate salts.

3. The aqueous suspension pesticide composition according to claim 1, wherein the weight ratio of the pesticide active ingredient to the natural rubber is 20:1 to 1:

2.

4. The aqueous suspension pesticide composition according to claim 1, wherein the aqueous suspension pesticide composition contains 1 to 50% by weight of the pesticide active ingredient, 0.03 to 40% by weight of the natural rubber, 0.1 to 10% by weight of the surfactant, and 20 to 90% by weight of the water.

5. The aqueous suspension pesticide composition according to any one of claims 1 to 4, wherein the aqueous suspension pesticide composition is for foliar application.

6. A method for producing an aqueous suspension pesticide composition according to any one of claims 1 to 4, comprising the step of adding natural rubber to a suspension containing a pesticide active ingredient, a surfactant, and water.