Liquid pesticide formulations

Abstract

A liquid composition comprises at least two agrochemical active compounds, a hydrophobic organic solvent, a first surfactant, a second surfactant, and water. The at least two agrochemical active compounds are a first component, which is a compound given by formula (I), and a second component comprising at least one agrochemical active compound that is different from the first component, is sparingly water soluble, and is a solid at a temperature of 25°C. The first surfactant is at least one nonionic surfactant other than acrylic acid polymer and polyoxyethylene-polyoxypropylene block copolymer, and the second surfactant is one or more surfactants selected from group (A). In the liquid composition, a liquid having the first component dissolved or suspended in the hydrophobic organic solvent is dispersed in the water, and at least one agrochemical active compound of the agrochemical active compound(s) of the second component is suspended in the water. Group (A): the group consisting of acrylic acid polymers and their salts, ligninsulfonate salts, salts of the formalin condensates of a possibly alkyl group-bearing naphthalenesulfonic acid, and polyoxyethylene-polyoxypropylene block copolymers.

Description

Technical Field

[0001] The present invention relates to liquid pesticide formulations.

Background Art

[0002] As a pesticide formulation containing two kinds of pesticidal active compounds, a suspoemulsion in which a liquid pesticide component containing a first pesticidal active compound is dispersed in water and a solid pesticide component containing a second pesticidal active compound is suspended is known (for example, see International Publication No. 2015 / 024410 (Patent Document 1)).

[0003] As a pesticidal active ingredient, a compound represented by the following formula (I), which is an active ingredient of a herbicide, is known (for example, see the specification of US Patent No. 6537948 (Patent Document 2)).

Chemical Formula

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] An object of the present invention is to provide a liquid pesticide formulation which is a liquid composition containing two or more pesticidal active compounds and in which aggregation of the pesticidal active compounds is suppressed.

Means for Solving the Problems

[0006] The present invention provides the following liquid composition. [1] Contains two or more pesticide-active compounds, a hydrophobic organic solvent, a first surfactant, a second surfactant, and water, The two or more pesticide-active compounds mentioned above consist of a first component which is a compound represented by the following formula (I), and a second component which consists of one or more pesticide-active compounds different from the first component that are sparingly soluble in water and solid at a temperature of 25°C. The first surfactant is one or more nonionic surfactants other than acrylic acid polymers and polyoxyethylene polyoxypropylene block copolymers. The aforementioned second surfactant is one or more surfactants selected from the following group (A): A liquid composition in which a liquid in which the first component is dissolved or suspended in the hydrophobic organic solvent is dispersed in water, and one or more pesticide-active compounds from among the pesticide-active compounds contained in the second component are suspended. Group (A): A group consisting of acrylic acid polymers and their salts, lignin sulfonates, salts of formalin condensates of naphthalene sulfonic acid which may have alkyl groups, and polyoxyethylene polyoxypropylene block copolymers. [ka] [2] The liquid composition according to [1], wherein the first surfactant comprises at least one of polyvinyl alcohol and polyoxyalkylene vegetable oil. [3] The liquid composition according to [1] or [2], wherein the first surfactant comprises at least one of polyvinyl alcohol and polyoxyethylene castor oil. [4] The liquid composition according to any one of [1] to [3], wherein all of the pesticide-active compounds contained in the second component are suspended in the water. [5] The liquid composition according to any one of [1] to [4], wherein the second component comprises one or more pesticide-active compounds selected from the group (B) below. Group (B): A group consisting of flumioxazine and mesotrione. [6] The liquid composition according to any one of [1] to [5], wherein the hydrophobic organic solvent comprises at least one of an aromatic hydrocarbon and butyl benzoate. [Effects of the Invention]

[0007] According to the present invention, it is possible to provide a liquid pesticide formulation in which the aggregation of pesticide active compounds is suppressed. [Modes for carrying out the invention]

[0008] The liquid composition according to the present invention (hereinafter sometimes referred to as "the present invention composition") contains two or more pesticide-active compounds, a hydrophobic organic solvent, a first surfactant, a second surfactant, and water. The pesticide-active compound is a first component which is a compound represented by the above formula (I) (hereinafter sometimes referred to as "compound (I)"), and a second component which consists of one or more pesticide-active compounds different from the first component that are poorly soluble in water and solid at a temperature of 25°C. The first surfactant is one or more nonionic surfactants other than acrylic acid polymers and polyoxyethylene polyoxypropylene block copolymers, and the second surfactant is one or more surfactants selected from the following group (A). Group (A): A group consisting of acrylic acid polymers and their salts, lignin sulfonates, salts of formalin condensates of naphthalene sulfonic acid which may have alkyl groups, and polyoxyethylene polyoxypropylene block copolymers.

[0009] In the composition of the present invention, a liquid in which the first component is dissolved or suspended in a hydrophobic organic solvent is dispersed in water, and one or more pesticide-active compounds from among the pesticide-active compounds contained in the second component are suspended therein. The composition of the present invention is a suspension emulsion in which the continuous phase is an aqueous phase, and liquid particles and solid particles are dispersed in the continuous phase, wherein the liquid particles contain the first component, and the solid particles are at least one of the pesticide-active compounds contained in the second component.

[0010] The composition of the present invention contains two or more pesticide-active compounds, which are a first component, compound (I), and a second component, which is one or more pesticide-active compounds other than compound (I).

[0011] The first component, compound (I), is a known compound and has excellent herbicidal properties. Compound (I) can be synthesized, for example, by the method described in Patent Document 1. Compound (I) is a solid at 25°C, and in the composition of the present invention, compound (I) exists dissolved or suspended in a hydrophobic organic solvent.

[0012] The content of the first component in the composition of the present invention is usually 0.01% by weight or more, preferably 0.05% by weight or more, more preferably 0.1% by weight or more, and even more preferably 0.3% by weight or more. The content of the first component in the composition of the present invention is usually 30% by weight or less, preferably 20% by weight or less, more preferably 15% by weight or less, and even more preferably 10% by weight or less.

[0013] The second component is a pesticide-active compound that is sparingly soluble in water and solid at 25°C, and is one or more pesticide-active compounds different from the first component. In this specification, a pesticide-active compound that is sparingly soluble in water means a pesticide-active compound whose solubility in 1 L of water at 25°C is 1 g or less. The second component is not particularly limited as long as it is a pesticide-active compound that is sparingly soluble in water and solid at 25°C.

[0014] The preferred second component is a herbicidal active compound. Examples of the herbicidal active compound contained in the second component include flumioxazin, mesotrione, pyroxasulfone, simetryn, dimefuron, propanil, mefenacet, fentrazamide, etobenzanid, suip, oxadiargyl, pyrazolate, prodiamine, cafenstrole, pentoxazone, chlormephrop, pyriftalid, benzobicyclon, bromobutide, imazosulfuron, propyrisulfuron, flumiclorac pentyl, lactofen, flufenacet, rimsulfuron, isoxaflutole, chlorimuron-ethyl, thifensulfuron-methyl, chloransulam-methyl, and the like.

[0015] Among these, the second component is preferably one or more pesticidal active compounds selected from the following group (B). Group (B): The group consisting of flumioxazin and mesotrione.

[0016] Flumioxazin is a known compound. Flumioxazin can be synthesized, for example, by the methods described in JP-A-61-76486 and JP-A-5-97848.

[0017] Mesotrione is a known compound. Mesotrione can be synthesized, for example, by the literature described in The Pesticide Manual Fifteenth Edition (2009), British Crop Production Council (ISBN: 978-1-901396-18-8), and the like.

[0018] The pesticidal active compounds contained in the above group (B) can exist in a suspended state in water in the composition of the present invention.

[0019] The content of the second component in the composition of the present invention is usually 0.01% by weight or more, preferably 0.1% by weight or more, more preferably 0.5% by weight or more, and even more preferably 1% by weight or more. The content of the second component in the composition of the present invention is usually 40% by weight or less, preferably 30% by weight or less, and more preferably 20% by weight or less. If the second component is two or more pesticide active compounds, the content of the second component refers to the total content thereof.

[0020] The composition of the present invention may further contain herbicidal active compounds in addition to the above-mentioned pesticide active compounds. Examples of herbicidal active compounds that may further be included are glyphosate potassium salt, glyphosate dimethylamine salt, glyphosate monoethanolamine salt, glufosinate ammonium salt, glufosinate P ammonium salt, glyphosate isopropylammonium salt, 2,4-D choline salt, 2,4-D dimethylamine salt, dicamba diglycolamine salt, dicamba BAPMA salt, dicamba tetrabutylamine salt, dicamba tetrabutylphosphonium salt, cretodymium, S metrachlor, metrivudine, nicosulfuron, acetochlor, imazetapyrammonium salt, and the like.

[0021] The composition of the present invention contains a hydrophobic organic solvent. In this specification, a hydrophobic organic solvent means an organic solvent having a water solubility of 10% by weight or less at a temperature of 25°C. The hydrophobic organic solvent is not particularly limited as long as it is an organic solvent that can dissolve or suspend compound (I). Furthermore, two or more hydrophobic organic solvents may be used in mixture form.

[0022] Examples of hydrophobic organic solvents include, Esters such as methyl caproate, methyl caprylate, methyl caprate, methyl laurate, methyl myristate, methyl palmitate, methyl stearate, methyl oleate, methyl linoleate, ethyl acetate, butyl acetate, hexyl acetate, octyl acetate, benzyl acetate, methyl benzoate, ethyl benzoate, butyl benzoate, dimethyl phthalate, diethyl phthalate, diethyl oxalate, dioctyl succinate, methyl salicylate, dimethyl adipate, dibutyl adipate, tert-butyl acetoacetate, and allyl acetoacetate; ethers such as propylene glycol phenyl ether; Ketones such as acetophenone; Amides such as N,N-dimethyldecanamide, N,N-dimethyldodecanamide, N,N-dimethyltetradecanamide, and N,N-dimethyloctadecanamide; Lactams such as N-octylpyrrolidone, N-decylpyrrolidone, and N-dodecylpyrrolidone; Aliphatic hydrocarbons such as hexane, octane, decane, tridecane, tetradecane, hexadecane, octadecane, normal paraffin, isoparaffin, cycloparaffin, 1-undecene, and 1-hexeicosene; Aromatic hydrocarbons such as toluene, xylene, ethylbenzene, methylnaphthalene, dimethylnaphthalene, dodecylnaphthalene, and tridecylnaphthalene, as well as mixtures thereof; Fatty acids such as caproic acid, caprylic acid, capric acid, oleic acid, linoleic acid, and enanthic acid; Animal and vegetable oils such as olive oil, soybean oil, rapeseed oil, castor oil, linseed oil, cottonseed oil, palm oil, avocado oil, coconut oil, and shark liver oil; Mineral oils such as machine oils These are some examples.

[0023] Preferred hydrophobic organic solvents include benzoic acid esters such as methyl benzoate, ethyl benzoate, butyl benzoate, and benzyl benzoate, aromatic hydrocarbons, and benzyl acetate, but aromatic hydrocarbons and butyl benzoate are more preferred.

[0024] By using at least one of aromatic hydrocarbons and butyl benzoate as the hydrophobic organic solvent, the liquid in which compound (I) is dissolved or suspended in the hydrophobic organic solvent can be well dispersed in water. This effectively suppresses the aggregation of the pesticide-active compound contained in the composition of the present invention.

[0025] The hydrophobic organic solvent content in the composition of the present invention is preferably 1% by weight or more, more preferably 5% by weight or more, and may be 10% by weight or more, and preferably 50% by weight or less, more preferably 40% by weight or less, may be 30% by weight or less, and may be 25% by weight or less. If two or more hydrophobic organic solvents are included, the hydrophobic organic solvent content refers to the total content thereof.

[0026] Of the hydrophobic organic solvent content in the composition of the present invention, the content of aromatic hydrocarbons and / or butyl benzoate organic solvents is preferably 30% by weight or more, more preferably 50% by weight or more, may be 70% by weight or more, may be 90% by weight or more, or may be 100% by weight.

[0027] The composition of the present invention may contain organic solvents other than hydrophobic organic solvents.

[0028] The composition of the present invention contains, as a first surfactant, one or more nonionic surfactants other than acrylic acid polymers and polyoxyethylene polyoxypropylene block copolymers.

[0029] Examples of such nonionic surfactants include polyvinyl alcohol, polyoxyalkylene vegetable oil, polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene distyrylphenyl ether, polyoxyethylene tristyrylphenyl ether, sucrose fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, alkyl alkanolamide, and alkyl polyglycoside.

[0030] The first surfactant is preferably at least one of polyvinyl alcohol and polyoxyalkylene vegetable oil, and more preferably at least one of polyvinyl alcohol and polyoxyethylene castor oil.

[0031] The content of the first surfactant in the composition of the present invention is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, may be 1% by weight or more, preferably 20% by weight or less, more preferably 15% by weight or less, may be 10% by weight or less, or may be 7% by weight or less. If the first surfactant contains two or more surfactants, the content of the first surfactant refers to the total content thereof.

[0032] The composition of the present invention contains one or more surfactants selected from the following group (A) as a second surfactant. Group (A): A group consisting of acrylic acid polymers and their salts, lignin sulfonates, salts of formalin condensates of naphthalene sulfonic acid which may have alkyl groups, and polyoxyethylene polyoxypropylene block copolymers.

[0033] Acrylic acid polymers included in group (A) refer to polymers composed of one or more monomers having an acryloyl group, such as acrylic acid or methacrylic acid and their esters or amides. There are no particular restrictions on the type of monomer; there may be one type or two or more types. There are also no particular restrictions on the sequence of monomers; examples include random polymers, alternating polymers, block polymers, graft polymers, star polymers, etc. Counterions for the anionic group of surfactants include alkali metal ions such as sodium ions and potassium ions; alkaline earth metal ions such as calcium ions and magnesium ions; ammonium ions; and organic ammonium ions derived from monoethanolamine, diethanolamine, triethanolamine, etc.

[0034] The HLB value of the polyoxyethylene polyoxypropylene block copolymers included in group (A) by the Griffin method is preferably 5 or higher, more preferably 6 or higher, and may be 7 or higher. It is also preferably 18 or lower, more preferably 17 or lower, and may be 16 or lower. Furthermore, the average molecular weight of the polyoxyethylene polyoxypropylene block copolymers is preferably 2000 or higher, more preferably 3000 or higher, and may be 4000 or higher. It is also preferably 15000 or lower, more preferably 14000 or lower, and may be 13000 or lower.

[0035] The content of the second surfactant in the composition of the present invention is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, may be 1% by weight or more, and preferably 10% by weight or less, more preferably 7% by weight or less, and may be 5% by weight or less. If the second surfactant contains two or more surfactants, the content of the second surfactant refers to the total content thereof.

[0036] The ratio of the content of the first surfactant to the content of the second surfactant in the composition of the present invention (first surfactant / second surfactant) is preferably 0.1 or more, may be 0.5 or more, may be 1 or more, and preferably 10 or less, may be 7 or less, or may be 5 or less.

[0037] The present invention can suppress the aggregation of pesticide active compounds by using the above-mentioned surfactant as the first surfactant and one or more surfactants selected from the above-mentioned group (A) as the second surfactant.

[0038] The composition of the present invention contains water. Examples of water include deionized water, tap water, and groundwater. The water content in the composition of the present invention is usually 30% by weight or more, may be 40% by weight or more, may be 50% by weight or more, and is usually 95% by weight or less, may be 90% by weight or less, or may be 85% by weight or less.

[0039] The composition of the present invention may contain other formulation aids as needed. Examples of other formulation aids include thickeners, defoamers, antifreezes, and preservatives.

[0040] Examples of thickening agents include polysaccharides such as xanthan gum, clay, and silicates. The content of the thickening agent in the composition of the present invention is usually 0.05% by weight or more, may be 0.07% by weight or more, and is usually 5% by weight or less, may be 3% by weight or less.

[0041] Examples of defoaming agents include silicone-based defoaming agents. The content of the defoaming agent in the composition of the present invention is usually 0.01% by weight or more, may be 0.05% by weight or more, and is usually 1% by weight or less, may be 0.5% by weight or less.

[0042] Examples of antifreeze agents include ethylene glycol, propylene glycol, urea, and glycerin. The content of the antifreeze agent in the composition of the present invention is usually 1% by weight or more, may be 2% by weight or more, and is usually 10% by weight or less, may be 8% by weight or less.

[0043] Examples of preservatives include isothiazolinone-based preservatives. The preservative content in the composition of the present invention is usually 0.05% by weight or more, may be 0.1% by weight or more, and is usually 0.5% by weight or less, may be 0.3% by weight or less.

[0044] The composition of the present invention can be prepared, for example, using a first component and a second component, which are pesticide active ingredients, a hydrophobic organic solvent, a first surfactant, a second surfactant, water, and optionally a formulation aid. When the first component is contained in the oil phase and all the pesticide active compounds contained in the second component are suspended in the aqueous phase, the composition of the present invention can be prepared, for example, by the following method.

[0045] (Method 1) An emulsion is prepared by adding the first component, the first surfactant, a hydrophobic organic solvent, and optionally a formulation aid to water, and stirring and dispersing them with a stirrer such as a homogenizer. At this time, the first surfactant may be added to the hydrophobic organic solvent, to water, or to both. On the other hand, a suspension is prepared by adding the second component, the first surfactant and / or the second surfactant, and optionally a formulation aid to water, and grinding and suspending them by wet grinding using a media such as glass beads or zirconia. Next, the emulsion, the suspension, and optionally a formulation aid such as a thickener, preservative, or defoamer are mixed to obtain the composition of the present invention.

[0046] (Method 2) The oil phase is prepared by mixing the first component, a hydrophobic organic solvent, and, if necessary, the first surfactant and formulation aids. Meanwhile, the aqueous phase is prepared by adding the second component, the first surfactant and / or the second surfactant, and, if necessary, formulation aids to water. The oil phase is added to the aqueous phase, and emulsification and simultaneous grinding and suspension are carried out by wet grinding using media such as glass beads and zirconia. The mixture is then mixed with formulation aids such as thickeners, preservatives, and defoamers as necessary to obtain the composition of the present invention.

[0047] (Method 3) An emulsion is prepared using the same procedure as in Method 1. To this emulsion, a second component that has been pre-ground by a dry grinding method such as a hammer mill or air mill, a first surfactant and / or a second surfactant, and, if necessary, formulation aids such as thickeners, preservatives, and defoamers are added and uniformly suspended to obtain the composition of the present invention.

[0048] The composition of the present invention can exhibit excellent weed control efficacy when used for soil treatment of agricultural land such as fields, orchards, pastures, lawns, and forestry areas; non-agricultural land such as embankment slopes, riverbeds, road shoulders and slopes, railway tracks, parks, grounds, parking lots, airports, industrial facility sites such as factories and storage facilities, fallow land, and idle land in urban areas. When cultivating crops that have been conferred resistance to herbicides by introducing herbicide resistance genes, etc., the composition of the present invention can be used for foliar treatment to remove undesirable plants.

[0049] Users typically prepare a spray solution by mixing the composition of the present invention with water and apply it using a backpack sprayer, spray tank, spray plane, or irrigation system. The amount to be sprayed varies depending on weather conditions, timing of application, soil conditions, target crop, target weed, etc., but is usually 10L to 2000L per hectare, preferably 50L to 400L. The spray solution is prepared by mixing the composition of the present invention with water at a ratio of 2 to 10000 times, preferably 10 to 8000 times, and more preferably 15 to 6000 times, relative to its volume.

[0050] When applying the spray solution, an adjuvant may be mixed in. The type of adjuvant is not particularly limited, but if it is an oil-based adjuvant such as Agri-Dex or MSO (mineral oil such as paraffinic hydrocarbons, naphthenic hydrocarbons, aromatic hydrocarbons, or methylated seed oil esterified from vegetable oils (soybean oil or rapeseed oil)), it is desirable to mix it in the spray solution at a concentration of 0.25%, 0.5%, 1%, 2%, 3%, 4%, 5%, or 6% (volume / volume). If it is a nonionic adjuvant such as Induce (polyoxyalkylene alkyl ether, polyoxyalkylene fatty acid ester, alkylaryl alkoxylate, or alkylaryl polyoxyalkylene glycol), it is desirable to mix it in the spray solution at a concentration of 0.05%, 0.1%, 0.25%, or 0.5% (volume / volume). Other examples include anionic adjuvants such as Gramin S (substituted sulfonates), cationic adjuvants such as Genamin T 200BM (polyoxyethyleneamines), and organosilicon adjuvants such as Silwet L77. Furthermore, drift reducers such as Intact (polyethylene glycol) and volatilization reducers such as Vapex, a VaporGrip Xtra Agent (a mixture of potassium hydroxide and acetic acid) may be mixed in. The pH and hardness of the above spray solution are not particularly limited. [Examples]

[0051] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.

[0052] The products used in the preparation of the liquid composition are listed below. (organic solvent) Solvesso 200ND: Aromatic hydrocarbon, mainly C10-C13 alkylnaphthalenes, manufactured by ExxonMobil. JEFFSOL AG1700: Butyl benzoate, manufactured by Huntsman. Agnique AMD810: C8-C10 fatty acid dimethylamide, manufactured by BASF.

[0053] (Surfactants) Stepflow 26F: Polyoxyethylene polyoxypropylene block copolymer, manufactured by Stepan. Selvol 523: Polyvinyl alcohol, manufactured by Sekisui Chemical Co., Ltd. Alkamuls OR / 40: Polyoxyethylene castor oil, manufactured by Solvay. Emulsogen TS290: Polyoxyethylene tristyrylphenyl ether, manufactured by Clariant. Toximul CA-7.5: Cocoamine ethoxylate, manufactured by Stepan. Phenylsulfonate CAL: A mixture of calcium dodecylbenzenesulfonate and iso-butanol, manufactured by Clariant. Soprophor FLK: A mixture of polyoxyethylene tristyrylphenyl ether phosphate salt and propylene glycol, manufactured by Solvay. Atlox 4913: Acrylic acid polymer (graft polymer of methyl methacrylate and polyethylene glycol), manufactured by Croda. Reax 910: Sodium lignin sulfonate, manufactured by Ingevity. Morwet D-425: Sodium formalin condensate of alkylnaphthalene sulfonic acid, manufactured by Noryon. Synperonic PE / F 127: Polyoxyethylene polyoxypropylene block copolymer, manufactured by Croda. Ethylan NS-500LQ: Polyoxyethylene polyoxypropylene block copolymer, manufactured by Noryon.

[0054] (Thickening agent) Kelzan S Plus: Xanthan gum, manufactured by CP Kelco. Veegum®: Magnesium aluminum silicate, manufactured by RTVanderbilt Company, Inc. (Antifoaming agent) XIAMETER ACP-1500: Silicone-based mixture, manufactured by Toray Dow Corning. (Antifreezing agent) Propylene glycol: Made by Adeka (Preservative) Proxel GXL: 1,2-Benzisothiazolin-3-one, manufactured by Lonza.

[0055] <Comparative Manufacturing Example 1> 2.00 parts by weight of compound (I) and 1.00 part by weight of Alkamuls OR / 40 were mixed with 30.00 parts by weight of Solvesso 200ND to prepare 33.00 parts by weight of the oil phase. 22.50 parts by weight of deionized water were mixed with 0.07 parts by weight of XIAMETER ACP-1500 and the prepared oil phase (33.00 parts by weight) and then stirred and emulsified using a homogenizer (product name TK Auto Homo Mixer, manufactured by Tokushu Kika Kogyo Co., Ltd.) to prepare 55.57 parts by weight of emulsion (1) with a median volume diameter of 2.8 μm. The median volume diameter was measured using a Mastersizer 2000 (manufactured by Spectris) under the following measurement conditions: particle shape: irregular, refractive index: 1.52, absorptive rate: 0.1, dispersion medium: water (refractive index: 1.33). The median volume diameters described in the following comparative production examples and production examples were also measured using the above measuring equipment and conditions.

[0056] To 18.27 parts by weight of deionized water, 0.20 parts by weight of Veegum R, 4.50 parts by weight of Propylene glycol, 0.07 parts by weight of XIAMETER ACP-1500, 1.00 part by weight of Soprophor FLK, and 7.00 parts by weight of Flumioxazine were added, stirred, and mixed. The mixture was then wet-milled using a bead mill (product name Dynomill, manufactured by Shinmaru Enterprises, glass bead diameter 1.0 mm, packing density 80%, peripheral speed 10 m / s) to obtain 31.04 parts by weight of suspension (1) with a median volume diameter of 2.2 μm.

[0057] 0.10 parts by weight of Kelzan S Plus, 0.20 parts by weight of Proxel GXL, and 13.03 parts by weight of deionized water were mixed to obtain 13.33 parts by weight of a thickening agent-containing solution (1).

[0058] A liquid composition (hereinafter referred to as "comparative liquid composition 1") was obtained by mixing 55.57 parts by weight of emulsion (1), 31.04 parts by weight of suspension (1), 13.33 parts by weight of thickener-containing liquid (1), and 0.06 parts by weight of XIAMETER ACP-1500.

[0059] <Comparative Manufacturing Example 2> 17.00 parts by weight of the oil phase was prepared by mixing 1.00 part by weight of compound (I), 0.50 parts by weight of Emulsogen TS290, and 0.50 parts by weight of Phenylsulfonat CAL with 15.00 parts by weight of Solvesso 200ND. 37.07 parts by weight of emulsion (2) with a median diameter of 2.1 μm was prepared by adding 0.07 parts by weight of XIAMETER ACP-1500 and the prepared oil phase to 20.00 parts by weight of deionized water, and then stirring and emulsifying with a homogenizer (product name TK Auto Homo Mixer, manufactured by Tokushu Kika Kogyo Co., Ltd.).

[0060] 23.87 parts by weight of deionized water was mixed with 0.40 parts by weight of Veegum R, 4.50 parts by weight of Propylene glycol, 0.07 parts by weight of XIAMETER ACP-1500, 3.00 parts by weight of Soprophor FLK, and 4.35 parts by weight of Flumioxazine. The mixture was stirred and mixed, and wet-milled using a bead mill (product name Dynomill, manufactured by Shinmaru Enterprises, glass bead diameter 1.0 mm, packing density 80%, peripheral speed 10 m / s) to obtain 36.19 parts by weight of suspension (2) with a median volume diameter of 2.3 μm.

[0061] 0.20 parts by weight of Kelzan S Plus, 0.20 parts by weight of Proxel GXL, and 26.28 parts by weight of deionized water were mixed to obtain 26.68 parts by weight of a thickening agent-containing solution (2).

[0062] Emulsion (2) 37.07 parts by weight, suspension (2) 36.19 parts by weight, thickener-containing liquid (2) 26.68 parts by weight, and XIAMETER ACP-1500 0.06 parts by weight were mixed to obtain a liquid composition (hereinafter referred to as "comparative liquid composition 2"). When comparative liquid composition 2 was diluted 100 times with water and observed under a microscope, aggregates were observed.

[0063] <Comparative Manufacturing Example 3> Emulsion (3) with a median volume diameter of 1.3 μm was prepared using the same procedure as in Comparative Production Example 2, except that 1.00 part by weight of Phenylsulfonat CAL was used instead of 0.50 parts by weight of Emulsogen TS290 and 0.50 parts by weight of Phenylsulfonat CAL, and 15.00 parts by weight of Agnique AMD810 was used instead of 15.00 parts by weight of Solvesso 200ND.

[0064] A liquid composition (hereinafter referred to as "comparative liquid composition 3") was obtained by mixing 37.07 parts by weight of emulsion (3), 36.19 parts by weight of suspension (2) obtained by the same preparation method as in comparative manufacturing example 2, 26.68 parts by weight of thickener-containing liquid (2) obtained by the same preparation method as in comparative manufacturing example 2, and 0.06 parts by weight of XIAMETER ACP-1500.

[0065] <Comparative Manufacturing Example 4> Emulsion (4) with a median volume diameter of 1.3 μm was prepared using the same procedure as in Comparative Production Example 2, except that 0.50 parts by weight of Toximul CA-7.5 was used instead of 0.50 parts by weight of Emulsogen TS290 in the preparation method of emulsion (2) obtained in Comparative Production Example 2.

[0066] A liquid composition (hereinafter referred to as "comparative liquid composition 4") was obtained by mixing 37.07 parts by weight of emulsion (4), 36.19 parts by weight of suspension (2) obtained by the same preparation method as in comparative manufacturing example 2, 26.68 parts by weight of thickener-containing liquid (2) obtained by the same preparation method as in comparative manufacturing example 2, and 0.06 parts by weight of XIAMETER ACP-1500. When comparative liquid composition 4 was diluted 100 times with water and observed under a microscope, aggregates were observed.

[0067] <Comparative Manufacturing Example 5> 16.00 parts by weight of the oil phase was prepared by mixing 1.00 part by weight of compound (I) with 15.00 parts by weight of Solvesso 200ND. 20.00 parts by weight of deionized water was mixed with 1.00 part by weight of Selvol 523, 0.07 parts by weight of XIAMETER ACP-1500, and the prepared oil phase (16.00 parts by weight) to prepare 37.07 parts by weight of emulsion (5) with a median diameter of 2.5 μm by mixing and emulsifying using a homogenizer (product name TK Auto Homo Mixer, manufactured by Tokushu Kika Kogyo Co., Ltd.).

[0068] Emulsion (5) 37.07 parts by weight, suspension (2) obtained by the same preparation method as in Comparative Production Example 2 36.19 parts by weight, thickener-containing liquid (2) obtained by the same preparation method as in Comparative Production Example 2 26.68 parts by weight, and XIAMETER ACP-1500 0.06 parts by weight were mixed to obtain a liquid composition (hereinafter referred to as "Comparative Liquid Composition 5").

[0069] <Manufacturing Example 1> 24.87 parts by weight of deionized water was mixed with 0.40 parts by weight of Veegum R, 4.50 parts by weight of Propylene glycol, 0.07 parts by weight of XIAMETER ACP-1500, 2.00 parts by weight of Atlox 4913, and 4.35 parts by weight of Flumioxazine. The mixture was stirred and mixed, and wet-milled using a bead mill (product name Dynomill, manufactured by Shinmaru Enterprises, glass bead diameter 1.0 mm, packing density 80%, peripheral speed 10 m / s) to obtain 36.19 parts by weight of suspension (3) with a median volume diameter of 2.1 μm.

[0070] A liquid composition (hereinafter referred to as "Liquid Composition 1") was obtained by mixing 37.07 parts by weight of emulsion (5) obtained in Comparative Production Example 5, 36.19 parts by weight of suspension (3), 26.68 parts by weight of thickener-containing liquid (2) obtained by the same preparation method as in Comparative Production Example 2, and 0.06 parts by weight of XIAMETER ACP-1500.

[0071] <Manufacturing Example 2> In the preparation method for suspension (3) obtained in Production Example 1, a suspension (4) with a median volume diameter of 2.1 μm was obtained using the same procedure as in Production Example 1, except that 2.00 parts by weight of Reax 910 were used instead of 2.00 parts by weight of Atlox 4913.

[0072] A liquid composition (hereinafter referred to as "liquid composition 2") was obtained by mixing 37.07 parts by weight of emulsion (5) obtained in comparative manufacturing example 5, 36.19 parts by weight of suspension (4), 26.68 parts by weight of thickener-containing liquid (2) obtained by the same preparation method as in comparative manufacturing example 2, and 0.06 parts by weight of XIAMETER ACP-1500.

[0073] <Manufacturing Example 3> In the preparation method for suspension (3) obtained in Production Example 1, a suspension (5) with a median volume diameter of 2.0 μm was obtained using the same procedure as in Production Example 1, except that 2.00 parts by weight of Morwet D-425 were used instead of 2.00 parts by weight of Atlox 4913.

[0074] A liquid composition (hereinafter referred to as "liquid composition 3") was obtained by mixing 37.07 parts by weight of emulsion (5) obtained in comparative manufacturing example 5, 36.19 parts by weight of suspension (5), 26.68 parts by weight of thickener-containing liquid (2) obtained by the same preparation method as in comparative manufacturing example 2, and 0.06 parts by weight of XIAMETER ACP-1500.

[0075] <Manufacturing Example 4> In the preparation method for emulsion (5) obtained in Comparative Production Example 5, emulsion (6) with a median volume diameter of 2.2 μm was obtained using the same procedure as in Comparative Production Example 5, except that 15.00 parts by weight of JEFFSOL AG1700 was used instead of 15.00 parts by weight of Solvesso 200ND.

[0076] Emulsion (6) 37.07 parts by weight, suspension (4) 36.19 parts by weight obtained by the same preparation method as in Production Example 2, thickener-containing liquid (2) 26.68 parts by weight obtained by the same preparation method as in Comparative Production Example 2, and XIAMETER ACP-1500 0.06 parts by weight were mixed to obtain a liquid composition (hereinafter referred to as "this liquid composition 4").

[0077] <Manufacturing Example 5> 17.00 parts by weight of the oil phase was prepared by mixing 1.00 part by weight of compound (I) and 1.00 part by weight of Alkamuls OR / 40 with 15.00 parts by weight of JEFFSOL AG1700. 37.07 parts by weight of emulsion (7) with a median diameter of 2.6 μm was prepared by adding 0.07 parts by weight of XIAMETER ACP-1500 and 17.00 parts by weight of the prepared oil phase to 20.00 parts by weight of deionized water, and stirring and emulsifying with a homogenizer (product name TK Auto Homo Mixer, manufactured by Tokushu Kika Kogyo Co., Ltd.).

[0078] A liquid composition (hereinafter referred to as "liquid composition 5") was obtained by mixing 37.07 parts by weight of emulsion (7), 36.19 parts by weight of suspension (3) obtained by the same preparation method as in Production Example 1, 26.68 parts by weight of thickener-containing liquid (2) obtained by the same preparation method as in Comparative Production Example 2, and 0.06 parts by weight of XIAMETER ACP-1500.

[0079] <Manufacturing Example 6> An emulsion (8) with a median volume diameter of 2.2 μm was obtained by the same procedure as in Production Example 5, except that Solvesso 200ND was used instead of 15.00 parts by weight of JEFFSOL AG1700 in the preparation method for emulsion (7) obtained in Production Example 5.

[0080] In the preparation method for suspension (2) obtained in Comparative Production Example 2, suspension (6) with a median volume diameter of 2.2 μm was obtained using the same procedure as in Comparative Production Example 2, except that 2.00 parts by weight of Morwet D-425 and 1.00 part by weight of Ethylan NS-500LQ were used instead of 3.00 parts by weight of Soprophor FLK.

[0081] Emulsion (8) 37.07 parts by weight, suspension (6) 36.19 parts by weight, thickener-containing liquid (2) obtained by the same preparation method as in Comparative Production Example 2 2 26.68 parts by weight, and XIAMETER ACP-1500 0.06 parts by weight were mixed to obtain a liquid composition (hereinafter referred to as "this liquid composition 6").

[0082] <Manufacturing Example 7> A liquid composition (hereinafter referred to as "liquid composition 7") was obtained by mixing 37.07 parts by weight of emulsion (7) obtained by the same preparation method as in Production Example 5, 36.19 parts by weight of suspension (6) obtained by the same preparation method as in Production Example 6, 26.68 parts by weight of thickener-containing liquid (2) obtained by the same preparation method as in Comparative Production Example 2, and 0.06 parts by weight of XIAMETER ACP-1500.

[0083] <Manufacturing Example 8> In the preparation method for suspension (3) obtained in Production Example 1, a suspension (7) with a median volume diameter of 1.5 μm was obtained using the same procedure as in Production Example 1, except that 2.00 parts by weight of Stepflow 26F were used instead of 2.00 parts by weight of Atlox 4913.

[0084] A liquid composition (hereinafter referred to as "liquid composition 8") was obtained by mixing 37.07 parts by weight of emulsion (5), 36.19 parts by weight of suspension (7), 26.68 parts by weight of thickener-containing liquid (2), and 0.06 parts by weight of XIAMETER ACP-1500, which were prepared using the same method as in comparative manufacturing example 5.

[0085] <Manufacturing Example 9> In the preparation method for the suspension (3) obtained in Production Example 1, a suspension (8) with a median volume diameter of 1.9 μm was obtained by the same procedure as in Production Example 1, except that 2.00 parts by weight of Synperonic PE / F 127 was used instead of 2.00 parts by weight of Atlox 4913.

[0086] A liquid composition (hereinafter referred to as "liquid composition 9") was obtained by mixing 37.07 parts by weight of emulsion (8) and 36.19 parts by weight of suspension (8) obtained by the same preparation method as in Production Example 6, 26.68 parts by weight of thickener-containing liquid (2) obtained by the same preparation method as in Comparative Production Example 2, and 0.06 parts by weight of XIAMETER ACP-1500.

[0087] <Manufacturing Example 10> A liquid composition (hereinafter referred to as "liquid composition 10") was obtained by mixing 37.07 parts by weight of emulsion (8) obtained by the same preparation method as in Production Example 6, 36.19 parts by weight of suspension (7) obtained by the same preparation method as in Production Example 8, 26.68 parts by weight of thickener-containing liquid (2) obtained by the same preparation method as in Comparative Production Example 2, and 0.06 parts by weight of XIAMETER ACP-1500.

[0088] [Test Example 1: Wet Sieve Test] Immediately after manufacturing and after storage at 54°C for two weeks, 10 g of the liquid composition was weighed into a 300 mL beaker, 100 mL of tap water was added, and the mixture was stirred for 5 minutes using a stirrer. The resulting suspension was transferred to a 100 mesh sieve, and after thoroughly rinsing with tap water, the residue was collected using deionized water and dried. The percentage of residue [%] was calculated from the weight of the dried residue. If the percentage of residue immediately after manufacturing and after storage at 54°C for two weeks is less than 0.1%, the aggregation of the pesticide active compound in the liquid composition is suppressed, and the formulation can be evaluated as having excellent storage stability. The results of measuring the percentage of residue immediately after manufacturing and after storage at 54°C for two weeks are shown in Table 1.

[0089] [Table 1]

[0090] [Test Example 2] Sow weeds (Amaranthus philoxeroides, Amaranthus oleraceus, Ragweed, Ragweed trifoliata, Erigeron annuus, Lagerstroemia indica, Kochia crustacean, Barnyard grass, and Setaria viridis) into plastic pots containing soil. On the same day, treat the soil surface with a mixture of one of the liquid compositions 1 to 10, Agri-Dex (a mixture of heavy paraffin oil, polyhydric alcohol fatty acid ester, and polyethoxylate derivative, manufactured by Helena Chemical, specific gravity: 0.88), Intact (a mixture of polyethylene glycol, choline chloride, and guar gum, manufactured by Precision Laboratories, specific gravity: 1.06), Vapex, a VaporGrip Xtra Agent (a mixture of potassium hydroxide and acetic acid, manufactured by Kalo, specific gravity: 1.27), XtendiMAX Herbicide with VaporGrip Technology (dicambadiglycolamine salt, manufactured by Bayer, specific gravity: 1.2), and water. The application rates for each formulation were 20 g / ha for the liquid composition as compound (I), 1232 g / ha for Agri-Dex, 742 g / ha for Intact, 1858 g / ha for Vapex, a VaporGrip Xtra Agent, and 1931 g / ha for XtendiMAX Herbicide with VaporGrip Technology, with a spray volume of 140 L / ha. The plants were then cultivated in a greenhouse, soybeans were sown 7 days later, and the weed control effect and phytotoxicity to soybeans were investigated 14 days later. Excellent weed control effects were confirmed with all formulations used.

[0091] [Test Example 3] Sow weeds (Amaranthus philoxeroides, Amaranthus oleraceus, Ragweed, Ragweed trifoliata, Erigeron annuus, Lagerstroemia indica, Kochia crustacean, Barnyard grass, and Setaria viridis) into plastic pots containing soil. On the same day, treat the soil surface with a mixture of one of the liquid compositions 1 to 10, Agri-Dex (a mixture of heavy paraffin oil, polyhydric alcohol fatty acid ester, and polyethoxylate derivative, manufactured by Helena Chemical, specific gravity: 0.88), Intact (a mixture of polyethylene glycol, choline chloride, and guar gum, manufactured by Precision Laboratories, specific gravity: 1.06), Vapex, a VaporGrip Xtra Agent (a mixture of potassium hydroxide and acetic acid, manufactured by Kalo, specific gravity: 1.27), XtendiMAX Herbicide with VaporGrip Technology (dicambadiglycolamine salt, manufactured by Bayer, specific gravity: 1.2), and water. The application rates for each formulation were 20 g / ha for the liquid composition as compound (I), 1232 g / ha for Agri-Dex, 742 g / ha for Intact, 389 g / ha for Vapex, a VaporGrip Xtra Agent, and 1931 g / ha for XtendiMAX Herbicide with VaporGrip Technology, with a spray volume of 140 L / ha. The plants were then cultivated in a greenhouse, soybeans were sown 7 days later, and the weed control effect and phytotoxicity to soybeans were investigated 14 days later. Excellent weed control effects were confirmed with all formulations used.

Claims

1. It contains two or more pesticide-active compounds, a hydrophobic organic solvent, a first surfactant, a second surfactant, and water. The two or more pesticide-active compounds mentioned above consist of a first component which is a compound represented by the following formula (I), and a second component which consists of one or more herbicidal-active compounds different from the first component that are sparingly soluble in water and solid at a temperature of 25°C. The first surfactant is one or more nonionic surfactants other than acrylic acid polymers and polyoxyethylene polyoxypropylene block copolymers, and comprises at least one of polyvinyl alcohol and polyoxyethylene castor oil. The second surfactant is one or more surfactants selected from the following group (A): A liquid composition in which a liquid in which the first component is dissolved or suspended in the hydrophobic organic solvent is dispersed in water, and all of the herbicidal active compounds contained in the second component are suspended. Group (A): A group consisting of acrylic acid polymers and their salts, lignin sulfonates, salts of formalin condensates of naphthalene sulfonic acid which may have alkyl groups, and polyoxyethylene polyoxypropylene block copolymers. 【Chemistry 1】

2. The liquid composition according to claim 1, wherein the first surfactant comprises polyvinyl alcohol.

3. The liquid composition according to claim 1, wherein the first surfactant comprises polyoxyethylene castor oil.

4. The liquid composition according to any one of claims 1 to 3, wherein a liquid in which the first component is dissolved in the hydrophobic organic solvent is dispersed in the water.

5. The liquid composition according to any one of claims 1 to 4, wherein the second component comprises one or more herbicidal active compounds selected from the group (B) below. Group (B): A group consisting of flumioxazine and mesotrione.

6. The liquid composition according to any one of claims 1 to 5, wherein the hydrophobic organic solvent comprises at least one of an aromatic hydrocarbon and butyl benzoate.

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