JP7223952B2 - Liquid composition for foliage and soil treatment herbicide - Google Patents

Description

The present invention relates to a formulation that contains a hydrophilic amino acid-based herbicidal compound and a hydrophobic soil-treating herbicidal compound, maintains a uniform liquid state, and has a stable diluted solution during spraying.

Glyphosate and glufosinate, which are amino acid-based herbicidal compounds, are non-selective herbicidally active compounds that are absorbed from the stems and leaves of weeds, migrate into the body of the plant, and exhibit relatively early effects. In addition, its salts are extremely hydrophilic and highly soluble in water, and are prepared as highly concentrated liquid formulations that are diluted with water and sprayed, and are widely used as herbicides for controlling weeds and shrubs during the growing season. . However, these amino acid-based herbicidal compounds rapidly lose their activity due to adsorption and decomposition after they fall on the soil, and have no soil treatment effect. are doing.
On the other hand, many of the soil treatment herbicidal compounds with excellent residual effects have poor penetration and migration into the plant body, so they cannot control weeds during the growing season, used for control. These soil-treating herbicidal compounds are hydrophobic, and formulations to be used after dilution are prepared as solid formulations such as wettable powders and wettable granules, or as suspensions dispersed in water or the like.

Mixed formulations of the above-mentioned compounds include, for example, a mixed herbicidal liquid agent in which glyphosate, glufosinate and its salts and a hydrophobic photosynthesis-inhibiting herbicidal compound are dissolved (see, for example, Patent Document 1), and salts of glyphosate and soil treatment herbicides. A herbicidal composition containing the compound flupoxam and having both rapid-acting and residual-acting properties has been disclosed (see, for example, Patent Document 2). The product according to Patent Document 1 includes 2% glyphosate isopropylamine salt, 0.4% bromacil liquid (Power Bomber (registered trademark), product of Maruwa Biochemical Co., Ltd.), 1.5% glyphosate isopropylamine salt, 0.4% bromacil. 75%, mecoprop P potassium salt 0.3% solution (Earth Kamyraz (registered trademark), product of Earth Chemical Co., Ltd.). Further, as a product according to Patent Document 2, there is a 0.96% glyphosate potassium salt, 0.25% flupoxam liquid preparation (Roundup Maxload (registered trademark) ALIII, product of Nissan Chemical Co., Ltd.). However, all of the products described in these patent documents are liquid formulations (AL agents) that are directly sprayed without dilution, and have low concentrations of active ingredients.
In addition, as a foliage and soil treatment herbicide that can be used only outside the planting area, a suspension containing 20% glyphosate isopropylamine salt and 4% bromacyl (Glyholong (registered trademark) herbicide, imported and sold by Yamashin Co., Ltd. ) are sold.

Japanese Patent Application Laid-Open No. 2007-224002 JP 2012-140381 A

Amino acid-based herbicides can kill weeds in the growing season, but cannot control weeds that grow later. On the other hand, most soil treatment herbicides, which are expected to have a lasting herbicidal effect, are difficult to control weeds during the growing season, or require a large amount of chemical input, so they have little impact on the environment. Concerned. Therefore, by having the characteristics of both, it is possible to control pests regardless of the growing season, and the development of a mixed agent that can reduce the amount of chemical dosage will save labor in agricultural chemical spraying, reduce environmental impact, and reduce transportation costs. are required from other points of view.

The herbicidal properties of these agents are due to the physicochemical properties of the compounds. That is, the amino acid-based herbicidal compound absorbed from the foliage is hydrophilic and has high solubility in water and low solubility in organic solvents. On the other hand, soil treatment herbicidal compounds, which are expected to have a sustained herbicidal effect, are hydrophobic and have solubility in certain organic solvents, but low solubility in water.
Due to such a significant difference in physicochemical properties, it is difficult to develop a liquid formulation in which both herbicidal compounds are dissolved.

Several methods have been proposed so far for the development of liquid preparations in which an amino acid-based herbicidal compound and a hydrophobic soil-treating herbicidal compound are dissolved. In other words, in order to dissolve the active ingredient uniformly, there is a method of lowering the concentration of the ingredient (see, for example, Patent Documents 1 and 2). On the other hand, there is a method of suspending to contain a high concentration of active ingredient.
The AL agents described in the above patent documents are excellent in terms of user convenience, but on the other hand, due to the low concentration of active ingredients, the required amount of chemical solution per application area is less than that of diluted and sprayed agents. increase. Along with this, the amount of discarded plastic containers, which are containers for the AL agents, is also increasing, which poses a problem of burdening the environment.
In addition, a high-concentration suspension that is diluted and sprayed aggregates over time during storage, and the product needs to be stirred again before use. Further, the hydrophobic herbicidal compound tends to be sprayed unevenly unless it is sprayed while being stirred or is not sprayed immediately after dilution.
As mentioned above, from the viewpoint of reducing the burden on the environment and stabilizing and improving the effectiveness of pesticide spraying, the development of a liquid agent that dissolves high-concentration active ingredients uniformly and dilutes before spraying has become an issue. .

The present inventors diligently investigated solvents and surfactants capable of dissolving both amino acid-based herbicidal compounds, which have low solubility in organic solvents, and soil treatment herbicidal compounds, which have low solubility in water, at high concentrations. As a result, by mixing the glycol-based solvent, it has the storage stability of the undiluted solution and the stability after dilution while maintaining the respective action characteristics. The described herbicidal liquid composition was completed.

All names of herbicidal compounds described herein are generic names. Moreover, all are marketed and can be obtained easily.

Representative amino acid-based herbicidal compounds include glyphosate ammonium, isopropylamine, potassium and other salts, glufosinate ammonium, glufosinate P sodium and other salts, and the like.

Amino acid-based herbicidal compounds are generally known to be hydrophilic, and have extremely high solubility in water even when compared with polar solvents such as methanol and ethanol. For example, glyphosate is 10.5 g/L in water (20°C), 0.231 g/L in methanol (20°C), glyphosate isopropylamine salt is 1050 g/L in water (25°C), methanol glyphosate potassium salt has a solubility of 918.7 g/L (20°C) in water and 217 mg/L (20°C) in methanol. In addition, glufosinate ammonium salt exhibits a solubility of 1370 g/L (22°C) in water and 0.65 g/L (20°C) in ethanol (Pesticide Handbook 2016 Edition, Japan Plant Protection Association, published in 2016. ).
Therefore, water is a more suitable solvent than polar solvents such as methanol and ethanol when preparing high-concentration solutions of amino acid-based herbicidal compounds.

The hydrophilic amino acid-based herbicidal compound in the present invention is one having hydrophilicity with a solubility in water of 1% (10 g/L) or more at 20 to 25°C.
These hydrophilic amino acid-based herbicidal compounds may be used alone or in combination of two or more in the composition of the present invention. The content of the amino acid-based herbicidal compound is preferably 2 to 25% by weight relative to the total amount of the composition of the present invention, and the appropriate content of water is 0.5 to 20% by weight of the total amount of the composition of the present invention. .

On the other hand, the solubility of representative hydrophobic soil treatment herbicidal compounds in 1 L of water at 19-25° C. is as follows. amicarbazone 4.6 g (20°C), alachlor 200 mg (20°C), isouron 0.585 g (22°C), isoxaben 1.42 mg (20°C), ipfencarbazone 0.515 mg (20°C). 20°C), imazaquin 58.3 mg (20°C), indaziflam 4.4 mg (20°C), indanophan 17.1 mg (25°C), esprocarb 4.92 mg (20°C), oxadiazon 0.57 mg (20°C). 20°C), oxadiargyl 0.37 mg (20°C), oxadiclomefone 0.15 mg (20°C), oryzarin 2.6 mg (25°C), caffenstrol 2.5 mg (20°C), chloridazone 422 mg (20°C). ), diuron 36.4 mg (25°C), dichlobenil 18 mg (20°C), dithiopyr 0.5 mg (25°C), diflufenican 0.05 mg or less (25°C), dimethenamide 1.2 g (25°C) , simetryn 482 mg (20°C), terbasil 710 mg (20°C), tebuthiuron 2.57 g (20°C), teflulitrione 0.016 mg (20°C), topramezone 0.106 g (20°C), triaziflam 7 Triclopyrbutoxyethyl 5.75 mg (20°C) Trifluralin 0.184 mg (20°C) Napropamide 74 mg (20°C) Pyrazoxifene 0.80 mg (20°C) Pyriftalid 1.8 mg (25°C), pyrimisulfan 114 mg (20°C), propyzamide 12.9 mg (25°C), pyraclonil 50.1 mg (20°C), pyroxasulfone 3.49 mg (25°C), Fenoxasulfone is 0.17 mg (20°C), fentrazamide is 2.3 mg (20°C), fluazifop is 1.54 mg (25°C), flufenacet is 56 mg (20°C), flupoxam is 2.42 mg (20°C). ), flumioxazin 1.79 mg (25°C), pretilachlor 74 mg (25°C), prosulfocarb 13 mg (20°C), prodiamine 0.072 mg (25°C), bromacil 0.81 g (20°C ), florasulam 0.084 g (20°C), penoxsulam 408 mg (19°C), benzofenap 0.12 mg (25°C), bentazone 570 mg (20°C), bentiocarb 16.7 mg (20°C), Pendimethalin is 0.23 mg (20° C.), pent Xazone 0.216 mg (25°C), benfuresate 261 mg (25°C), mesotrione 0.16 g (20°C), metribuzine 1.05 g (20°C), mefenacet 5.2 mg (20°C), renacil It exhibits a solubility of 0.003 g (20° C.) (Agricultural Chemical Handbook 2016 Edition, Japan Plant Protection Association, 2016 issue/The Pesticide Manual Sixteenth Edition, BCPC, 2013 issue).

The soil treating herbicidal compound in the present invention is intended to be hydrophobic with a water solubility of 0.5% (5 g/L) or less at 19 to 25°C.
These hydrophobic soil treating herbicidal compounds may be used alone or in combination of two or more in the composition of the present invention.
Also, the content is desirably 0.2 to 15% by weight based on the total amount of the composition of the present invention.

In addition, the present invention is characterized by using a mixture of one or more of each of amino acid-based herbicidal compounds and hydrophobic soil-treating herbicidal compounds. - It is also possible to mix highly water-soluble foliar treatment compounds and soil treatment compounds such as PA, MCPA, MCPP and their salts, or hexazinone.

TECHNICAL FIELD The present invention relates to a formulation that mixes a hydrophilic amino acid-based herbicidal compound and a hydrophobic soil-treating herbicidal compound, maintains a uniform liquid state, and has a stable diluted solution during spraying.
Hydrophilic organic solvents other than water, hydrophobic organic solvents, and surfactants necessary for dissolving and stably maintaining two or more compounds having contradictory physicochemical properties will be clarified below.

Hydrophilic organic solvents that are highly safe and have a boiling point of 150° C. or higher include alcohols such as cyclohexanol, glycols such as ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol and polypropylene glycol, and diethylene glycol monoethyl ether. Glycol ethers, ketones such as cyclohexanone, γ-butyrolactone, fatty acid derivatives such as lactate, lower alkylpyrrolidones such as N-methylpyrrolidone and N-ethylpyrrolidone, lower alkylamides such as dimethylformamide and dimethylacetamide, and dimethyl sulfoxide and the like.

As a result of intensive studies, it was found that a glycol-based solvent is an essential hydrophilic organic solvent in the present invention. Here, the glycol-based solvent includes general glycol-based compounds having two hydroxyl groups in a lower alkyl group, polymers and copolymers of these compounds, and glycol ethers.
Glycol-based solvents are more compatible with water and surfactants than other hydrophilic organic solvents, and are also superior in terms of safety and cost.
These glycol-based solvents may be used alone or in combination of two or more in the composition of the present invention. When using a hydrophobic herbicidal compound with low solubility, it is also possible to use other hydrophilic organic solvents in combination.
Also, the appropriate content is 5 to 60% by weight based on the total amount of the composition of the present invention.

In the present invention, the solvent solubility of the active ingredient and the stability of the diluent can be improved by combining the hydrophilic organic solvent with a widely used general hydrophobic organic solvent.
Use examples of hydrophobic organic solvents include high-boiling hydrocarbon solvents, fatty acid esters, various vegetable oils, intermediate alkylpyrrolidones such as N-octylpyrrolidone and N-dodecylpyrrolidone, dimethyl C8-10 alkylamide, dimethyl C10 alkylamide, and the like. and intermediate alkylamides of
These hydrophobic organic solvents are not essential in the composition of the present invention, but when used, they may be used alone or in combination of two or more.
Also, the appropriate content is 0 to 35% by weight based on the total amount of the composition of the present invention.

In the present invention, general surfactants that are widely used can be used. For example, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene styrylphenyl ether, polyoxyalkylene styrylphenyl ether, polyoxyethylene fatty acid ester, sugar fatty acid ester, polyoxyethylene sugar fatty acid ester, polyoxyethylene castor oil Nonionic surfactants such as ether, polyoxyethylene hydrogenated castor oil ether, acetylene glycol ethylene oxide adduct, polyoxyethylene laurylamine, polyoxyethylene tallowamine, alkyl sulfate, alkylbenzene sulfonate, alkyl sulfosuccinate, anionic surfactants such as naphthalene sulfonates, alkylnaphthalene sulfonates, alkylnaphthalene sulfonic acid formalin condensate salts, polyoxyethylene alkyl ether sulfates, polyoxyethylene styrylphenyl ether sulfates, polycarboxylates; Amphoteric surfactants such as amino acid type and betaine type surfactants, silicone surfactants and fluorosurfactants are included.
These surfactants may be used alone or in combination of two or more in the composition of the present invention.
Also, the content is suitably 10 to 50% by weight with respect to the total amount of the composition of the present invention.

(Preparation method)
In preparing this herbicidal liquid agent, as shown in the preparation examples below, after dissolving a hydrophobic herbicidal compound in an organic solvent, a surfactant and an aqueous solution of an amino acid-based herbicidal compound are added to prepare a uniform liquid agent. can.

(Spraying method)
When using this herbicide solution to control weeds, after diluting it with water that is 20 to 200 times the herbicide solution, use a chemical sprayer or watering can to spread 50 to 200 ml per square meter evenly from the top of the weeds. It is desirable to disperse.
The amount of liquid agent per area and the amount of diluted water correspond to the growth of weeds. For example, when large weeds are targeted, it is necessary to reduce the dilution rate and increase the amount of sprayed water.

By simultaneously dissolving an amino acid-based herbicide compound that dissolves in water and a hydrophobic soil-treating herbicide compound that dissolves in an organic solvent, an economical herbicide that is easy to use and controls weeds from the growing season to later weeds. offer.

(Preparation Example 1) Preparation of 5% by weight of glufosinate ammonium salt and 12% by weight of bromacil mixed herbicide liquid Bromacil raw material 12.4 g, propylene glycol (product of Wako Pure Chemical Industries, Ltd.) 34.6 g, dimethyl C8-10 alkylamide (HALLCOMID M-8-10, product of Stepan Co., Ltd.) was added and dissolved, followed by 23 g of polyoxyethylene laurylamine (Brownon (registered trademark) L-205, product of Aoki Yushi Kogyo Co., Ltd.) and a 50% by weight aqueous solution of glufosinate ammonium salt. 10 g were mixed to prepare 100 g of a liquid agent.

(Preparation Example 2) Preparation of 4% by weight of glufosinate ammonium salt and 12% by weight of bromacil mixed herbicide liquid 34.6 g of propylene glycol and 18 g of dimethyl C8-10 alkylamide were added to 12.4 g of bromacil raw material and dissolved. Oxyethylene tristyryl phenyl ether (Solpol (registered trademark) T-10, product of Toho Chemical Industry Co., Ltd.) 9 g, 80% polyoxyethylene tristyryl phenyl ether sulfate ammonium salt (Solpol T-10SPG, product of Toho Chemical Industry Co., Ltd.) 18 g and 8 g of a 50% by weight aqueous solution of glufosinate ammonium salt were mixed to prepare 100 g of a liquid preparation.

(Preparation Example 3) Preparation of 20% by weight of glyphosate isopropylamine salt and 12% by weight of bromacil mixed herbicide liquid Bromacil 12.5 g, dipropylene glycol (product of Wako Pure Chemical Industries, Ltd.) 9.1 g, dimethyl C8-10 alkylamide9. After adding and dissolving 1 g of the solution, 37 g of polyoxyethylene laurylamine (Braunon L-205) and 32.3 g of a 62% by weight aqueous solution of glyphosate isopropylamine salt were mixed to prepare 100 g of a liquid preparation.

(Preparation Example 4) Preparation of 5% by weight of glufosinate ammonium salt and 6% by weight of Terbasil mixed herbicide liquid To 6.3 g of Terbasil, 40.4 g of propylene glycol and 16 g of dimethyl C8-10 alkylamide were added and dissolved, followed by polyoxyethylene. 9.1 g of tristyrylphenyl ether (SOLPOL T-10), 18.2 g of 80% polyoxyethylene tristyrylphenyl ether sulfate ammonium salt (SOLPOL T-10SPG) and 10 g of a 50% by weight aqueous solution of glufosinate ammonium salt were mixed to obtain 100 g of liquid agent. prepared.

(Preparation Example 5) Preparation of 5% by weight of glufosinate ammonium salt and 6% by weight of metribuzin mixed herbicide liquid To 6.3 g of metribuzin, 40.4 g of propylene glycol and 16 g of dimethyl C8-10 alkylamide were added and dissolved, followed by polyoxyethylene. 9.1 g of tristyrylphenyl ether (SOLPOL T-10), 18.2 g of 80% polyoxyethylene tristyrylphenyl ether sulfate ammonium salt (SOLPOL T-10SPG) and 10 g of a 50% by weight aqueous solution of glufosinate ammonium salt were mixed to obtain 100 g of liquid agent. prepared.

(Preparation Example 6) Preparation of 5% by weight of glufosinate ammonium salt and 6% by weight of isouron mixed herbicide liquid To 6.3 g of isouron, 40.4 g of propylene glycol and 16 g of dimethyl C8-10 alkylamide were added and dissolved, followed by polyoxyethylene. 9.1 g of tristyrylphenyl ether (SOLPOL T-10), 18.2 g of 80% polyoxyethylene tristyrylphenyl ether sulfate ammonium salt (SOLPOL T-10SPG) and 10 g of a 50% by weight aqueous solution of glufosinate ammonium salt were mixed to obtain 100 g of liquid agent. prepared.

(Preparation Example 7) Preparation of 7.5% by weight of glufosinate ammonium salt and 3.5% by weight of flupoxam mixed herbicide liquid To 3.6 g of flupoxam, 40.5 g of propylene glycol and 19.5 g of dimethyl C8-10 alkylamide were added and dissolved. After that, polyoxyethylene tristyryl phenyl ether (Solpol T-15, product of Toho Chemical Industry Co., Ltd.) 13 g, polyoxyethylene laurylamine (Brownon L-210, product of Aoki Yushi Kogyo Co., Ltd.) 5.5 g and glufosinate ammonium salt 100 g of a liquid agent was prepared by mixing 17.9 g of a 42 wt % aqueous solution.

(Preparation Example 8) Preparation of 10% by weight of glyphosate isopropylamine salt and 3.75% by weight of flupoxam mixed herbicide liquid To 3.8 g of flupoxam, 39.7 g of propylene glycol and 17.5 g of dimethyl C8-10 alkylamide were added and dissolved. After that, 16 g of polyoxyethylene tristyrylphenyl ether (Solpol T-15), 3 g of polyoxyethylene laurylamine (Braunon L-210) and 20 g of a 50% by weight glyphosate isopropylamine salt aqueous solution were mixed to prepare 100 g of a liquid preparation.

(Preparation Example 9) Preparation of 10% by weight of glufosinate ammonium salt and 0.4% by weight of indadifuram mixed herbicide solution Part 1
After adding and dissolving 45.1 g of propylene glycol and 15.5 g of dimethyl C8-10 alkylamide to 0.4 g of indazifuram, 13.5 g of polyoxyethylene tristyrylphenyl ether (Solpol T-15) and polyoxyethylene laurylamine were added. 5.5 g of (Brownon L-210) and 20 g of a 50% by weight aqueous solution of glufosinate ammonium salt were mixed to prepare 100 g of a liquid preparation.

(Preparation Example 10) Preparation of 10% by weight of glufosinate ammonium salt and 0.4% by weight of indadifuram mixed herbicide liquid preparation Part 2
After adding and dissolving 44.6 g of propylene glycol and 15.5 g of dimethyl C8-10 alkylamide to 0.4 g of indadifram, 13 g of polyoxyethylene tristyryl phenyl ether (SOLPOL T-15) and 80% polyoxyethylene tristyryl were added. 6.5 g of phenyl ether sulfate ammonium salt (Solpol T-15SPG, product of Toho Kagaku Kogyo Co., Ltd.) and 20 g of a 50% by weight aqueous solution of glufosinate ammonium salt were mixed to prepare 100 g of a liquid preparation.

(Preparation Example 11) Preparation of 10% by weight of glufosinate ammonium salt and 2.3% by weight of triadifuram mixed herbicide liquid After adding and dissolving 46.7 g of propylene glycol and 15 g of dimethyl C8-10 alkylamide to 2.3 g of triadifuram, poly 12 g of oxyethylene tristyrylphenyl ether (Solpol T-15), 4 g of 80% polyoxyethylene tristyrylphenyl ether sulfate ammonium salt (Solpol T-15SPG) and 20 g of 50% by weight aqueous solution of glufosinate ammonium salt were mixed to prepare 100 g of a liquid preparation. .

(Preparation Example 12) Preparation of 5% by weight of glufosinate ammonium salt and 0.3% by weight of diflufenican mixed herbicide solution To 0.3 g of diflufenican, 51.2 g of propylene glycol and 17.5 g of dimethyl C8-10 alkylamide were added and dissolved. , 15 g of polyoxyethylene tristyrylphenyl ether (Solpol T-15), 6 g of 80% polyoxyethylene tristyrylphenyl ether sulfate ammonium salt (Solpol T-15SPG) and 10 g of a 50% by weight aqueous solution of glufosinate ammonium salt were mixed to obtain 100 g of a liquid agent. prepared.

(Preparation Example 13) Preparation of 5% by weight of glufosinate ammonium salt and 0.5% by weight of pyroxasulfone mixed herbicide liquid 48 g of propylene glycol and 22.5 g of dimethyl C8-10 alkylamide were added to 0.5 g of pyroxasulfone and dissolved. After that, 13 g of polyoxyethylene tristyrylphenyl ether (SOLPOL T-15), 4 g of 80% polyoxyethylene tristyrylphenyl ether sulfate ammonium salt (SOLPOL T-15SPG) and 12 g of 50% by weight aqueous solution of glufosinate ammonium salt were mixed to obtain a liquid agent. 100 g was prepared.

(Preparation Example 14) Preparation of 10% by weight of glufosinate ammonium salt and 4% by weight of dithiopyr mixed herbicide liquid preparation Part 1
After adding 48.9 g of propylene glycol and 13 g of dimethyl C8-10 alkylamide to 4.1 g of dithiopyr and dissolving them, 10 g of polyoxyethylene tristyrylphenyl ether (SOLPOL T-15) and 80% polyoxyethylene tristyrylphenyl ether were added. 4 g of ammonium sulfate (Solpol T-15SPG) and 20 g of a 50% by weight aqueous solution of glufosinate ammonium salt were mixed to prepare 100 g of a liquid preparation.

(Preparation Example 15) Preparation of 10% by weight of glufosinate ammonium salt and 4% by weight of dithiopyr mixed solution Part 2
43.9 g of propylene glycol and 15.5 g of dimethyl C8-10 alkylamide were added to 4.1 g of dithiopyr and dissolved. 4.5 g of L-210) and 20 g of a 50% by weight aqueous solution of glufosinate ammonium salt were mixed to prepare 100 g of a liquid preparation.

(Preparation Example 16) Preparation of 10% by weight of glyphosate isopropylamine salt and 2% by weight of dithiopyr mixed herbicide liquid To 2.1 g of dithiopyr, 43.9 g of propylene glycol and 15 g of dimethyl C8-10 alkylamide were added and dissolved. 10 g of ethylene tristyrylphenyl ether (SOLPOL T-15), 4 g of 80% polyoxyethylene tristyrylphenyl ether sulfate ammonium salt (SOLPOL T-15SPG), and 25 g of a 40% by weight aqueous solution of glyphosate isopropylamine salt were mixed to prepare 100 g of a liquid preparation. .

(Preparation Example 17) Preparation of mixed herbicide liquid of 5% by weight of glufosinate ammonium salt, 1% by weight of isoxaben, and 1% by weight of oxadiclomefone To 1 g of isoxaben and 1 g of oxadiclomefone, 54 g of propylene glycol and 16 g of dimethyl C8-10 alkylamide were added and dissolved. , 12 g of polyoxyethylene tristyrylphenyl ether (Solpol T-15), 4 g of 80% polyoxyethylene tristyrylphenyl ether sulfate ammonium salt (Solpol T-15SPG), and 12 g of 42% by weight aqueous solution of glufosinate ammonium salt were mixed to obtain 100 g of liquid agent. prepared.

(Preparation Example 18) Preparation of 6.5% by weight of glufosinate ammonium salt, 0.14% by weight of indadifuram, and 6% by weight of bromacil mixed herbicide liquid 0.14 g of indadifuram, 6.2 g of bromacil, 46.16 g of propylene glycol, dimethyl C8-10 After adding and dissolving 17.5 g of alkylamide, 12 g of polyoxyethylene tristyrylphenyl ether (Solpol T-15), 5 g of 80% polyoxyethylene tristyrylphenyl ether sulfate ammonium salt (Solpol T-15SPG) and glufosinate ammonium salt. 100 g of a liquid agent was prepared by mixing 13 g of a 50% by weight aqueous solution.

(Preparation Example 19) Preparation of 5% by weight of glufosinate ammonium salt and 1.2% by weight of triazifuram mixed herbicide solution Part 1
26.2 g of propylene glycol, 26.2 g of diethylene glycol (product of Wako Pure Chemical Industries, Ltd.), and 16.4 g of dimethyl C8-10 alkylamide were added to 1.2 g of triazifuram and dissolved. 15 g of T-15), 5 g of 80% polyoxyethylene tristyrylphenyl ether sulfate ammonium salt (Solpol T-15SPG) and 10 g of a 50% by weight aqueous solution of glufosinate ammonium salt were mixed to prepare 100 g of a liquid preparation.

(Preparation Example 20) Preparation of 5% by weight of glufosinate ammonium salt and 1.2% by weight of triazifuram mixed herbicide solution Part 2
After adding and dissolving 26 g of propylene glycol, 26 g of dipropylene glycol and 16.8 g of dimethyl C8-10 alkylamide to 1.2 g of triazifuram, 15 g of polyoxyethylene tristyrylphenyl ether (Solpol T-15) and 80% polyoxy 5 g of ethylene tristyrylphenyl ether sulfate ammonium salt (Solpol T-15SPG) and 10 g of a 50% by weight aqueous solution of glufosinate ammonium salt were mixed to prepare 100 g of a liquid preparation.

(Preparation Example 21) Preparation of 5% by weight of glufosinate ammonium salt and 1.2% by weight of triazifuram mixed herbicide liquid preparation Part 3
After adding and dissolving 51.8 g of propylene glycol and 16.5 g of N-octylpyrrolidone (1-octyl-2-pyrrolidone, Wako Pure Chemical Industries, Ltd.) to 1.2 g of triazifuram, polyoxyethylene tristyrylphenyl ether ( 16.5 g of Sorpol T-15), 4 g of 80% polyoxyethylene tristyrylphenyl ether sulfate ammonium salt (Solpol T-15SPG) and 10 g of a 50% by weight aqueous solution of glufosinate ammonium salt were mixed to prepare 100 g of a liquid preparation.

(Preparation Example 22) Preparation of 5% by weight of glufosinate ammonium salt and 1.2% by weight of triazifuram mixed herbicide solution Part 4
After adding and dissolving 52.3 g of propylene glycol and 16.5 g of dimethyl C8-10 alkylamide to 1.2 g of triazifuram, polyoxyethylene castor oil ether (Nucalgen D-236, product of Takemoto Yushi Co., Ltd.) 15 g, 80% 5 g of ammonium polyoxyethylene tristyrylphenyl ether sulfate (Solpol T-15SPG) and 10 g of a 50% by weight aqueous solution of glufosinate ammonium salt were mixed to prepare 100 g of a liquid preparation.

(Preparation Example 23) Preparation of mixed herbicide liquid containing 15% by weight of glyphosate isopropylamine salt, 7.5% by weight of bromacil, and 3% by weight of MCPP Bromacil 7.8 g, MCPP 3.2 g, propylene glycol 7.8 g, dimethyl C8-10 alkylamide 15 g , and 42 g of polyoxyethylene laurylamine (Brownon L-207, product of Aoki Yushi Kogyo Co., Ltd.) were added and dissolved, and then mixed with 24.2 g of a 62% by weight aqueous solution of glyphosate isopropylamine salt to prepare 100 g of a liquid agent.

(Preparation Example 24) Preparation of 5% by weight of glufosinate ammonium salt and 6% by weight of bromacil mixed herbicide liquid To 6.3 g of bromacil was added 35.7 g of diethylene glycol monoethyl ether (product of Wako Pure Chemical Industries, Ltd.) and 3 g of dimethyl C8-10 alkylamide. After addition and dissolution, 26.7 g of polyoxyethylene tristyrylphenyl ether (Solpol T-15), 13.3 g of 80% polyoxyethylene tristyrylphenyl ether sulfate ammonium salt (Solpol T-15SPG) and 34 weights of glufosinate ammonium salt. % aqueous solution was mixed to prepare 100 g of a liquid agent.

(Preparation Example 25) Preparation of 5% by weight of glufosinate ammonium salt and 6% by weight of bromacil mixed herbicidal liquid agent 15) 15 g of 80% polyoxyethylene tristyrylphenyl ether sulfate ammonium salt (SOLPOL T-15SPG) and 12 g of 42% by weight aqueous solution of glufosinate ammonium salt were mixed to prepare 100 g of liquid preparation.

[Formulation stability test]
The prepared undiluted solution was stored in a thermostat set at 15° C. and −15° C. for one week, and the color tone of the solution and precipitation of crystals were observed. In addition, 1 ml of the prepared solution stock solution was added to 50 ml of water having a German hardness of 3, and after stirring, the mixture was stored in a thermostat at 15° C., and crystal precipitation was observed after 3 hours, 6 hours, and 1 day. As a control, suspension glyphorong herbicide was compared under similar conditions. Table 1 shows the results.
Regarding the preparation examples, the state of precipitation of crystals was determined as follows.
-: No crystal precipitation ±: Slight crystal precipitation +: Slight crystal precipitation ++: Crystal precipitation

As is clear from the formulation stability test, all of the examples of the present invention were found to be superior in stock solution stability and diluent stability as compared to the control suspension.

(Comparative Example 1) Citation of Prior Art Literature According to the description of Formulation Example 2 described in Patent Document 2 (Japanese Patent Application Laid-Open No. 2012-140381), 0.182 g of flupoxam, 1.364 g of N-methylpyrrolidone, and xylene After adding and dissolving 6.567 g, 1.705 g of Sorpol 2680X (a product obtained by diluting Sorpol 2680 with xylene to 80% by weight) and 0.182 g of glyphosate potassium salt were mixed to prepare 10 g of the emulsion. Observed the appearance.
As a result, Comparative Example 1 was found to be in a suspended state during preparation, indicating that the active ingredient was not uniformly dissolved.

In comparison with the prior art, Patent Document 2 gives formulation examples of emulsions and suspensions other than those cited in Comparative Example 1, but in any case, each component is uniformly dissolved. Data not shown.

(Comparative Examples 2 to 5) Preparation of mixed herbicidal suspension containing 10% by weight of glyphosate isopropylamine salt and 3.75% by weight of flupoxam According to Preparation Example 8, the same amount of hydrophilic organic solvent other than the glycol solvent was used. A comparative example was prepared. As the hydrophilic organic solvent, one was selected from aprotic solvents such as dimethylsulfoxide and N-methylpyrrolidone, and protic solvents such as 2-propanol and glycerin, and compared with Preparation Example 8 using a glycol solvent.

[Study test of hydrophilic organic solvent]
In Preparation Example 8 and Comparative Examples 2 to 5, the appearance was observed before adding a 50% by weight aqueous solution of glyphosate isopropylamine salt and after 6 hours at room temperature after the addition. Table 2 shows the results.
The symbols shown in Table 2 represent active ingredients and solvents in parentheses below.
(Hydrophilic organic solvent)
PG (propylene glycol), DMSO (dimethyl sulfoxide)
N-MP (N-methylpyrrolidone), 2-PrOH (2-propanol)
Glyc (glycerin)
(active ingredient)
GlyIPA (50% by weight aqueous solution of glyphosate isopropylamine salt)

As is clear from the results described in the study test for hydrophilic organic solvents, Preparation Example 8 containing a glycol-based solvent uniformly dissolves the hydrophobic active ingredient, After 6 hours at room temperature after the addition, both showed a clear appearance. On the other hand, in Comparative Examples 2 to 5 using hydrophilic organic solvents other than glycol-based solvents, there are also comparative examples in which two-layer separation is observed before the addition of the 50% glyphosate isopropylamine salt aqueous solution, and after 6 hours at room temperature after addition. Both comparative examples separated into two layers. From the above, the contribution of the glycol-based solvent to the effects of the present invention was clear.

[Herbicidal effect test]
Sow in 100 cm ² pots and dilute 50 times with water for crabgrass, shiroza, and china that have grown to a plant height of about 15 to 20 cm. , Preparation Examples 1, 9, 10, 11, 14 and 15 were diluted 100-fold with water and sprayed at 100 ml per square meter. As a control, indazifuram 19.1% suspension (Spectacle (registered trademark) flowable, product of Bayer Crop Science Co., Ltd.) 0.021 g, bromacyl 80% wettable powder (Maruwa Hyper (registered trademark) X wettable powder, Maruwa Bio Chemical Co., Ltd. product) 0.5 g, glufosinate 18.5% liquid (Busta (registered trademark) liquid, Bayer Crop Science Co., Ltd. product) 0.5 ml, glyphosate isopropylamine salt 41% liquid (Kusaclean (registered trademark) liquid, Mitsui Chemicals Agro Co., Ltd. product) and 2 ml of a suspension of 20% glyphosate isopropylamine salt and 4% bromacil (glyhorong herbicide) were diluted with 100 ml of water and sprayed at 100 ml per square meter. In addition, glyphosate isopropylamine salt 1.5%, bromacil 0.75%, mecoprop P potassium salt 0.3% solution (Earthkamyraz), and glyphosate potassium salt 0.96%, flupoxam 0.25% solution (Roundup Maxload ALIII) was sprayed at 40 ml per square meter. At the same time, a drug-untreated plot was provided as a control. In addition, before spraying the chemicals, each pot was lightly covered with the seeds of crabgrass, shiroza and china.
The herbicidal effect was evaluated by the degree of reaction to the chemicals after 3 days, 1 week, 2 weeks and 4 weeks. The degree of response to the drug was evaluated on an 11-grade scale from 0 (no drug reaction) to 10 (complete kill). Table 3 shows the results for crabgrass, Table 4 shows the results for the broadleaf weeds Chromosa and Bidensa, and Table 5 shows the number of subsequent emergence of each weed 4 weeks after spraying, which is the average value of two repetitions of each agent.

As is clear from the results described in the herbicidal effect test, the liquid composition according to the present invention, in which a hydrophilic amino acid herbicidal compound and a hydrophobic soil-treating herbicidal compound are uniformly dissolved, has a rapid effect on growing weeds. It exhibits a strong herbicidal action and at the same time suppresses the subsequent growth of weeds.

Claims (3)

2 to 25 weight percent of a hydrophilic amino acid herbicidal compound and 0.2 to 15 weight percent of isouron, isoxaben, indaziflam, oxadiclomefone, dithiopyr, diflufenican, terbacil, triaziflam, pyroxasulfone, flupoxam, bromacil and metribuzine. at least one selected hydrophobic herbicidal compound, 5 to 60 weight percent of a glycol solvent, 0.5 to 20 weight percent of water, 0 to 35 weight percent of a hydrophobic organic solvent, and a basic surfactant and acid phosphorus A clear herbicidal liquid composition containing from 10 to 50 weight percent surfactant without simultaneously containing an acid ester surfactant. 2. The herbicidal liquid composition according to claim 1, wherein the glycol solvent contains at least one compound selected from the group consisting of propylene glycol, dipropylene glycol, diethylene glycol and diethylene glycol monoethyl ether. 2. The herbicidal liquid composition according to claim 1, wherein the hydrophilic amino acid herbicidal compound contains at least one compound selected from the group consisting of glyphosate, glufosinate and salts thereof.