JP4237311B2 - Stabilized aqueous suspension herbicidal composition - Google Patents

Description

本発明のフェノールスルホン酸Ｎａ塩縮合物を用いたものは、ベンスルフロンメチルの分解がほとんど見られなかったが、その他の界面活性剤を用いたものでは、約１０％又はそれ以上の分解が見られた．
【００７８】
【試験例２】
ｐＨによるベンスルフロンメチルの残存率試験
試験例１と同様にスラリーＡを得、得られたスラリーＡ３０．００部に、ＴａｍｏｌＰＰ２．００部、ニューコール７１０（日本乳化剤（株））０．１０部、エチレングリコール（三井東圧化学（株））５．００部、ロードポール２３の１％水溶液（ローヌプーラン（株））３．００部、クニピアＦの５％水分散液（クニミネ工業（株））２０．００部、プロクセルＧＸＬ（ゼネカ（株））０．２０部及び水を添加し混合し、０．６Ｎ塩酸を添加して混合物のｐＨを６．０、６．５、７．１、７．５及び８．０に調整し、更に、水残部を加えてベンスルフロンメチル１．５４％及びピリブチカルブ１２．６０％を含有する水性懸濁状除草組成物（フロアブル）を得た。
【００７９】
得られた水性懸濁状除草組成物を５０℃の恒温機中に保存し、１４日間の経時変化を試験例１と同様にして評価した。その結果、経時後のベンスルフロンメチルの残存率として下記表２に示す。
【００８０】
【表２】

【００８１】
【試験例３】
界面活性剤による水中分散性試験
ベンスルフロンメチル原体（９７．０％）３．７８部、ピリブチカルブ原体（９６．８％）４３．３９部、サーフィノール１０４Ｅ（日信化学工業（株））０．１７部、ＫＰ−１４３６（２５％水溶液、花王（株））４．００部及び水４８．６６部を混合し、この混合物２．５ｋｇを、４．７６ｍｍφのスチールボール１７ｋｇを充填した湿式粉砕機アトライターＭＡ−１ＮＳ型を用いて、ローター回転数２００ｒｐｍにて６０分間粉砕し、スラリーを得た。
【００８２】
得られたスラリー３０．００部に、下記表４中に示した界面活性剤０．１〜３．０部、ＴａｍｏｌＰＰ（ＢＡＳＦジャパン（株））０．５０部、エチレングリコール（三井東圧化学（株））５．００部、ロードポール２３の１％水溶液（ローヌプーラン（株））５．００部、ウエランガムの１％水分散液（三晶（株））１３．００部、プロクセルＧＸＬ（ゼネカ（株））０．２０部及び水を添加、混合し、０．６Ｎ塩酸にてｐＨ７．５に調整し、更に水残部を加えて、ベンスルフロンメチル１．１０％及びピリブチカルブ１２．６０％を含有する水性懸濁状除草組成物（フロアブル）を得た。
【００８３】
得られた水性懸濁状除草組成物を、下記水中分散性試験の方法にしたがって、水面に落下させ、水性懸濁状除草組成物の水中への分散性を比較した。評価は次の試験方法による目視により判定し、水中分散指数を求め、下記表４に示した。
【００８４】
（水中分散性試験の方法）
水を入れたとゆの端約１０ｃｍ（注下）のところへ、水面上約１０ｃｍより注射器にてフロアブル１ｍｌを滴下し、滴下後、扇風機（注下地点で風速２ｍ／ｓｅｃ）を回した時のフロアブルの分散状態を、下記表３記載の項目について目視にて評価する。これら４項目の評点を合計したものを水中分散指数とし、合計点が９点以上のものを合格とする。なお、水中分散性試験の試験方法の概要を図１に示す。
【００８５】
【表３】

【００８６】
【表４】

なお、表中の界面活性剤の組成は、ニューコールＰＢ６０：ポリオキシエチレンビススチリルフェニルエーテル；ニューコール６１０：ポリオキシエチレンジスチレン化フェニルエーテル；ニューコール７０４：ポリオキシエチレンジスチレン化メチルフェニルエーテル；ニューコール７０７：ポリオキシエチレンジスチレン化メチルフェニルエーテル；ニューコール７１０：ポリオキシエチレンジスチレン化メチルフェニルエーテル；ニューコール７１４Ｆ：ポリオキシアルキレンジスチレン化メチルフェニルエーテル；ニューコール２６０７：ポリオキシエチレントリスチレン化メチルフェニルエーテルである。
【００８７】
界面活性剤にポリオキシアルキレンスチリルフェニルエーテルを用いたフロアブルは、いずれも９点以上の評価を得た。
【００８８】
【試験例４】
水性懸濁状除草組成物の経時安定性試験（活性成分の安定性試験）
実施例１乃至８の水性懸濁状除草組成物を、４０℃の恒温機中で保存し、９０日後の活性成分の安定性を、試験例１と同様にして評価した。その結果を、スルホニルウレア活性成分の残存率として下記表５に示す。
【００８９】
【表５】
活性成分の安定性試験
───────────────────────
試験製剤 ベンスルフロンメチルの残存率（％）
───────────────────────
実施例１ 99.1%
実施例２ 99.0%
実施例３ 99.5%
実施例４ 99.0%
実施例５ 99.1%
実施例６ 99.5%
実施例７ 99.2%
実施例８ 99.5%
───────────────────────
これら実施例の水性懸濁状除草組成物のベンスルフロンメチルは極めて安定で、４０℃で９０日間保存後も、ほとんど分解が見られなかった．
【００９０】
【試験例５】
水性懸濁状除草組成物の経時安定性試験（物理性の安定性試験）
実施例３乃至８の水性懸濁状除草組成物を、４０℃の恒温機中で保存し、９０日後の物理性の安定性を測定した。物理性の測定は通常の方法を用いた。その結果を、下記表６に示す。
【００９１】
【表６】

これら実施例のフロアブル剤の物理性は極めて安定で、40℃で90日間保存後もほとんど劣化は見られなかった。
【００９２】
【発明の効果】
本発明のスルホニルウレア系農薬活性成分を含有する水性懸濁状除草組成物は、経時による分解及び物理性の劣化が顕著に抑制され、安定性の良好な製剤を得ることが可能となった。
【図面の簡単な説明】
【図１】水中分散性試験の試験方法の概要である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a stabilized aqueous suspension herbicidal composition comprising one or more sulfonylurea herbicidal active ingredients and phenol sulfonates as active ingredients and a method of using the same.
[0002]
[Prior art]
Conventional herbicide dosage forms have mainly been wettable powders, aqueous solvents, emulsions, aqueous solutions, granules and the like. Of these, spraying agents such as wettable powder, aqueous solvent, emulsion, and aqueous solution are mainly used in upland fields and non-agricultural land. There is a problem of influence on the environment, and emulsions have a problem of environmental pollution due to solvents and emulsifiers and a fire risk due to organic solvents. Many herbicidal active ingredients are difficult to dissolve in water and are difficult to formulate in aqueous solutions. From these facts, recent preparations are being changed to such aqueous suspension compositions and dry flowables with less problems.
[0003]
On the other hand, the herbicide for paddy field has been mainly composed of granules. Granules are generally applied in an amount of 3 to 4 kg per 10 ares. In recent years, there has been an increasing demand for labor-saving spraying of agricultural chemicals, and a small amount of spraying agent that reduces the application amount of the preparation has become necessary. However, when it is attempted to reduce the application amount of the granule, the herbicidal active ingredient content in the granule inevitably increases, and the number of grains per unit area decreases. This is a factor that directly affects the effects of herbicides and phytotoxicity, and it is required to treat the entire paddy field as uniformly as possible. However, in order to evenly spread 1 kg granules developed in recent years to paddy fields, a certain level of skill and skill is required, and in some cases, a spraying device is required. The dosage form is not always satisfactory.
[0004]
In view of this, in the field of herbicides for paddy fields, aqueous suspension compositions have been developed for the purpose of saving labor and increasing efficiency during spraying. Unlike the aqueous suspension composition used in fields, non-agricultural lands, etc., this dosage form drops and dispenses the formulation directly from the container to the paddy field without requiring any special spraying equipment. In addition, since the processing amount is as small as about 100 milliliters to 1 liter per 10 ares, it has a feature that it is light and easy to handle, and depending on the field area, it can be transferred from the bank (so-called frame processing), It can be treated simply by pouring from the mouth when entering the water (so-called water mouth treatment), and is extremely labor-saving. However, since the aqueous suspension composition is a preparation in which an agrochemical active ingredient is dispersed or emulsified in water, it has a problem that it is difficult to apply to an agrochemical active ingredient that is easily hydrolyzed.
[0005]
Among the herbicidal active ingredients, in particular, sulfonylurea herbicidal active ingredients are widely used because they exhibit a high control activity at a low dose against many perennial weeds and broad-leaved weeds. However, sulfonylurea herbicidal active ingredients are relatively unstable in aqueous suspension compositions and often degrade during storage.
[0006]
For this reason, several methods have been proposed so far for stabilizing sulfonylurea herbicidal active ingredients in agricultural chemical formulations. That is, in solid preparations, those relating to stabilization in granules by the combination of calcium carbonate and phosphate (Japanese Patent Publication Nos. 6-60084, 62-84004 and 62-277306). Gazette), vegetable oil, high-boiling solvent or epoxidized vegetable oil (JP-B-7-74129 and JP-A-8-104603), iron oxide blend (JP-A-6-65010) ), Alkaline white carbon is used (JP-A-6-145015, JP-A-7-179304, JP-A-7-179305, JP-A-7-196413, and JP-A-8-283108), poly Granules using acrylate and dialkylsulfosuccinate (JP-A-7-165507), granules using zinc oxide (JP-A-8- 25416 JP) have been proposed. In addition, in aqueous suspension compositions, those using specific surfactants (JP-A-5-163106 and JP-A-9-183704) and sulfonylurea herbicides are easily decomposed under alkali. Those for adjusting the pH to the acidic side (Japanese Patent Publication No. 5-8164, Japanese Patent Application Laid-Open No. 5-105606, Japanese Patent Application Laid-Open No. 5-320012, Japanese Patent Application Laid-Open No. 6-321713, and Japanese Patent Application Laid-Open No. 7-157401) Has been proposed. Furthermore, as an oily suspension composition, an oily sol to which urea is added (Japanese Patent Laid-Open No. 6-40823) has been proposed.
[0007]
However, particularly in the case of an aqueous suspension composition, it is difficult to completely stabilize the active ingredient because it is a preparation in which an active ingredient that is easily degraded by water is suspended in water. Could not be avoided.
[0008]
[Problems to be solved by the invention]
If the solid herbicidal active ingredient is atomized at room temperature, the contact area with water increases, and in the case of a herbicidal active ingredient that is easily hydrolyzed, hydrolysis is further promoted as a result. Further, in order to disperse and suspend as fine particles in water, the action of a surfactant is essential. When the aqueous suspension composition is used, it is necessary to effectively suppress the decomposition of the active ingredient that is easily hydrolyzed in the aqueous system in which the herbicidal active ingredient and the surfactant are coexisted. As a method of suppressing such hydrolysis, it is necessary to select a surfactant, and when the hydrolysis rate depends on pH, it is effective to suppress hydrolysis by controlling pH.
[0009]
In order to obtain an aqueous suspension composition by these methods to obtain a physically and chemically stable preparation, the stability of the surfactant used must not be inhibited by pH.
[0010]
Since the sulfonylurea herbicidal active ingredient is unstable in the preparation, it is necessary to prepare for a considerable degree of degradation during the storage period, particularly in an aqueous suspension composition.
[0011]
As a result of intensive studies on an aqueous suspension herbicidal composition having a better storage stability and containing a sulfonylurea herbicidal active ingredient, the present inventors have obtained a sulfonylurea-based herbicidal composition by using a specific surfactant. It was found that an aqueous suspension herbicidal composition excellent in terms of chemical stability of the herbicidal active ingredient and physicochemical stability of the preparation could be obtained, and the present invention was completed.
[0012]
[Means for Solving the Problems]
The present invention relates to a stabilized aqueous suspension herbicidal composition containing one or more sulfonylurea herbicidal active ingredients and a phenol sulfonate as active ingredients, and the aqueous suspension herbicide thereof It is the method of applying a composition directly to a paddy field.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
Examples of the sulfonylurea herbicidal active ingredient in the aqueous suspension herbicidal composition of the present invention include methyl α- (4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl) -o-toluylate (general) Name: Bensulfuronmethyl), N- [4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -1-methyl-4- (2-methyl-2H-tetrazol-5-yl) -1H-pyrazolesulfonamide (Generic name: azimusulfuron), 3- (4,6-dimethoxypyrimidin-2-yl) -1- (2-ethoxyphenoxysulfonyl) urea (generic name: ethoxysulfuron), N- (2-chloroimidazo [ 1,2-α] pyridin-3-ylsulfonyl) -N′-3- (4,6-dimethoxypyrimidin-2-yl) ure (Generic name: imazosulfuron), ethyl 5- (4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl) -1-methylpyrazole-4-carboxylate (generic name: pyrazosulfuronethyl), 3- (4 , 6-Dimethoxy-1,3,5-triazin-2-yl) -1- [2- (2-methoxyethoxy) phenylsulfonyl] urea (generic name: synosulfuron), 1- [2- (cyclopropylcarbonyl) Anilinosulfonyl] -3- (4,6-dimethoxypyrimidin-2-yl) urea (generic name: cyclosulfamuron) and the like, and preferably, bensulfuron methyl, ethoxysulfuron, imazosulfuron or pyrazos Ruflon-ethyl, and chlorsulfuron and chlorimuron ethyl for field or non-agricultural land Neo fence iodosulfuron-methyl, flazasulfuron, sulfometuron methyl, can be mentioned primisulfuron methyl, rimsulfuron, the thifensulfuron methyl and the like, preferably a sulfometuron methyl or thifensulfuron-methyl.
[0014]
The compounding amount of the sulfonylurea herbicidal active ingredient in the aqueous suspension herbicidal composition of the present invention may be an amount that allows the suspension preparation to be prepared, and is usually 0.01 to 60% by weight in the preparation, preferably Is 0.1 to 40% by weight, more preferably 0.2 to 30% by weight.
[0015]
The aqueous suspension herbicidal composition of the present invention can contain two or more different sulfonylurea herbicidal active ingredients, and also contains herbicidal active ingredients, insecticidal active ingredients, or bactericidal active ingredients other than sulfonylurea-based herbicidal active ingredients. It is possible. In this case, the total content of active ingredients in the aqueous suspension herbicidal composition is usually 0.05 to 70% by weight, preferably 1 to 60% by weight, more preferably 5 to 50% by weight. is there.
[0016]
The herbicidal active ingredient other than the sulfonylurea herbicidal active ingredient to be used is not particularly limited as long as it is a normal herbicidal active ingredient. Daimlon, Caffentrol, Cyhalohop Butyl, Benzofenap, Pyrazolate, Pyrazoxifene, Benfresate, Beniocurve, Epoprodan, ACN, Cimetrine, Dimetamethrin, Pentoxazone, Edbenzanide, Dithiopyr, Butachlor, Oxadiargyl, Naproanilide, Simmesrin, 2,4-D Alkyl esters and salts thereof, MCPB, oxadichromephone, NBA-061, MT-128, SB-500 MK243, JC940 and the like, preferably, mefenacet, pyributicarb, bromobutide, daimuron, cafenstrole, a pyrazolate or SB-500.
[0017]
The insecticidal active ingredient used may be a long-lasting insecticide having osmotic transferability or an insecticide effective against pests that live on the water surface such as rice weevil and rice beetle, such as silafluophene, cycloprotorin, etho Fenprox, isoxathione, ethylthiomethone, imidacloprid, nitenpyram, acetamiprid and the like can be mentioned, and silafluophene, etofenprox or imidacloprid is preferred.
[0018]
The bactericidal active ingredient used may be a long-lasting bactericidal agent having osmotic transfer properties, such as carpropamide, pyroxylone, isoprothiolane, probenazole, iprobenphos, fipronil, flutolanil, Examples include flametopyr, and preferred are probenazole, fipronil, flutolanil, and flametopyr.
[0019]
The phenol sulfonates in the aqueous suspension herbicidal composition of the present invention are phenol sulfonates or condensates thereof.
[0020]
The salt of the phenol sulfonate used is not particularly limited as long as it is a salt usually used for agricultural chemicals, and examples thereof include sodium, potassium, lithium, calcium, ammonium, various amine salts, and the like. Is a sodium, potassium or ammonium salt.
[0021]
The phenol sulfonate condensate used is a product obtained by formalin condensation of a phenol sulfonate, and the degree of condensation is usually 20 to 60, preferably 30 to 50.
[0022]
The molecular weight of the phenol sulfonates to be used is usually 2000 to 50000, and preferably 5000 to 20000.
[0023]
Specific examples of the phenol sulfonates used in the present invention include TamolPP and Wetdol D1 (both BASF Japan Ltd.), but the present invention is not limited thereto.
[0024]
The amount of the phenol sulfonates used in the present invention is usually 0.01 to 40% by weight, preferably 0.05 to 30% by weight, more preferably in the aqueous suspension herbicidal composition. 0.1 to 20% by weight.
[0025]
These phenol sulfonates can be used alone or in combination of two or more, and other anionic surfactants, nonionic surfactants, zwitterionic surfactants and the like can also be blended.
[0026]
The amount of all surfactants including phenol sulfonates is usually 0.005 to 20% by weight in the aqueous suspension herbicidal composition, preferably 0.01 to 10% by weight, Preferably it is 0.1 to 5 weight%.
[0027]
As the surfactant other than the phenol sulfonates, a styryl phenyl ether condensate is particularly preferable in order to improve the dispersibility in water without impairing the stability and dispersion action of the sulfonylurea herbicidal active ingredient.
[0028]
The styryl phenyl ether condensate is, for example, styryl phenyl such as polyoxyethylene distyrenated phenyl ether, polyoxyethylene distyrenated methyl phenyl ether, polyoxyethylene tristyrenated phenyl ether, polyoxyethylene bisstyryl phenyl ether. Ethylene oxide adduct of ether {as specific examples, New Coal 710 (polyoxyethylene distyrenated methylphenyl ether, manufactured by Nippon Emulsifier Co., Ltd.), New Coal PB60 (Polyoxyethylene bisstyryl phenyl ether, Japanese emulsifier) Co., Ltd.), New Coal 610 (polyoxyethylene distyrenated phenyl ether, manufactured by Nippon Emulsifier Co., Ltd.), New Coal 2609 (Polyoxyethylene tristyrenated phenyl ether) Made in Japan emulsifier Co., Ltd.), and the like. } And those obtained by further adding propylene oxide to these ethylene oxide adducts {as specific examples, New Coal 714F (polyoxypropylene polyoxyethylene distyrenated methylphenyl ether, manufactured by Nippon Emulsifier Co., Ltd.), New Coal 2608F (polyoxypropylene polyoxyethylene tristyrenated phenyl ether, manufactured by Nippon Emulsifier Co., Ltd.). }, Such as polyoxyalkylene styryl phenyl ether in which alkylene oxide is added to styryl phenyl ether, preferably polyoxyethylene distyrenated methyl phenyl ether, polyoxyethylene bisstyryl phenyl ether or polyoxypropylene poly It is oxyethylene tristyrenated phenyl ether, more preferably polyoxyethylene distyrenated methyl phenyl ether or polyoxyethylene bisstyryl phenyl ether. Moreover, the polyoxyalkylene styryl phenyl ether used can use 1 type (s) or 2 or more types together.
[0029]
The blending amount of the styryl phenyl ether condensate is not particularly limited, but is preferably 0.01 to 10% by weight, more preferably 0.1 to 3% by weight.
[0030]
The pH of the aqueous suspension herbicidal composition of the present invention is usually 8.0 or less, preferably 4.0 to 8.0, and more preferably 6.0 to 8.0.
[0031]
In the aqueous suspension herbicidal composition of the present invention, a pH adjusting agent can be used to adjust the pH.
[0032]
Examples of the pH adjuster used include inorganic acids such as hydrochloric acid and phosphoric acid; organic acids such as citric acid, phthalic acid and succinic acid; organometallic salts such as sodium citrate and potassium hydrogen phthalate; Inorganic metal salts such as disodium hydrogen phosphate, sodium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, sodium carbonate, potassium carbonate, sodium borate; like sodium hydroxide, potassium hydroxide And hydroxides; and organic amines such as triethanolamine, and the like, preferably inorganic acids, inorganic metal salts, hydroxides or organic amines, more preferably hydrochloric acid, Phosphoric acid, sodium hydroxide, potassium hydroxide or sodium carbonate. Moreover, the pH adjuster used can use 1 type (s) or 2 or more types together.
[0033]
The pH adjuster is usually used by diluting with water to an appropriate concentration of 0.1 to 5 N and adding the diluted solution to 0.01 to 5% by weight, preferably 0.05 to 2% by weight. The
[0034]
The pH is measured by using a digital pH meter (castani LAB F-13 type, manufactured by Horiba, Ltd.) and measuring the aqueous suspension herbicidal composition itself (so-called stock solution).
[0035]
The aqueous suspension herbicidal composition of the present invention can further contain a thickener as necessary, and the viscosity varies depending on the presence and type of the thickener, but is usually 30 to 2000 mPa · s. , Preferably it is 100-1000 mPa * s, More preferably, it is 200-600 mPa * s.
[0036]
The viscosity is a value measured using a digital viscometer (DVL-BII type, manufactured by Tokimec Co., Ltd.). The measurement conditions are rotor No. 2, rotor rotation speed 30 rpm, and formulation temperature 20 ° C.
[0037]
Examples of the thickener used include fine powders of inorganic minerals such as smectite, sepiolite, attapulgite, laponite, montmorillonite, hectorite; carboxymethylcellulose, hydroxyethylcellulose, carboxyethylcellulose, methylcellulose, hydroxypropylcellulose, hydroxyethylcellulose, etc. Cellulose derivatives and salts thereof; natural gums such as xanthan gum, welan gum, guar gum, tragacanth gum and gum arabic; starch derivatives such as various grades of dextrin and sodium carboxymethyl starch; natural products such as sodium alginate and sodium caseinate and the like Derivatives of water-soluble synthetic polymers such as polyvinyl alcohol, polyacrylic acid and its derivatives, polyvinyl pyrrolidone, etc. And the like. Moreover, the thickener to be used can use 1 type (s) or 2 or more types together.
[0038]
The blending amount of the thickener used varies depending on the type of the thickener, but is usually 0.01 to 10% by weight, preferably 0.05 to 5% by weight.
[0039]
Moreover, the aqueous suspension herbicidal composition of this invention can contain another adjuvant as needed. Examples of other adjuvants include antifreezing agents, antifoaming agents, antibacterial agents, and stabilizers, but are not limited to the adjuvants exemplified herein.
[0040]
The antifreezing agent to be used is not particularly limited as long as it is a commonly used antifreezing agent, and examples thereof include ethylene glycol, propylene glycol, polyethylene glycol, and glycerin.
[0041]
The amount of the cryoprotectant used is usually 1 to 20% by weight, preferably 2 to 10% by weight in the aqueous suspension herbicidal composition.
[0042]
Examples of the antifoaming agent used include acetylene glycol-based, silicone-based, fluorine-based, and fatty acid-based antifoaming agents.
[0043]
The amount of the antifoaming agent used is usually 0.001 to 10% by weight, preferably 0.01 to 5% by weight, in the aqueous suspension herbicidal composition.
[0044]
Examples of the antibacterial agent used include benzothiazole derivatives, sorbic acid, potassium sorbate, butyl ρ-oxybenzoate, glutaraldehyde, thiazolone, and BNPK (2-bromo-2-nitropropane-1,3-diol). Etc.
[0045]
The amount of the antibacterial agent to be used is usually 0.01 to 5% by weight, preferably 0.05 to 2% by weight in the aqueous suspension herbicidal composition.
[0046]
Examples of the stabilizer used include an antioxidant, an ultraviolet ray inhibitor, and a crystal precipitation inhibitor.
[0047]
The aqueous suspension herbicidal composition of the present invention can be produced by various methods. For example, when wet pulverizing the active ingredient, the active ingredient, surfactant and antifoaming agent are added to water and mixed and suspended, and then wetted to a predetermined particle size using a wet pulverizer as described below. Pulverized, then pre-mixed with a thickener, antifreeze, antibacterial agent and other auxiliary ingredients mixed in water, dispersed and dissolved, and homogenized. Further, the pH of the composition is adjusted with a pH regulator. By adjusting, the aqueous suspension herbicidal composition of the present invention can be obtained.
[0048]
Examples of the wet pulverizer include attritor mills such as Atreiter (Mitsui Mine Co., Ltd.); Co., Ltd.), Super Apex Mill (Kotobuki Giken Kogyo Co., Ltd.), Diamond Fine Mill (Mitsubishi Heavy Industries, Ltd.), Coball Mill (Shinko Pantech Co., Ltd.), Dries Velke Pearl Mill (Nihon Eirich Co., Ltd.) Bead mills such as colloid mills (Special Machine Industries Co., Ltd.), wet atomizers (Fuji Powder Co., Ltd.) and the like.
[0049]
The pulverization of the active ingredient is not limited to wet pulverization. For example, if necessary, the active ingredient is mixed with a mineral carrier and other auxiliary agents, and pulverized to a predetermined particle size using a dry pulverizer. Is also possible. The obtained pulverized product is suspended and dispersed in water together with a surfactant, antifoaming agent, thickener, antifreeze agent, antibacterial agent and other auxiliary agents, mixed and homogenized, and further a pH adjuster. The aqueous suspension herbicidal composition of the present invention can be obtained by adjusting the pH of the composition to 8.0 or less.
[0050]
Examples of dry pulverizers include jet mills such as SK-Jet O Mizer (Seishin Company), Single Track Jet Mill (Seishin Company); ACM Pulperizer (Hosokawa Micron Corp.), Sample Mill Hammer mills such as (Fuji Powder Co., Ltd.), pin mills, ball mills, turbo mills and the like.
[0051]
Furthermore, the pulverization of the active ingredient can be appropriately combined with the pulverization by these pulverizers. For example, after preliminarily pulverizing with a wet pulverizer such as a colloid mill or wet atomizer, finely pulverizing with a bead mill or pre-dry pulverizing active ingredients together with a surfactant or antifoaming agent in water Can be further finely pulverized using the above-mentioned wet pulverizer. It is also possible to pre-pulverize with a batch-type pulverizer such as an attritor and then finely pulverize with a continuous bead mill.
[0052]
The degree of pulverization of the active ingredient is usually pulverized so that the majority of the active ingredient is 10 μm or less in both wet pulverization and dry pulverization, and preferably has a weight median diameter of 0.1 to 5 μm. Grind to make
[0053]
The particle size of the active ingredient is measured by the following measuring method.
(Measurement of weight median diameter)
About 0.5 g of a sample, 0.2% POLYFON H solution {POLYFON H (lignin sulfonate, manufactured by Westvaco) was dissolved in purified water and adjusted to 0.2%. } Add 100 milliliters and ultrasonically disperse for 3 minutes to obtain a sample solution.
[0054]
About 250 milliliters of a dispersion medium (purified water) is placed in an ultrasonic bath of a laser diffraction / light scattering particle size measuring instrument (LA-700, manufactured by Horiba Ltd.), and the sample liquid has a transmittance of 70 to 90%. The particle size distribution is obtained by using a particle size measuring machine in which the following conditions are set in advance. The weight median diameter (μm) is determined from the obtained particle size distribution.
[0055]
The measurement conditions of the particle size measuring device (LA-700) are as follows: stirring motor speed: “4”, ultrasonic dispersion operation time: “5 min”, waiting time after completion of ultrasonic: “0 sec”, circulation pump Speed: “3”, number of data acquisition: “10”, distribution form: “1”, and refractive index setting: “not”.
[0056]
Hereinafter, the present invention will be described more specifically with reference to examples and test examples, but the present invention is not limited to these examples.
[0057]
【Example】
[0058]
[Example 1]
Aqueous suspension herbicidal composition (500 ml / 10a treated preparation)
1.40 parts of bensulfuron methyl base, 12.00 parts of pyributycarb base, Surfynol 104E (50% ethylene glycol solution of tertiary acetylene glycol, Nissin Chemical Industry Co., Ltd.) 0.05 part, KP-1436 (POE alkylallyl phosphate ester salt 25% aqueous solution, Kao Corporation) 1.30 parts and water 25.25 parts were mixed, and 2.5 kg of this mixture was filled with 17 kg of 4.76 mmφ steel balls. Using a pulverizer Attritor MA-1NS type, the slurry was pulverized for 60 minutes at a rotor rotational speed of 200 rpm to obtain a slurry.
[0059]
To 40.00 parts of the resulting slurry, 0.50 part of TamolPP (a salt of phenol sulfonic acid condensate, BASF Japan Ltd.), 5.00 parts of ethylene glycol (Mitsui Toatsu Chemicals Co., Ltd.), Roadpole 23 20.00 parts of 1% aqueous solution (xanthan gum, Rhone-Poulenc Co., Ltd.), 5% aqueous dispersion of Kunipia F (purified bentonite, Kunimine Industries Co., Ltd.) 16.00 parts, Proxel GXL (30% of benzothiazole derivative) Dipropylene glycol solution, Zeneca Co., Ltd. (0.20 part), 0.6N hydrochloric acid (0.20 part) and water (18.10 parts) were added. Aqueous suspension herbicidal composition containing 1.40% bensulfuron methyl and 12.00% pilibutycarb (flowable) It was obtained.
[0060]
[Example 2]
Aqueous suspension herbicidal composition (500 ml / 10a treated preparation)
1.40 parts of bensulfuron methyl base, 12.00 parts of pyributicarb base, 0.12 part of Surfinol 104E (Nissin Chemical Industry Co., Ltd.), KP-1436 (25% aqueous solution, Kao Co., Ltd.) 20 parts and 15.28 parts of water were mixed, and 2.5 kg of this mixture was used for 60 minutes at a rotor rotational speed of 200 rpm using a wet crusher Atreiter MA-1NS type filled with 17 kg of 4.76 mmφ steel balls. Crushing to obtain a slurry.
[0061]
To 30.00 parts of the obtained slurry, 2.00 parts of TamolPP (BASF Japan Co., Ltd.), 5.00 parts of propylene glycol (Mitsui Toatsu Chemical Co., Ltd.), 1% aqueous solution of Rhode Paul 23 (Rhone-Poulenc ( Co., Ltd.)) 3.00 parts, Agrisol FL100F (31% aqueous solution of acrylic acid derivative, Kao Corporation) 20.00 parts, Proxel GXL (Zeneca Co., Ltd.) 0.20 part, 4% sodium hydroxide aqueous solution 0 .35 parts and 39.45 parts of water were added, and the whole amount was stirred and mixed using a three-one motor (1200G, manufactured by HEIDON Co., Ltd.) and contained 1.40% bensulfuron methyl and 12.00% pyributycarb. An aqueous suspension herbicidal composition (flowable) was obtained.
[0062]
[Example 3]
Aqueous suspension herbicidal composition (500 ml / 10a treated preparation)
1.40 parts of bensulfuron methyl base, 12.00 parts of pyributycarb base, Surfynol 104E (50% ethylene glycol solution of tertiary acetylene glycol, Nissin Chemical Industry Co., Ltd.) 0.05 part, KP-1436 (POE alkylallyl phosphate ester salt 25% aqueous solution, Kao Corporation) 1.30 parts and water 25.25 parts were mixed, and 2.5 kg of this mixture was filled with 17 kg of 4.76 mmφ steel balls. Using a pulverizer Attritor MA-1NS type, the slurry was pulverized for 60 minutes at a rotor rotational speed of 200 rpm to obtain a slurry.
[0063]
To 40.00 parts of the obtained slurry, 0.50 part of TamolPP (a salt of phenolsulfonic acid condensate, BASF Japan Ltd.), 0.15 part of New Coal PB60 (Japan Emulsifier Co., Ltd.), ethylene glycol (Mitsui 5.00 parts of Toatsu Chemical Co., Ltd., 20.00 parts of 1% aqueous solution (Xanthan Gum, Rhone-Poulenc Co., Ltd.) of Roadpol 23, 5% aqueous dispersion of Kunipia F (refined bentonite, Kunimine Industries Co., Ltd. ) 16.00 parts, Proxel GXL (30% dipropylene glycol solution of benzothiazole derivative, Zeneca) 0.20 part, 0.6N hydrochloric acid 0.20 part and water 17.95 parts, the total amount Was stirred and mixed using a three-one motor (1200G, manufactured by HEIDON Co., Ltd.). Aqueous suspended herbicidal compositions containing .00% of (flowable) was obtained.
[0064]
[Example 4]
Aqueous suspension herbicidal composition (500 ml / 10a treated preparation)
Bensulfuron methyl base 1.40 parts, Cavenstrol base 5.50 parts, Daimlon base 10.00 parts, Surfinol 104E (Nissin Chemical Industry Co., Ltd.) 0.15 parts, KP-1436 (25% aqueous solution) , Kao Corp.) 2.00 parts and water 12.95 parts were mixed, and this mixture was used with Apex Mill AM-1 having a capacity of 1 L vessel filled with 800 ml of 1.0 mmφ zirconia beads and a power of 1 KW The slurry was continuously pulverized at a slurry supply amount of 47 kg / H to obtain a slurry.
[0065]
To 32.00 parts of the resulting slurry, 0.50 part of TamolPP (BASF Japan Co., Ltd.), 0.15 part of New Coal PB60 (Nippon Emulsifier Co., Ltd.), ethylene glycol (Mitsui Toatsu Chemical Co., Ltd.) 5 0.000, 1% aqueous solution of Rhodopol 23 (Rhone-Poulein Co., Ltd.) 17.00 parts, 5% aqueous dispersion of Kunipia F (Kunimine Industries Co., Ltd.) 13.00 parts, Proxel GXL (Zeneca Co., Ltd.) ) 0.20 parts, 0.6N hydrochloric acid 0.70 parts and 31.45 parts of water were added, and the whole amount was stirred and mixed using a three-one motor (1200G, manufactured by HEIDON Co., Ltd.). An aqueous suspension herbicidal composition (floorable) containing 40%, Cavenstrol 5.50% and Daimlon 10.00% was obtained.
[0066]
[Example 5]
Aqueous suspension herbicidal composition (500 ml / 10a treated preparation)
1.40 parts of bensulfuron methyl base, 10.00 parts of pilibutycarb base, 8.00 parts of mefenacet base, 0.15 part of Surfinol 104E (Nissin Chemical Industry Co., Ltd.), KP-1436 (25% aqueous solution) 2.00 parts of Kao Co., Ltd. and 23.45 parts of water were mixed, and this mixture was mixed with a Dynomill KDL type having a capacity of 0.6 L vessel filled with 480 ml of 1.0 mmφ zirconia beads. Continuous grinding was performed at 3000 rpm and a slurry supply rate of 15 kg / H to obtain a slurry.
[0067]
To 45.00 parts of the resulting slurry, 0.50 part of TamolPP (BASF Japan), 0.20 part of New Coal 710 (Nippon Emulsifier), ethylene glycol (Mitsui Toatsu Chemicals) 5 0.000, 1% aqueous solution of Rhodopol 23 (Rhone-Poulein Co., Ltd.) 17.00 parts, 5% aqueous dispersion of Kunipia F (Kunimine Industries Co., Ltd.) 13.00 parts, Proxel GXL (Zeneca Co., Ltd.) ) 0.20 parts, 0.6N hydrochloric acid 0.20 parts and water 18.90 parts were added, and the whole amount was stirred and mixed using a three-one motor (1200 G, manufactured by HEIDON Co., Ltd.). An aqueous suspension herbicidal composition (flowable) containing 40%, piributicalbu 10.00% and mefenacet 8.00% was obtained.
[0068]
[Example 6]
Aqueous suspension herbicidal composition (250 ml / 10a treated preparation)
2.80 parts of bensulfuron methyl base, 11.00 parts of caffrontrol base, 20.00 parts of Daimlon base, 0.15 part of Surfinol 104E (Nissin Chemical Industry Co., Ltd.), KP-1436 (25% aqueous solution) , Kao Co., Ltd.) 2.60 parts and 28.45 parts of water were mixed, and this mixture was subjected to a rotor rotation speed using a wet crusher attritor MA-1NS type filled with 4.75 mmφ steel balls 17 kg. The slurry was pulverized at 200 rpm for 20 minutes to obtain a slurry.
[0069]
To 65.00 parts of the resulting slurry, 1.00 part of TamolPP (BASF Japan Ltd.), 0.30 part of New Coal PB60 (Nippon Emulsifier Co., Ltd.), ethylene glycol (Mitsui Toatsu Chemical Co., Ltd.) 5 0.000 parts, 1% aqueous solution of Rhodopol 23 (Rhone-Poulein Co., Ltd.) 12.75 parts, 5% aqueous dispersion of Kunipia F (Kunimine Industries Co., Ltd.) 9.75 parts, Proxel GXL (Zeneca Co., Ltd.) ) 0.20 parts, 0.6N hydrochloric acid 0.75 parts and water 5.25 parts were added, and the whole amount was stirred and mixed using a three-one motor (1200G, manufactured by HEIDON Co., Ltd.). An aqueous suspension herbicidal composition (floorable) containing 80%, Caventrol 11.00% and Daimlon 20.00% was obtained.
[0070]
[Example 7]
Aqueous suspension herbicidal composition (300 ml / 10a treated preparation)
2.30 parts of bensulfuron methyl base, 9.20 parts of cfentrole base, 16.70 parts of dimelon base, 20.00 parts of bromobutide base, 0.15 part of Surfinol 104E (Nisshin Chemical Industry Co., Ltd.) , KP-1436 (25% aqueous solution, Kao Corp.) 2.00 parts, TamolPP (BASF Japan Ltd.) 1.00 parts, New Coal 710 (Nippon Emulsifier Co., Ltd.) 0.30 parts, Ethylene glycol 5 0.000 part, 0.8N part of 0.6N hydrochloric acid and 34.55 parts of water were mixed, and this mixture was mixed with a rotor using a wet pulverizer Attritor MA-1NS type filled with 17 kg of 4.76 mmφ steel balls. The slurry was pulverized at a rotation speed of 200 rpm for 18 minutes to obtain a slurry.
[0071]
To 92.00 parts of the resulting slurry, 4.33 parts of a 1% aqueous solution of Rhodopol 23 (Rhone-Poulein Co., Ltd.), 5.47 parts of a 5% aqueous dispersion of Kunipia F (Kunimine Industries Co., Ltd.) and Proxel 0.20 part of GXL (Zeneca Co., Ltd.) was added, and the whole amount was stirred and mixed using a three-one motor (1200G, HEIDON Co., Ltd.). Bensulfuron methyl 2.30%, Cavenstrol 9.20%, An aqueous suspension herbicidal composition (flowable) containing 16.70% Daimlon and 20.00% bromobutide was obtained.
[0072]
[Example 8]
Aqueous suspension herbicidal composition (500 ml / 10a treated preparation)
1.40 parts of bensulfuron methyl base, 12.00 parts of pyributicarb base, 0.12 part of Surfinol 104E (Nissin Chemical Industry Co., Ltd.), KP-1436 (25% aqueous solution, Kao Co., Ltd.) 20 parts and 15.28 parts of water were mixed, and 2.5 kg of this mixture was used for 60 minutes at a rotor rotational speed of 200 rpm using a wet crusher Atreiter MA-1NS type filled with 17 kg of 4.76 mmφ steel balls. Crushing to obtain a slurry.
[0073]
To 30.00 parts of the obtained slurry, 2.00 parts of TamolPP (BASF Japan Co., Ltd.), 0.30 parts of New Coal 714F (Nippon Emulsifier Co., Ltd.), 5 propylene glycol (Mitsui Toatsu Chemical Co., Ltd.) 0.000 parts, 1% aqueous solution of Rhodopol 23 (Rhone-Poulein Co., Ltd.) 3.00 parts, Agrisol FL100F (31% aqueous solution of acrylic acid derivative, Kao Co., Ltd.) 20.00 parts, Proxel GXL (Zeneca ( Ltd.) 0.20 part, 0.35 part of 4% sodium hydroxide aqueous solution and 39.15 part of water were added, and the whole amount was stirred and mixed using a three-one motor (1200G, manufactured by HEIDON Co., Ltd.). An aqueous suspended herbicidal composition (flowable) containing 1.40% of ruflon methyl and 12.00% of pyributycarb was obtained.
[0074]
[Test Example 1]
Stability test of sulfonylurea herbicidal active ingredients with surfactants over time
Bensulfuron methyl drug substance (95%) 5.40 parts, Pyributicarb drug substance (98.8%) 42.51 parts, Surfynol 104E (Nisshin Chemical Industry Co., Ltd.) 0.40 part, KP-1436 (25 % Aqueous solution, Kao Co., Ltd. (4.00 parts) and water (47.69 parts) were mixed, and 2.5 kg of this mixture was used in a wet crusher attritor MA-1NS type filled with 4.76 mmφ steel balls (17 kg). Then, it was pulverized for 60 minutes at a rotor rotational speed of 200 rpm to obtain a slurry (hereinafter referred to as slurry A).
[0075]
To the obtained slurry A, 30.00 parts, 2.00 parts (pure component) of the surfactant shown in Table 1 below, 0.10 parts of New Coal 710 (Nippon Emulsifier Co., Ltd.), ethylene glycol (Mitsui Toatsu) Chemical Co., Ltd.) 5.00 parts, Rhodopol 23 1% aqueous solution (Rhone-Poulenc Co., Ltd.) 3.00 parts, Kunipia F 5% aqueous dispersion (Kunimine Industries Co., Ltd.) 20.00 parts, Proxel GXL (Zeneca Co., Ltd.) 0.20 part and water are added and mixed, 0.6N hydrochloric acid is added to adjust the pH of the mixture to 7.5, and the remainder of the water is added to add 1. An aqueous suspension herbicidal composition (flowable) containing 54% and 12.60% pilibutycarb was obtained.
[0076]
The obtained aqueous suspension herbicidal composition was stored in a thermostat at 40 ° C. for 90 days. The content of bensulfuron methyl in the aqueous suspension before and after aging was quantified by liquid chromatography, and the change with time was evaluated. The results are shown in Table 1 below as the residual rate of bensulfuron methyl after aging.
[0077]
[Table 1]

In the case of using the phenolsulfonic acid sodium salt condensate of the present invention, the decomposition of bensulfuron methyl was hardly observed, but in the case of using other surfactants, the decomposition was about 10% or more. It was.
[0078]
[Test Example 2]
Residual rate test of bensulfuron methyl by pH
Slurry A was obtained in the same manner as in Test Example 1, and 2.00 parts of TamolPP, 0.10 parts of New Coal 710 (Nippon Emulsifier Co., Ltd.), ethylene glycol (Mitsui Toatsu Chemical Co., Ltd.) were obtained. )) 5.00 parts, 1% aqueous solution of Rhodopol 23 (Rhone-Poulein Co., Ltd.) 3.00 parts, 5% aqueous dispersion of Kunipia F (Kunimine Industries Co., Ltd.) 20.00 parts, Proxel GXL (Zeneca) Ltd.) 0.20 parts and water were added and mixed, and 0.6N hydrochloric acid was added to adjust the pH of the mixture to 6.0, 6.5, 7.1, 7.5 and 8.0. Furthermore, an aqueous suspension herbicidal composition (flowable) containing 1.54% bensulfuron methyl and 12.60% pyributycarb was obtained by adding water residue.
[0079]
The obtained aqueous suspension herbicidal composition was stored in a thermostat at 50 ° C., and the change over time for 14 days was evaluated in the same manner as in Test Example 1. As a result, the residual ratio of bensulfuron methyl after aging is shown in Table 2 below.
[0080]
[Table 2]

[0081]
[Test Example 3]
Dispersibility test in water with surfactants
Bensulfuron methyl drug substance (97.0%) 3.78 parts, Pyributicarb drug substance (96.8%) 43.39 parts, Surfynol 104E (Nisshin Chemical Industry Co., Ltd.) 0.17 parts, KP-1436 (25% aqueous solution, Kao Co., Ltd.) 4.00 parts and 48.66 parts of water were mixed, 2.5 kg of this mixture was filled with 17 kg of steel balls of 4.76 mmφ, Attritor MA-1NS type Was used for 60 minutes at a rotor rotation speed of 200 rpm to obtain a slurry.
[0082]
To 30.00 parts of the obtained slurry, 0.1 to 3.0 parts of the surfactant shown in Table 4 below, 0.50 parts of TamolPP (BASF Japan Ltd.), ethylene glycol (Mitsui Toatsu Chemicals ( Ltd.) 5.00 parts, 1% aqueous solution of Rhodopol 23 (Rhone-Poulein Co., Ltd.) 5.00 parts, 1% aqueous dispersion of Welan Gum (Sanki Co., Ltd.), Proxel GXL (Zeneca) Ltd.) 0.20 part and water were added and mixed, adjusted to pH 7.5 with 0.6N hydrochloric acid, and the remaining water was further added to obtain 1.10% bensulfuron methyl and 12.60% pyributycarb. An aqueous suspension herbicidal composition (flowable) was obtained.
[0083]
The obtained aqueous suspension herbicidal composition was dropped on the water surface in accordance with the method for water dispersibility test described below, and the dispersibility of the aqueous suspension herbicidal composition in water was compared. Evaluation was made by visual inspection according to the following test method, and the dispersion index in water was determined and shown in Table 4 below.
[0084]
(Method of water dispersibility test)
When water is added, 1 ml of flowable is dripped with a syringe from about 10 cm above the surface of the water with a syringe. After dropping, the fan (wind speed 2 m / sec at the pouring point) is turned on. The dispersion state of the flowable is visually evaluated for the items shown in Table 3 below. The sum of the scores of these four items is the underwater dispersion index, and those with a total score of 9 or more are accepted. An outline of the test method for the dispersibility test in water is shown in FIG.
[0085]
[Table 3]

[0086]
[Table 4]

The composition of the surfactant in the table is as follows: New Coal PB60: Polyoxyethylene bisstyryl phenyl ether; New Coal 610: Polyoxyethylene distyrenated phenyl ether; New Coal 704: Polyoxyethylene distyrenated methyl phenyl ether New Coal 707: Polyoxyethylene distyrenated methyl phenyl ether; New Coal 710: Polyoxyethylene distyrenated methyl phenyl ether; New Coal 714F: Polyoxyalkylene distyrenated methyl phenyl ether; New Coal 2607: Polyoxyethylene Tristyrenated methyl phenyl ether.
[0087]
All the flowables using polyoxyalkylene styryl phenyl ether as the surfactant obtained an evaluation of 9 points or more.
[0088]
[Test Example 4]
Aging stability test of aqueous suspension herbicidal composition (active ingredient stability test)
The aqueous suspension herbicidal compositions of Examples 1 to 8 were stored in a thermostat at 40 ° C., and the stability of the active ingredients after 90 days was evaluated in the same manner as in Test Example 1. The results are shown in Table 5 below as the residual rate of the sulfonylurea active ingredient.
[0089]
[Table 5]
Active ingredient stability test
───────────────────────
Test preparation Bensulfuron methyl remaining rate (%)
───────────────────────
Example 1 99.1%
Example 2 99.0%
Example 3 99.5%
Example 4 99.0%
Example 5 99.1%
Example 6 99.5%
Example 7 99.2%
Example 8 99.5%
───────────────────────
Bensulfuron methyl in the aqueous suspension herbicidal compositions of these examples was extremely stable and hardly decomposed even after storage at 40 ° C. for 90 days.
[0090]
[Test Example 5]
Time stability test of aqueous suspension herbicidal composition (physical stability test)
The aqueous suspension herbicidal compositions of Examples 3 to 8 were stored in a thermostat at 40 ° C., and the physical stability after 90 days was measured. An ordinary method was used for the measurement of physical properties. The results are shown in Table 6 below.
[0091]
[Table 6]

The physical properties of the flowables of these examples were extremely stable, and almost no deterioration was observed after storage at 40 ° C. for 90 days.
[0092]
【The invention's effect】
The aqueous suspension herbicidal composition containing the sulfonylurea pesticidal active ingredient of the present invention is remarkably suppressed from degradation over time and physical deterioration, and can have a stable preparation.
[Brief description of the drawings]
FIG. 1 is an outline of a test method for a dispersibility test in water.

Claims (9)

A stabilized aqueous suspension herbicidal composition comprising one or more sulfonylurea herbicidal active ingredients and a sodium or potassium salt of phenolsulfonic acid or a formalin condensate thereof as active ingredients object.   The aqueous suspension herbicidal composition according to claim 1, wherein the pH of the aqueous suspended herbicidal composition is 4.0 to 8.0.   The aqueous suspension herbicidal composition according to claim 1, wherein the pH of the aqueous suspended herbicidal composition is 6.0 to 8.0.   The aqueous suspension herbicidal composition according to any one of claims 1 to 3, further comprising a styryl phenyl ether condensate.   The aqueous suspension herbicidal composition according to claim 4, wherein the styryl phenyl ether condensate is a polyoxyalkylene styryl phenyl ether.   The aqueous suspension herbicidal composition according to any one of claims 1 to 5, further comprising a herbicidal active ingredient other than the sulfonylurea agrochemical active ingredient.   The aqueous suspension herbicidal composition according to claim 6, wherein the sulfonylurea herbicidal active ingredient is bensulfuron methyl, azimusulfuron, ethoxysulfuron, imazosulfuron, pyrazosulfuronethyl, sinosulfuron, or cyclosulfamuron. The aqueous suspension herbicidal composition according to any one of claims 1 to 7 , wherein the aqueous suspension herbicidal composition has a dispersion index in water of 9 or more. The method to apply the aqueous suspension herbicidal composition in any one of Claims 1 thru | or 8 directly to a paddy field.

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