JP2009084180A - Aqueous suspension-type herbicide composition for water surface scattering - Google Patents

Aqueous suspension-type herbicide composition for water surface scattering Download PDF

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JP2009084180A
JP2009084180A JP2007254160A JP2007254160A JP2009084180A JP 2009084180 A JP2009084180 A JP 2009084180A JP 2007254160 A JP2007254160 A JP 2007254160A JP 2007254160 A JP2007254160 A JP 2007254160A JP 2009084180 A JP2009084180 A JP 2009084180A
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aqueous suspension
herbicide composition
specific gravity
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Shoji Okada
昭二 岡田
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous suspension-type herbicide composition for water surface scattering, having excellent properties in the diffusivity on the water surface or the like. <P>SOLUTION: The aqueous suspension-type herbicide composition for the water surface scattering comprises at least one kind of compounds solid at normal temperature and having herbicidal activity, a specific gravity regulator, a surface-active component, a thickening component, an antifoaming agent and water, wherein the surface-active component contains an ionic surface-active component and a nonionic surface-active component having >15 HLB value. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

本発明は、水面散布用の水性懸濁状除草剤組成物に関する。   The present invention relates to an aqueous suspension herbicide composition for spraying water.

従来、湛水下水田等の水面への除草剤散布としては、一般に粒剤による散布が中心に行われていた。しかしながら、粒剤による散布は、例えば10アールあたりの3キログラム程度の多量の散布量を必要とし、且つ、広い水田に均等に散布する必要があるなどの労力面での負担が大きいこともあり、より簡便に除草活性化合物を施用できる製剤化技術の提供が求められていた。
かかる課題の解決手段の一つとして、常温で固体の除草活性化合物を含有し、且つ、有機若しくは無機中空担体やイソパラフィン系炭化水素を比重調節剤として含有することにより比重が軽減されてなる水性懸濁状除草剤組成物を、湛水下水田等の水面に散布し速やかに水面上で拡散させることにより、常温で固体の除草活性化合物の薬効を水田全面で発現させる方法が提供されている(例えば、特許文献1参照。)。
しかしながら、かかる水性懸濁状除草剤組成物は、必ずしも十分に満足できる水面上での拡散性を有するものではなく、より優れた性能を有する水性懸濁状除草剤組成物の提供が求められている。
Conventionally, as a herbicide spraying on the surface of a flooded sewage paddy field or the like, generally spraying with a granule has been mainly performed. However, spraying with granules requires a large amount of spraying, for example, about 3 kilograms per 10 ares, and it may be burdensome in terms of labor, such as evenly spraying over a wide paddy field, There has been a demand for provision of a formulation technique that can more easily apply the herbicidal active compound.
As one means for solving such a problem, an aqueous suspension comprising a herbicidal active compound that is solid at room temperature and a specific gravity reduced by containing an organic or inorganic hollow carrier or isoparaffin hydrocarbon as a specific gravity regulator. There is provided a method for expressing a medicinal effect of a herbicidal active compound that is solid at room temperature on the entire surface of a paddy field by spraying a turbid herbicide composition on the surface of a submerged paddy field and quickly diffusing on the surface of the water ( For example, see Patent Document 1.)
However, such an aqueous suspension herbicide composition does not necessarily have a sufficiently satisfactory diffusivity on the water surface, and there is a demand for providing an aqueous suspension herbicide composition having superior performance. Yes.

特開2001−106601号公報JP 2001-106601 A

本発明は、水面上での拡散性などにおいて優れた性能を有する水性懸濁状除草剤組成物を提供することを課題とする。   An object of the present invention is to provide an aqueous suspension herbicide composition having excellent performance in terms of diffusibility on the water surface.

本発明者は、優れた性能を有する水性懸濁状除草剤組成物を提供すべく検討の結果、特定の界面活性成分を含有する水性懸濁状除草剤組成物が優れた性能を有することを見出し、本発明に至った。
すなわち、本発明は以下の〔1〕〜〔9〕の通りである。
〔1〕 少なくとも1種の常温で固体の除草活性化合物、比重調節剤、界面活性成分、増粘性成分、消泡剤及び水を含有する水面散布用水性懸濁状除草剤組成物であって、
界面活性成分として、イオン性界面活性成分及びHLB値が15より大きい非イオン性界面活性成分を含有することを特徴とする水性懸濁状除草剤組成物。
〔2〕 比重が0.90以上1.05以下であり、且つ、粘度が600〜1200mPa・sである〔1〕記載の水性懸濁状除草剤組成物。
〔3〕 非イオン性界面活性成分のHLB値が、15.5以上20以下である〔1〕又は〔2〕記載の水性懸濁状除草剤組成物。
〔4〕 非イオン性界面活性成分の少なくとも1種が、HLB値が15.5以上20以下であるショ糖脂肪酸エステルである〔1〕〜〔3〕いずれか一項記載の水性懸濁状除草剤組成物。
〔5〕 イオン性界面活性成分が、ポリオキシエチレントリスチリルフェニルエーテルリン酸エステル塩である〔1〕〜〔4〕いずれか一項記載の水性懸濁状除草剤組成物。
〔6〕 比重調節剤が、無機中空担体、有機中空担体及びパラフィン系炭化水素からなる群より選ばれる少なくとも1種である〔1〕〜〔5〕いずれか一項記載の水性懸濁状除草剤組成物。
〔7〕 比重調節剤が、パラフィン系炭化水素である〔1〕〜〔5〕いずれか一項記載の水性懸濁状除草剤組成物。
〔8〕 常温で固体の除草活性化合物の少なくとも1種が、常温で固体のスルホニル尿素系除草活性化合物である〔1〕〜〔7〕いずれか一項記載の水性懸濁状除草剤組成物。
〔9〕 さらに防腐剤を含有する〔1〕〜〔8〕いずれか一項記載の水性懸濁状除草剤組成物。
As a result of studies to provide an aqueous suspension herbicide composition having excellent performance, the present inventor has found that an aqueous suspension herbicide composition containing a specific surfactant component has excellent performance. The headline, the present invention has been reached.
That is, the present invention is as follows [1] to [9].
[1] An aqueous suspension herbicide composition for spraying on the water surface comprising at least one herbicidal active compound that is solid at room temperature, a specific gravity regulator, a surface active component, a thickening component, an antifoaming agent and water,
An aqueous suspension herbicide composition comprising an ionic surfactant component and a nonionic surfactant component having an HLB value greater than 15 as the surfactant component.
[2] The aqueous suspension herbicide composition according to [1], wherein the specific gravity is 0.90 or more and 1.05 or less and the viscosity is 600 to 1200 mPa · s.
[3] The aqueous suspension herbicide composition according to [1] or [2], wherein the HLB value of the nonionic surfactant component is 15.5 or more and 20 or less.
[4] The aqueous suspension herbicide according to any one of [1] to [3], wherein at least one of the nonionic surfactant components is a sucrose fatty acid ester having an HLB value of 15.5 or more and 20 or less. Agent composition.
[5] The aqueous suspension herbicide composition according to any one of [1] to [4], wherein the ionic surfactant component is polyoxyethylene tristyryl phenyl ether phosphate ester salt.
[6] The aqueous suspension herbicide according to any one of [1] to [5], wherein the specific gravity regulator is at least one selected from the group consisting of an inorganic hollow carrier, an organic hollow carrier, and a paraffinic hydrocarbon. Composition.
[7] The aqueous suspension herbicide composition according to any one of [1] to [5], wherein the specific gravity regulator is a paraffinic hydrocarbon.
[8] The aqueous suspension herbicidal composition according to any one of [1] to [7], wherein at least one herbicidal active compound that is solid at normal temperature is a sulfonylurea herbicidal active compound that is solid at normal temperature.
[9] The aqueous suspension herbicide composition according to any one of [1] to [8], further comprising a preservative.

本発明により、湛水下水田等の水面に散布した場合に、十分な水面上での拡散性が付与されてなる、常温で固体の除草活性化合物を含有する水性懸濁状除草剤組成物を提供することができる。   According to the present invention, an aqueous suspension herbicide composition containing a herbicidal active compound that is solid at room temperature, imparted with sufficient diffusibility on the water surface when sprayed on the surface of a flooded sewage paddy field or the like. Can be provided.

本発明の水面散布用の水性懸濁状除草剤組成物は、少なくとも1種の常温で固体の除草活性化合物、比重調節剤、界面活性成分、増粘性成分、消泡剤及び水を含有する水面散布用水性懸濁状除草剤組成物であって、界面活性成分として、イオン性界面活性成分及びHLB値が15より大きい非イオン性界面活性成分を含有することを特徴とするものである。   The aqueous suspension herbicide composition for spraying on the water surface of the present invention comprises at least one herbicidal active compound that is solid at room temperature, a specific gravity regulator, a surface active component, a thickening component, an antifoaming agent and water. An aqueous suspension herbicide composition for spraying, characterized in that it contains an ionic surfactant component and a nonionic surfactant component having an HLB value greater than 15 as the surfactant component.

本発明の水性懸濁状除草剤組成物に含有される常温で固体の除草活性化合物とは、20℃において固体である除草活性化合物であり、例えばスルホニル尿素系除草活性化合物が挙げられ、具体的には以下のものが挙げられる。
2,4,6−トリクロルフェニル−4’−ニトロフェニルエーテル(CNP);
α−(2−ナフトキシ)プロピオンアニリド(ナプロアニリド);
5−(2,4−ジクロロフェノキシ)−2−ニトロ安息香酸メチル(ビフェノックス);
O−3−tert−ブチルフェニル=6−メトキシ−2−ピリジル(メチル)チオカルバマート(ピリブチカルブ);
(RS)−2−ブロモ−N−(α,α−ジメチルベンジル)−3,3−ジメチルブチルアミド(ブロモブチド);
2−ベンゾチアゾール−2−イルオキシ−N−メチルアセトアニリド(メフェナセット);
1−(α,α−ジメチルベンジル)−3−(パラトリル)尿素(ダイムロン);
メチル=α−(4,6−ジメトキシピリミジン−2−イルカルバモイルスルファモイル)−O−トルアート(ベンスルフロンメチル);
1−(2−クロロイミダゾ[1,2−a]ピリジン−3−イルスルホニル)−3−(4,6−ジメトキシピリミジン−2−イル)尿素(イマゾスルフロン);
エチル=5−(4,6−ジメトキシピリミジン−2−イルカルバモイルスルファモイル)−1−メチルピラゾール−4−カルボキシラート(ピラゾスルフロンエチル);
2−メチルチオ−4,6−ビス(エチルアミノ)−s−トリアジン(シメトリン);
2−メチルチオ−4,6−ビス(イソプロピルアミノ)−s−トリアジン(プロメトリン);
2−メチルチオ−4−エチルアミノ−6−(1,2−ジメチルプロピルアミノ)−s−トリアジン(ジメタメトリン);
2,4−ジクロロフェニル−3’−メトキシ−4’−ニトロフェニルエーテル(クロメトキシニル);
5−ターシャリーブチル−3−(2,4−ジクロロ−5−イソプロポキシフェニル)−1,3,4−オキサジアゾリン−2−オン(オキサジアゾン);
4−(2,4−ジクロロベンゾイル)−1,3−ジメチル−5−ピラゾリル−p−トルエンスルホネート(ピラゾレート);
2−[4−(2,4−ジクロロベンゾイル)−1,3−ジメチルピラゾール−5−イルオキシ]アセトフェノン(ピラゾキシフェン);
(RS)−2−(2,4−ジクロロ−m−トリルオキシ)プロピオンアニリド(クロメプロップ);
2−[4−[2,4−ジクロロ−m−トルオイル]−1,3−ジメチルピラゾール−5−イルオキシ]−4’−メチルアセトフェノン(ベンゾフェナップ);
2−クロロ−N−(3−メトキシ−2−テニル)−2’,6’−ジメチルアセトアニリド(テニルクロール);
3−[1−(3,5−ジクロルフェニル)−1−メチルエチル]−2,3−ジヒドロ−6−メチル−5−フェニル−4H−1,3−オキサジン−4−オン(オキサジクロメホン);
3−(4−クロロ−5−シクロペンチルオキシ−2−フルオロフェニル)−5−イソプロピリデン−1,3−オキサゾリジン−2,4−ジオン(ペントキサゾン);
1−(ジエチルカルバモイル)−3−(2,4,6−トリメチルフェニルスルホニル)−1,2,4−トリアゾール(カフェンストロール);
N−{[(4,6−ジメトキシピリミジン−2−イル)アミノカルボニル]}−1−メチル−4−(2−メチル−2H−テトラゾール−5−イル)(アジムスルフロン);
メチル 2−[(4,6−ジメトキシピリミジン−2−イル)オキシ]−6−[(E)−1−(メトキシイミノ)エチル]ベンゾエート(ピリミノバックメチル);
4−(2−クロロフェニル)−N−シクロへキシル−N−エチル−4,5−ジヒドロ−5−オキソ−1H−テトラゾール−1−カルボキサミド(フェントラザミド);
ナトリウム=N−(ホスホノメチル)グリシナート(グリホサートナトリウム塩);
トリメシウム=N−(ホスホノメチル)グリシナート(グリホサートトリメシウム塩);
アンモニウム=N−(ホスホノメチル)グリシナート(グリホサートアンモニウム塩);
イソプロピルアミン=N−(ホスホノメチル)グリシナート(グリホサートイソプロピルアミン塩);
L−2−アミノ−4−[(ヒドロキシ)(メチル)ホスフィノイル]ブチリル−L−アラニル−L−アラニンナトリウム塩(ビアラホス);
アンモニウム=DL−ホモアラニン−4−イル(メチル)ホスフィナート(グルホシネート);及び
ナトリウム=2,6−ビス[(4,6−ジメトキシピリミジン−2−イル)オキシ]ベンゾエート(ビスピリバックナトリウム塩)。
The herbicidal active compound that is solid at room temperature contained in the aqueous suspension herbicidal composition of the present invention is a herbicidal active compound that is solid at 20 ° C., and examples thereof include sulfonylurea herbicidal active compounds. Include the following:
2,4,6-trichlorophenyl-4′-nitrophenyl ether (CNP);
α- (2-naphthoxy) propionanilide (naproanilide);
Methyl 5- (2,4-dichlorophenoxy) -2-nitrobenzoate (biphenox);
O-3-tert-butylphenyl = 6-methoxy-2-pyridyl (methyl) thiocarbamate (pyributycarb);
(RS) -2-bromo-N- (α, α-dimethylbenzyl) -3,3-dimethylbutyramide (bromobutide);
2-benzothiazol-2-yloxy-N-methylacetanilide (mefenacet);
1- (α, α-dimethylbenzyl) -3- (paratolyl) urea (Dimron);
Methyl = α- (4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl) -O-toluate (bensulfuronmethyl);
1- (2-chloroimidazo [1,2-a] pyridin-3-ylsulfonyl) -3- (4,6-dimethoxypyrimidin-2-yl) urea (imazosulfuron);
Ethyl = 5- (4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl) -1-methylpyrazole-4-carboxylate (pyrazolsulfuronethyl);
2-methylthio-4,6-bis (ethylamino) -s-triazine (cimetrine);
2-methylthio-4,6-bis (isopropylamino) -s-triazine (promethrin);
2-methylthio-4-ethylamino-6- (1,2-dimethylpropylamino) -s-triazine (dimetamethrin);
2,4-dichlorophenyl-3'-methoxy-4'-nitrophenyl ether (clomethoxynil);
5-tertiarybutyl-3- (2,4-dichloro-5-isopropoxyphenyl) -1,3,4-oxadiazolin-2-one (oxadiazone);
4- (2,4-dichlorobenzoyl) -1,3-dimethyl-5-pyrazolyl-p-toluenesulfonate (pyrazolate);
2- [4- (2,4-dichlorobenzoyl) -1,3-dimethylpyrazol-5-yloxy] acetophenone (pyrazoxifene);
(RS) -2- (2,4-dichloro-m-tolyloxy) propionanilide (chromeprop);
2- [4- [2,4-dichloro-m-toluoyl] -1,3-dimethylpyrazol-5-yloxy] -4′-methylacetophenone (benzophenap);
2-chloro-N- (3-methoxy-2-enyl) -2 ′, 6′-dimethylacetanilide (tenyl chlor);
3- [1- (3,5-dichlorophenyl) -1-methylethyl] -2,3-dihydro-6-methyl-5-phenyl-4H-1,3-oxazin-4-one (oxadichromemephone);
3- (4-chloro-5-cyclopentyloxy-2-fluorophenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione (pentoxazone);
1- (diethylcarbamoyl) -3- (2,4,6-trimethylphenylsulfonyl) -1,2,4-triazole (cafentrol);
N-{[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl]}-1-methyl-4- (2-methyl-2H-tetrazol-5-yl) (azimylsulfuron);
Methyl 2-[(4,6-dimethoxypyrimidin-2-yl) oxy] -6-[(E) -1- (methoxyimino) ethyl] benzoate (pyriminobacmethyl);
4- (2-chlorophenyl) -N-cyclohexyl-N-ethyl-4,5-dihydro-5-oxo-1H-tetrazole-1-carboxamide (fentrazamide);
Sodium = N- (phosphonomethyl) glycinate (glyphosate sodium salt);
Trimesium = N- (phosphonomethyl) glycinate (glyphosate trimesium salt);
Ammonium = N- (phosphonomethyl) glycinate (glyphosate ammonium salt);
Isopropylamine = N- (phosphonomethyl) glycinate (glyphosate isopropylamine salt);
L-2-amino-4-[(hydroxy) (methyl) phosphinoyl] butyryl-L-alanyl-L-alanine sodium salt (bialaphos);
Ammonium = DL-homoalanin-4-yl (methyl) phosphinate (glufosinate); and sodium = 2,6-bis [(4,6-dimethoxypyrimidin-2-yl) oxy] benzoate (bispyribac sodium salt).

本発明の水性懸濁状除草剤組成物には、常温で固体の除草活性化合物が通常0.1〜50重量パーセント、好ましくは0.5〜30重量パーセント程度含有される。   In the aqueous suspension herbicide composition of the present invention, the herbicidal active compound that is solid at room temperature is usually contained in an amount of 0.1 to 50 percent by weight, preferably about 0.5 to 30 percent by weight.

本発明の水性懸濁状除草剤組成物には、本発明の効果を損なわない範囲で常温で固体の除草活性化合物とともに、常温で液体の除草剤活性化合物、並びに、常温で固体若しくは液体の殺虫活性化合物及び殺菌活性化合物等の他の生理活性化合物を含有することもできる。   The aqueous suspension herbicide composition of the present invention includes herbicidally active compounds that are solid at room temperature as long as the effects of the present invention are not impaired, herbicide active compounds that are liquid at room temperature, and insecticides that are solid or liquid at room temperature Other physiologically active compounds such as active compounds and bactericidal active compounds can also be contained.

本発明の水性懸濁状除草剤組成物に含有される比重調節剤とは、比重が1未満である固体担体で、本発明の水性懸濁状除草剤組成物自体の比重を軽減させることにより、本発明の水性懸濁状除草剤組成物の比重を1.05以下、好ましくは0.90〜1.05程度に調節でき得る担体であれば特に限定するものではない。   The specific gravity regulator contained in the aqueous suspension herbicide composition of the present invention is a solid carrier having a specific gravity of less than 1, and by reducing the specific gravity of the aqueous suspension herbicide composition itself of the present invention. The carrier is not particularly limited as long as the specific gravity of the aqueous suspension herbicide composition of the present invention can be adjusted to 1.05 or less, preferably about 0.90 to 1.05.

かかる比重調節剤としては、例えば、発泡パーライト、発泡シラス、発泡珪酸ソーダ、発泡ホウ珪酸ソーダ等のガラス質中空体及びセラミック中空体などの無機中空担体、プラスチック中空体などの有機中空担体、ポリエチレン粉末やポリプロピレン粉末等の樹脂粉末、木粉、コルク粉、パラフィン系炭化水素等が挙げられ、好ましくは、無機中空担体、有機中空担体等の固体中空担体及びパラフィン系炭化水素が挙げられる。
かかる比重調節剤のうち、パラフィン系炭化水素としては、常温で不揮発性である点、及び、臭気等の点からは炭素数7〜13の液状のノルマルパラフィンが好ましい。また、かかる比重調節剤が固体である場合、その平均粒径が通常100μm以下、好ましくは50μm以下であるものが用いられる。
本発明の水性懸濁状除草剤組成物には、比重調節剤が通常3〜30重量%、好ましくは5〜20重量%程度含有される。
Examples of the specific gravity adjusting agent include inorganic hollow carriers such as glassy hollow bodies and ceramic hollow bodies such as foamed perlite, foamed shirasu, foamed sodium silicate and foamed borosilicate soda, organic hollow carriers such as plastic hollow bodies, polyethylene powder, and the like. And resin powders such as polypropylene powder, wood powder, cork powder, paraffinic hydrocarbons and the like, preferably solid hollow carriers such as inorganic hollow carriers and organic hollow carriers, and paraffinic hydrocarbons.
Among such specific gravity regulators, the paraffinic hydrocarbon is preferably a liquid normal paraffin having 7 to 13 carbon atoms from the viewpoint of non-volatility at room temperature and odor. Further, when the specific gravity regulator is a solid, those having an average particle size of usually 100 μm or less, preferably 50 μm or less are used.
In the aqueous suspension herbicidal composition of the present invention, a specific gravity regulator is usually contained in an amount of about 3 to 30% by weight, preferably about 5 to 20% by weight.

本発明の水性懸濁状除草剤組成物には、界面活性成分としてイオン性界面活性成分及びHLB値が15より大きい非イオン性界面活性成分が含有される。   The aqueous suspension herbicidal composition of the present invention contains an ionic surfactant component and a nonionic surfactant component having an HLB value greater than 15 as the surfactant component.

かかる界面活性成分のうち、イオン性界面活性成分としては、例えば、リグニンスルホン酸塩、アルキルアリールスルホン酸塩、ジアルキルスルホサクシネート、ポリオキシエチレンアルキルアリールホスフェート、ポリオキシエチレンアルキルアリールエーテルサルフェート、アルキルナフタレンスルホン酸塩、ポリオキシエチレンスチリルフェニルエーテルサルフェート及びポリオキシエチレントリスチリルフェニルエーテルリン酸エステル塩等のアニオン性界面活性成分が挙げられる。   Among such surfactant components, examples of the ionic surfactant component include lignin sulfonate, alkylaryl sulfonate, dialkyl sulfosuccinate, polyoxyethylene alkylaryl phosphate, polyoxyethylene alkylaryl ether sulfate, and alkylnaphthalene. Anionic surface active components such as sulfonate, polyoxyethylene styryl phenyl ether sulfate, and polyoxyethylene tristyryl phenyl ether phosphate ester salt may be mentioned.

界面活性成分のうち、HLB値が15より大きい非イオン性界面活性成分としては、例えば、ショ糖脂肪酸エステルが挙げられる。ショ糖脂肪酸エステルとしては、例えばニューカルゲンFS−30(竹本油脂社製、商品名、HLB値 16)が挙げられる。本発明においては、HLB値が15以下である非イオン性界面活性成分であっても、HLB値が15より大きい非イオン性界面活性成分との組合わせにより、非イオン性界面活性成分の全体のHLB値が15より大きい値、例えば15.5以上20以下程度となるものであれば本発明に用いることができる。   Among the surfactant components, examples of the nonionic surfactant component having an HLB value greater than 15 include sucrose fatty acid esters. Examples of the sucrose fatty acid ester include New Calgen FS-30 (manufactured by Takemoto Yushi Co., Ltd., trade name, HLB value 16). In the present invention, even if a nonionic surfactant component having an HLB value of 15 or less is combined with a nonionic surfactant component having an HLB value of greater than 15, the entire nonionic surfactant component is Any HLB value greater than 15, for example, about 15.5 or more and 20 or less can be used in the present invention.

本発明の水性懸濁状除草剤組成物には、HLB値が15より大きい非イオン性界面活性成分が通常0.1〜10重量%、好ましくは0.5〜3重量%程度含有され、また、界面活性成分が合計量で通常0.1〜20重量%、好ましくは0.5〜10重量%程度含有される。   In the aqueous suspension herbicidal composition of the present invention, a nonionic surfactant component having an HLB value greater than 15 is usually contained in an amount of about 0.1 to 10% by weight, preferably about 0.5 to 3% by weight. The surfactant component is contained in a total amount of usually 0.1 to 20% by weight, preferably about 0.5 to 10% by weight.

本発明の水性懸濁状除草剤組成物に含有される増粘性成分としては、有機系増粘性成分及び無機系増粘性成分が挙げられ、詳しくは、キサンタンガム、グアガム、アラビアガム、カゼイン、デキストリン、カルボキシメチルセルロース、カルボキシメチルセルロースナトリウム塩、アルギン酸ナトリウム、ヒドロキシエチルセルロース、カルボキシエチルセルロース、メチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシエチルセルロース、ポリビニルアルコール、ポリアクリル酸とその誘導体、コロイド性含水ケイ酸アルミニウム、コロイド性含水ケイ酸マグネシウム、コロイド性含水ケイ酸アルミニウムマグネシウム等が挙げられる。本発明の水性懸濁状除草剤組成物には、かかる増粘性成分の1種又は2種以上、好ましくは1種以上の有機系増粘性成分及び1種以上の無機系増粘性成分の混合物が含有され、その含有量は特に制限されるものではなく、本発明の水性懸濁状除草剤組成物の粘度が20℃でB型粘度計 No.2ローター、12rpmの測定条件において、通常は100〜1200mPa・s、製造面から好ましくは600〜1200mPa・sとなるように含有されていればよいが、通常は0.01〜10重量パーセント、好ましくは0.1〜5重量パーセント程度の含有量である。   Examples of the thickening component contained in the aqueous suspension herbicide composition of the present invention include an organic thickening component and an inorganic thickening component. Specifically, xanthan gum, guar gum, gum arabic, casein, dextrin, Carboxymethylcellulose, sodium carboxymethylcellulose, sodium alginate, hydroxyethylcellulose, carboxyethylcellulose, methylcellulose, hydroxypropylcellulose, hydroxyethylcellulose, polyvinyl alcohol, polyacrylic acid and its derivatives, colloidal hydrous aluminum silicate, colloidal hydrous magnesium silicate, Examples thereof include colloidal hydrous aluminum magnesium silicate. The aqueous suspension herbicidal composition of the present invention includes a mixture of one or more of these thickening components, preferably one or more organic thickening components and one or more inorganic thickening components. And the content is not particularly limited, and the viscosity of the aqueous suspension herbicide composition of the present invention is 20.degree. In the measurement condition of 2 rotors and 12 rpm, the content is usually 100 to 1200 mPa · s, preferably from 600 to 1200 mPa · s from the production side, but usually 0.01 to 10 weight percent, preferably Is a content of about 0.1 to 5 weight percent.

本発明の水性懸濁状除草剤組成物に含有される消泡剤としては、例えばシリコーン系消泡剤及び脂肪酸系消泡剤が挙げられる。本発明の水性懸濁状除草剤組成物には、かかる消泡剤が通常0.01〜3重量パーセント程度含有される。   As an antifoamer contained in the aqueous suspension herbicide composition of this invention, a silicone type antifoamer and a fatty acid type antifoamer are mentioned, for example. Such an antifoaming agent is usually contained in an aqueous suspension herbicide composition of the present invention in an amount of about 0.01 to 3 weight percent.

本発明の水性懸濁状除草剤組成物には、その分散媒として用いられる水としては、水道水及び地下水のほか、これらをイオン交換した水が挙げられ、特に限定されるものではないが、硬度が3度以下の水が好ましい。   In the aqueous suspension herbicidal composition of the present invention, the water used as the dispersion medium includes tap water and groundwater, as well as water obtained by ion exchange of these, and is not particularly limited. Water with a hardness of 3 degrees or less is preferred.

本発明の水性懸濁状除草剤組成物には、さらに防腐剤を含有することができる。かかる防腐剤としては、例えば、5−クロロ−2−メチル−4−イソチアゾリン−3−オン(CMT)、ソルビン酸、p−クロロ−m−キシレノ−ル、p−オキシ安息香酸ブチル、1,2−ベンゾチアゾリン−3−オン、2−ブロモ−2−ニトロプロパン−1,3−ジオール(BNPK)、2−メチル−4−イソチアゾリン−3−オン(MT)等が挙げられる。本発明の水性懸濁状除草剤組成物には、かかる防腐剤を0.005〜0.1重量パーセント程度含有させることができる。   The aqueous suspension herbicide composition of the present invention may further contain a preservative. Such preservatives include, for example, 5-chloro-2-methyl-4-isothiazolin-3-one (CMT), sorbic acid, p-chloro-m-xylenol, butyl p-oxybenzoate, 1,2 -Benzothiazoline-3-one, 2-bromo-2-nitropropane-1,3-diol (BNPK), 2-methyl-4-isothiazolin-3-one (MT) and the like. The aqueous suspension herbicidal composition of the present invention can contain about 0.005 to 0.1 weight percent of such an antiseptic.

本発明の水性懸濁状除草剤組成物には、さらに必要に応じて凍結防止剤、酸化防止剤、紫外線防止剤及び/又は結晶析出防止剤等を安定化剤として添加することもできる。   If necessary, the aqueous suspension herbicide composition of the present invention may further contain an antifreezing agent, an antioxidant, an ultraviolet ray inhibitor and / or a crystal precipitation inhibitor as a stabilizer.

本発明の水性懸濁状除草剤組成物は、少なくとも1種の常温で固体の除草活性化合物、比重調節剤、増粘性成分、消泡剤、水、イオン性界面活性成分及びHLB値が15より大きい非イオン性界面活性成分と、防腐剤、ならびに、酸化防止剤、紫外線防止剤及び結晶析出防止剤等の安定化剤を用いて得ることができるが、その製造方法は特に限定されるものではない。   The aqueous suspension herbicidal composition of the present invention has at least one herbicidal active compound that is solid at room temperature, a specific gravity regulator, a thickening component, an antifoaming agent, water, an ionic surfactant, and an HLB value of 15 It can be obtained by using a large nonionic surfactant component, a preservative, and a stabilizer such as an antioxidant, an ultraviolet ray inhibitor and a crystal precipitation inhibitor, but its production method is not particularly limited. Absent.

例えば、水にイオン性界面活性成分、消泡剤、必要に応じて凍結防止剤を均一に溶かした後、該溶液に少なくとも1種の常温で固体の除草活性化合物及び増粘性成分、好ましくは無機系増粘性成分を加え、ディスパーミル等により分散させ、スラリー状にしてからビーズミル等で平均粒子径を10μm以下、好ましくは5μm以下となるように微粉砕する。次に微粉砕されたスラリーに比重調節剤を加え、ディスパーミル等により分散させ、次いで、HLB値が15より大きい非イオン性界面活性成分及び増粘性成分、好ましくは有機系増粘性成分と、さらに必要に応じて防腐剤等とを均一に混合することにより、本発明の水性懸濁状除草剤組成物を製造することができる。
かかる製造方法において少なくとも1種の常温で固体の除草活性化合物は、保存安定性や除草活性の面から、予め平均粒子径が通常は10μm以下、好ましくは5μm以下となるように粉砕されたものが用いられる。
For example, after uniformly dissolving an ionic surfactant component, an antifoaming agent and, if necessary, an antifreeze in water, at least one herbicidal active compound and a thickening component, preferably an inorganic component, at room temperature. A system thickening component is added and dispersed by a disper mill or the like, and is then pulverized by a bead mill or the like so as to have an average particle size of 10 μm or less, preferably 5 μm or less. Next, a specific gravity adjusting agent is added to the finely pulverized slurry and dispersed with a disper mill or the like, and then a nonionic surfactant component and a thickening component having an HLB value greater than 15, preferably an organic thickening component, The aqueous suspension herbicidal composition of the present invention can be produced by uniformly mixing an antiseptic or the like as necessary.
In such a production method, at least one kind of herbicidal active compound that is solid at room temperature is preliminarily pulverized so that the average particle size is usually 10 μm or less, preferably 5 μm or less, from the viewpoint of storage stability and herbicidal activity. Used.

本発明の水性懸濁状除草剤組成物は、従来の水性懸濁状除草剤組成物に用いられる公知の施用方法に用いることができる。かかる施用方法は特に限定されるものではないが、例えば、代掻き作業時以降の湛水下水田に、稲の移植前、移植時及び移植後のうち任意の時期に施用することができる。施用方法としては、湛水下水田への滴下処理が挙げられ、本発明の水性懸濁状除草剤組成物をプラスチック製の容器に入れて手振り散布する、或いは、加圧式散布機を用いて本発明の水性懸濁状除草剤組成物を噴射又は噴霧する方法が挙げられ、また、水田の水口で流入水に滴下散布し、流入水と共に水田に流し込む方法も挙げられる。   The aqueous suspension herbicide composition of this invention can be used for the well-known application method used for the conventional aqueous suspension herbicide composition. The application method is not particularly limited. For example, the application method can be applied to a flooded sewage paddy field at or after the pricking operation at any time before, during and after rice transplanting. Examples of the application method include dripping treatment in a flooded sewage paddy field. The aqueous suspension herbicide composition of the present invention is placed in a plastic container and sprayed by hand, or by using a pressurized sprayer. Examples include a method of spraying or spraying the aqueous suspension herbicide composition of the invention, and a method of dropping and spraying the inflowing water at the water inlet of the paddy field and pouring into the paddy field together with the inflowing water.

本発明の水性懸濁状除草剤組成物の施用量は、特に限定されるものではないが、散布省力化の点からは、施用面積10アールあたりの施用量は、通常は1000ml以下、好ましくは100〜500ml程度である。   The application amount of the aqueous suspension herbicide composition of the present invention is not particularly limited, but from the viewpoint of labor saving of application, the application amount per application area of 10 are usually 1000 ml or less, preferably About 100 to 500 ml.

次に、本発明を製造例及び試験例等の実施例により具体的に説明するが、本発明はこれらの例に限定されるものではない。
なお、部とは重量部を示す。
Next, the present invention will be specifically described with reference to examples such as production examples and test examples, but the present invention is not limited to these examples.
In addition, a part shows a weight part.

製剤例1
SUSビーカーにイオン交換水 370.5部、ソプロホールFLK(ローディア日華製、ポリオキシエチレントリスチリルフェニルエーテルリン酸エステルカリウム塩) 30部、凍結防止剤(プロピレングリコール:和光純薬製) 100部及び消泡剤(アンチフォームE−20:花王製) 2.5部を加え、小型撹拌機で均一に分散させた。この分散液に、イマゾスルフロン18部、ブロモブチド80部及び無機系増粘剤(クニピアF:クニミネ工業製)5部を加え、小型オートホモミキサー(特殊機化工業製)で徐々に分散させてスラリー状にして、次いで、ビーズミルであるダイノミル(KDL型:シンマルエンタプライズ製)を用いて2000rpmで粉砕化を行い、平均粒子径3.5μmの粉砕スラリーとした。
この粉砕スラリーに、n−パラフィン(ノルマルウンデカン:ジャパンエナジー製) 180部を加え小型オートホモミキサー(特殊機化工業製)5000rpmで分散させた。次に、予め調製した1%有機系増粘剤液(ケルザンS:三晶製) 200部、ショ糖脂肪酸エステル(ニューカルゲンFS−30:竹本油脂製、HLB値 16) 10部、消泡剤(アンチフォームE−20:花王製)2.5部及び防腐剤(バイオホープL:ケイ・アイ化成製) 1部を加え、小型ミキサーで均一にした。最後にpHメーターでpHを確認しながら予め調製した30%硫酸0.5部を徐々に加え、pHを5.8に合わせ、比重が0.97〜0.99の水性懸濁状除草剤組成物(以下、本発明組成物1と記す。)を得た。
Formulation Example 1
370.5 parts of ion-exchanged water in a SUS beaker, 30 parts of Soprohole FLK (manufactured by Rhodia Nikka, polyoxyethylene tristyryl phenyl ether phosphate potassium salt), 100 parts of antifreezing agent (propylene glycol: Wako Pure Chemical Industries, Ltd.) 2.5 parts of antifoaming agent (Antifoam E-20: manufactured by Kao) was added and dispersed uniformly with a small stirrer. To this dispersion, add 18 parts of imazosulfuron, 80 parts of bromobutide and 5 parts of an inorganic thickener (Kunipia F: manufactured by Kunimine Industries), and gradually disperse them with a small auto homomixer (manufactured by Special Machine Industries) to form a slurry. Then, pulverization was performed at 2000 rpm using a dyno mill (KDL type: manufactured by Shinmaru Enterprise), which is a bead mill, to obtain a pulverized slurry having an average particle diameter of 3.5 μm.
To this pulverized slurry, 180 parts of n-paraffin (normal undecane: manufactured by Japan Energy) was added and dispersed at 5000 rpm with a small auto homomixer (manufactured by Special Machine Industries). Next, 200 parts of 1% organic thickener liquid (Kelzan S: made by Sanki) prepared in advance, 10 parts of sucrose fatty acid ester (New Calgen FS-30: made by Takemoto Yushi, HLB value 16), 10 parts, antifoaming agent (Antifoam E-20: manufactured by Kao) 2.5 parts and 1 part of an antiseptic (Biohope L: manufactured by Kay Chemical Co., Ltd.) were added and homogenized with a small mixer. Finally, 0.5 parts of 30% sulfuric acid prepared in advance was gradually added while checking the pH with a pH meter, the pH was adjusted to 5.8, and the aqueous suspension herbicide composition having a specific gravity of 0.97 to 0.99 A product (hereinafter referred to as the present composition 1) was obtained.

製剤例2
SUSビーカーにイオン交換水 480.5部、ソプロホールFLK(ローディア日華製、ポリオキシエチレントリスチリルフェニルエーテルリン酸エステルカリウム塩) 30部、凍結防止剤(プロピレングリコール:和光純薬製) 100部及び消泡剤(アンチフォームE−20:花王製) 2.5部を加え、小型撹拌機で均一に分散させた。この分散液に、イマゾスルフロン18部、ブロモブチド80部及び無機系増粘剤(クニピアF:クニミネ工業製)5部を加え、小型オートホモミキサー(特殊機化工業製)で徐々に分散させてスラリー状にして、次いで、ビーズミルであるダイノミル(KDL型:シンマルエンタプライズ製)を用いて2000rpmで粉砕化を行い、平均粒子径3.5μmの粉砕スラリーとした。
この粉砕スラリーに、ホウ珪酸ソーダ(グラスバブルスS60:住友スリーエム製) 70部を加え小型オートホモミキサー(特殊機化工業製)5000rpmで分散させた。次に、予め調製した1%有機系増粘剤液(ケルザンS:三晶製) 200部、ショ糖脂肪酸エステル(ニューカルゲンFS−30:竹本油脂製、HLB値 16) 10部、消泡剤(アンチフォームE−20:花王製)2.5部及び防腐剤(バイオホープL:ケイ・アイ化成製) 1部を加え、小型ミキサーで均一にした。最後にpHメーターでpHを確認しながら予め調製した30%硫酸0.5部を徐々に加え、pHを5.8に合わせ、比重が0.98の水性懸濁状除草剤組成物(以下、本発明組成物2と記す。)を得た。
Formulation Example 2
In a SUS beaker, 480.5 parts of ion-exchanged water, 30 parts of Soprohol FLK (manufactured by Rhodia Nikka, polyoxyethylene tristyryl phenyl ether phosphate potassium salt), 100 parts of antifreezing agent (propylene glycol: Wako Pure Chemical Industries, Ltd.) 2.5 parts of antifoaming agent (Antifoam E-20: manufactured by Kao) was added and dispersed uniformly with a small stirrer. To this dispersion, add 18 parts of imazosulfuron, 80 parts of bromobutide and 5 parts of an inorganic thickener (Kunipia F: manufactured by Kunimine Industries), and gradually disperse them with a small auto homomixer (manufactured by Special Machine Industries) to form a slurry. Then, pulverization was performed at 2000 rpm using a dyno mill (KDL type: manufactured by Shinmaru Enterprise), which is a bead mill, to obtain a pulverized slurry having an average particle diameter of 3.5 μm.
To this pulverized slurry, 70 parts of sodium borosilicate (Glass Bubbles S60: manufactured by Sumitomo 3M) was added and dispersed at 5000 rpm with a small auto homomixer (manufactured by Koki Kogyo Co., Ltd.). Next, 200 parts of 1% organic thickener liquid (Kelzan S: made by Sanki) prepared in advance, 10 parts of sucrose fatty acid ester (New Calgen FS-30: made by Takemoto Yushi, HLB value 16), 10 parts, antifoaming agent (Anti-foam E-20: manufactured by Kao) 2.5 parts and preservative (Biohope L: manufactured by Kay Kasei Chemical Co., Ltd.) 1 part was added, and the mixture was made uniform with a small mixer. Finally, while confirming the pH with a pH meter, 0.5 part of 30% sulfuric acid prepared in advance was gradually added, the pH was adjusted to 5.8, and an aqueous suspension herbicide composition having a specific gravity of 0.98 (hereinafter, This is referred to as the present composition 2.).

次に試験例に用いた比較組成物について参考製造例を示す。   Next, reference production examples are shown for the comparative compositions used in the test examples.

参考製造例1
ショ糖脂肪酸エステルの代わりに、ポリオキシエチレンスチリルフェニルエーテル(ソルポールT−20:東邦化学製、HLB値 13.3)を用いた以外は製剤例1と同様の操作を行い、比重が0.98の水性懸濁状除草剤組成物(以下、比較組成物1と記す。)を得た。
Reference production example 1
The same operation as in Formulation Example 1 was carried out except that polyoxyethylene styryl phenyl ether (Solpol T-20: manufactured by Toho Chemical Co., Ltd., HLB value 13.3) was used instead of sucrose fatty acid ester, and the specific gravity was 0.98. An aqueous suspension herbicide composition (hereinafter referred to as Comparative composition 1) was obtained.

参考製造例2
ショ糖脂肪酸エステルの代わりに、ポリオキシエチレンスチリルフェニルエーテル(ソルポールT−20:東邦化学製、HLB値 13.3)を用いた以外は製剤例2と同様の操作を行い、比重が0.98の水性懸濁状除草剤組成物(以下、比較組成物2と記す。)を得た。
Reference production example 2
The same operation as in Formulation Example 2 was carried out except that polyoxyethylene styryl phenyl ether (Solpol T-20: manufactured by Toho Chemical Co., Ltd., HLB value 13.3) was used instead of sucrose fatty acid ester, and the specific gravity was 0.98. An aqueous suspension herbicide composition (hereinafter referred to as Comparative composition 2) was obtained.

本発明組成物1及び2、並びに、比較組成物1及び2はいずれも、20℃でB型粘度計 No.2ローター、12rpmの測定条件における粘度は850〜1000mPa・sの範囲内であった。   The compositions 1 and 2 of the present invention and the comparative compositions 1 and 2 are both B-type viscometer No. The viscosity under the measurement conditions of 2 rotors and 12 rpm was in the range of 850 to 1000 mPa · s.

次に本発明が有する優れた効果を試験例に示す。   Next, the excellent effect which this invention has is shown to a test example.

試験例
1000ml容のガラス製ビーカーに3度硬水800mlを入れて、その水面から30cmの高さより、ポリスポイドで採取した供試組成物を3滴落下さた。落下した液滴が水面全体(約50cm2)に完全に拡散するまでの時間を目視により測定した。その結果を〔表1〕に示す。
Test Example 800 ml of hard water 3 times was put in a 1000 ml glass beaker, and 3 drops of the test composition collected with a polyspoid were dropped from the surface of the water at a height of 30 cm. The time until the dropped droplet completely diffused over the entire water surface (about 50 cm 2 ) was measured visually. The results are shown in [Table 1].

Figure 2009084180
Figure 2009084180

試験例により、本発明の水性懸濁状除草剤組成物を湛水下水田等で水面上に直接散布した際に、優れた拡展性を示すことが確認できる。   From the test examples, it can be confirmed that when the aqueous suspension herbicide composition of the present invention is sprayed directly on the water surface in a submerged paddy field or the like, it exhibits excellent spreadability.

Claims (9)

少なくとも1種の常温で固体の除草活性化合物、比重調節剤、界面活性成分、増粘性成分、消泡剤及び水を含有する水面散布用水性懸濁状除草剤組成物であって、
界面活性成分として、イオン性界面活性成分及びHLB値が15より大きい非イオン性界面活性成分を含有することを特徴とする水性懸濁状除草剤組成物。
An aqueous suspension herbicide composition for spraying water, comprising at least one herbicidal active compound that is solid at room temperature, a specific gravity regulator, a surfactant component, a thickening component, an antifoaming agent and water,
An aqueous suspension herbicide composition comprising an ionic surfactant component and a nonionic surfactant component having an HLB value greater than 15 as the surfactant component.
比重が0.90以上1.05以下であり、且つ、粘度が600〜1200mPa・sである請求項1記載の水性懸濁状除草剤組成物。   The aqueous suspension herbicidal composition according to claim 1, wherein the specific gravity is 0.90 or more and 1.05 or less and the viscosity is 600 to 1200 mPa · s. 非イオン性界面活性成分のHLB値が、15.5以上20以下である請求項1又は2記載の水性懸濁状除草剤組成物。   The aqueous suspension herbicidal composition according to claim 1 or 2, wherein the nonionic surfactant component has an HLB value of 15.5 or more and 20 or less. 非イオン性界面活性成分の少なくとも1種が、HLB値が15.5以上20以下であるショ糖脂肪酸エステルである請求項1〜3いずれか一項記載の水性懸濁状除草剤組成物。   The aqueous suspension herbicide composition according to any one of claims 1 to 3, wherein at least one of the nonionic surfactant components is a sucrose fatty acid ester having an HLB value of 15.5 or more and 20 or less. イオン性界面活性成分が、ポリオキシエチレントリスチリルフェニルエーテルリン酸エステル塩である請求項1〜4いずれか一項記載の水性懸濁状除草剤組成物。   The aqueous suspension herbicide composition according to any one of claims 1 to 4, wherein the ionic surfactant component is polyoxyethylene tristyryl phenyl ether phosphate ester salt. 比重調節剤が、無機中空担体、有機中空担体及びパラフィン系炭化水素からなる群より選ばれる少なくとも1種である請求項1〜5いずれか一項記載の水性懸濁状除草剤組成物。   The aqueous suspension herbicide composition according to any one of claims 1 to 5, wherein the specific gravity adjusting agent is at least one selected from the group consisting of an inorganic hollow carrier, an organic hollow carrier and a paraffinic hydrocarbon. 比重調節剤が、パラフィン系炭化水素である請求項1〜5いずれか一項記載の水性懸濁状除草剤組成物。   The aqueous suspension herbicide composition according to any one of claims 1 to 5, wherein the specific gravity regulator is a paraffinic hydrocarbon. 常温で固体の除草活性化合物の少なくとも1種が、常温で固体のスルホニル尿素系除草活性化合物である請求項1〜7いずれか一項記載の水性懸濁状除草剤組成物。   The aqueous suspension herbicide composition according to any one of claims 1 to 7, wherein at least one herbicidal active compound that is solid at room temperature is a sulfonylurea herbicidal active compound that is solid at room temperature. さらに防腐剤を含有する請求項1〜8いずれか一項記載の水性懸濁状除草剤組成物。   Furthermore, the aqueous suspension herbicide composition as described in any one of Claims 1-8 containing antiseptic | preservative.
JP2007254160A 2007-09-28 2007-09-28 Aqueous suspension-type herbicide composition for water surface scattering Pending JP2009084180A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103039441A (en) * 2013-01-24 2013-04-17 凤台县精华助剂有限公司 Water emulsion type l40 surface active agent
JP2017155041A (en) * 2016-02-26 2017-09-07 三井化学アグロ株式会社 Method of controlling paddy weeds

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JPH05163106A (en) * 1990-04-27 1993-06-29 Takeda Chem Ind Ltd Aqueous suspension-like agricultural chemical composition
JP2001106601A (en) * 1999-08-04 2001-04-17 Nissan Chem Ind Ltd Suspension composition and spraying method
JP2002068903A (en) * 2000-08-29 2002-03-08 Sds Biotech:Kk Emulsion/suspension-type agrochemical composition for applying on water surface
JP2002193701A (en) * 2000-12-08 2002-07-10 E I Du Pont De Nemours & Co Aqueous suspension agrochemical formulation

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JPH05163106A (en) * 1990-04-27 1993-06-29 Takeda Chem Ind Ltd Aqueous suspension-like agricultural chemical composition
JP2001106601A (en) * 1999-08-04 2001-04-17 Nissan Chem Ind Ltd Suspension composition and spraying method
JP2002068903A (en) * 2000-08-29 2002-03-08 Sds Biotech:Kk Emulsion/suspension-type agrochemical composition for applying on water surface
JP2002193701A (en) * 2000-12-08 2002-07-10 E I Du Pont De Nemours & Co Aqueous suspension agrochemical formulation

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103039441A (en) * 2013-01-24 2013-04-17 凤台县精华助剂有限公司 Water emulsion type l40 surface active agent
JP2017155041A (en) * 2016-02-26 2017-09-07 三井化学アグロ株式会社 Method of controlling paddy weeds

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